银纳米线/聚乙烯醇导电复合材料的逾渗特性研究

采用多元醇法制备了长径比约为240的银纳米线(AgNWs),以聚乙烯醇(PVA)为基体、AgNWs为导电填料制备了导电复合材料;基于排斥体积理论和几何相变理论对银纳米线/聚乙烯醇导电复合材料的逾渗阈值进行了分析和预测。结果表明,基于排斥体积理论计算得到的逾渗阈值(0.5816%)小于实际复合材料的实测数据;基于几何相变理论模型对材料逾渗阈值的拟合数据约为1.25%～1.31%,与实验测试得到的复合材料逾渗转变浓度范围一致性较好。因此,利用几何相变理论进行复合材料逾渗阈值和电导率的预测对于AgNWs/PVA导电复合材料的设计、制备及性能评价具有重要的指导作用。     

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。     

基于交流阻抗的聚乙烯/碳纳米管导电复合材料的室温逾渗性能

聚合物基导电复合材料的室温逾渗机理是其使用和制备的重要基础。为了阐述聚乙烯/碳纳米管导电复合材料的室温逾渗性能,文中基于交流阻抗的分析思路和方法,采用电阻电容的等效电路模拟复合材料中的电学性能。以熔融法制备的高密度聚乙烯(HDPE)/碳纳米管(CNTs)复合材料为研究对象,测试其室温下的电学性能与CNTs含量间的关系,其中交流(AC)阻抗测试频率范围为100Hz到106.5Hz。当碳纳米管质量分数为0.5%时复合材料的电导率升至10~(-6)S/cm,表明复合材料中逾渗网络已初步形成。随频率变化的AC阻抗可清晰地展示HDPE/CNTs中导电网络的形成过程,并表明在导电复合材料的电学逾渗中,复合材料的导电机理逐渐由电容主导向电阻主导变化。     

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。     

预制炭黑/尼龙6纤维网络在导电高分子复合材料中的逾渗行为

通过超声法将炭黑(CB)粒子固定在静电纺丝尼龙6(PA6)纤维膜表面,制备出一系列具有不同CB含量的CB/PA6导电纤维薄膜。利用热压成型法将制备的导电纤维膜与高密度聚乙烯(HDPE)粉末热压复合,制备出CB/PA6/HDPE导电高分子复合材料(CPC)。扫描电子显微镜图片显示,CB粒子均匀地锚固在PA6纤维表面,且CB/PA6导电纤维膜在HDPE基体中形成连续的导电网络结构。研究了材料的导电逾渗行为,发现CB/PA6/HDPE复合材料的逾渗值仅为2.5%,显著低于传统的CB/HDPE复合材料的逾渗值(8.5%)。同时,由于CB/PA6/HDPE复合材料具有特殊的预制CB/PA6导电纤维网络状结构,PA6电纺纤维膜的含量在复合材料体系中也呈现出有趣的逾渗行为。     

用定向冷冻干燥法制备具有一维取向微孔结构的炭黑/聚乙烯醇导电复合材料

通过定向冷冻干燥法,制得了具有一维取向微孔结构的导电炭黑(CB)/聚乙烯醇(PVA)复合材料。对CB/PVA复合材料的导电性测试结果表明,该复合材料的导电逾渗行为并不完全符合经典的逾渗理论。由于CB/PVA复合材料特殊的取向微孔结构和炭黑于PVA基体的非均匀分布,使得其电阻率临界指数t值高于经典的逾渗理论的取值范围。     

原位膨胀法制备PMMA/EG复合材料及其导电和流变性能的研究

使用低温可膨胀石墨,通过"原位膨胀-机械剥离"的方法制备了PMMA/EG复合材料,研究了可膨胀石墨含量对其电导率的影响。电导率、SEM、动态流变等测试表明膨胀后的石墨片层在树脂基体中分散良好;从10~20 phr开始,石墨鳞片相互接触形成网络结构显著地提高电导率,最高达12个数量级。采用原位膨胀法可以制备逾渗阈值较小的导电复合材料,填充少量低温可膨胀石墨就可以大幅度提高PMMA电导率。     

类石墨烯/氯化聚乙烯-聚氯乙烯复合材料的制备与性能

采用微波辐照法制备了膨胀石墨(EG),利用EG、氯化聚乙烯(CPE)和聚氯乙烯(PVC)的固相剪切碾磨(S³M)制备了EG-CPE-PVC复合粉体,复合粉体进一步与PVC、热稳定剂和增塑剂混匀,经塑化和模压成型得到类石墨烯/CPE-PVC复合材料。用粒度分析、XRD、AFM、SEM和TEM等手段表征了复合粉体及其复合材料的结构与性能。结果表明: S³M实现了体系的粉碎、分散,EG片层的剥离及与CPE-PVC的纳米复合。CPE的加入实现了EG的进一步剥层,使EG片层的厚度达到1~3层,达到了EG的石墨烯化目标。当EG质量分数为3%时,类石墨烯/CPE-PVC复合材料的电导率呈指数上升,与PVC相比提高了8个数量级;当EG质量分数超过4%时,电导率再次激增,出现逾渗现象;在EG质量分数为5%时,电导率达到0.01 S/m,复合材料表现出良好的抗静电性能。     

石墨的固相剪切石墨烯化及其与聚氯乙烯的纳米复合

采用微波辐照市售可膨胀石墨制备膨胀石墨(EG),通过EG-聚氯乙烯(PVC)、EG-PVC-氯化聚乙烯(CPE)和EG-PVC-聚氨酯热塑性弹性体(TPU)等的固相剪切共碾磨(S³M)制备了EG/PVC,EG/PVC-CPE和EG-PVC-TPU复合粉体,进一步模压成型得到EG/PVC,类石墨烯/PVC/CPE和石墨烯-PVC-TPU复合材料。用粒度分析、扫描电镜、透射电镜、X射线衍射和原子力显微镜等手段表征了复合粉体及其复合材料的结构与性能。结果表明,S³M实现了体系的粉碎、分散和EG与PVC的纳米复合;CPE和TPU的加入实现了EG的进一步剥层,使石墨片层的厚度达到1～5层,达到了少层石墨烯水平,实现了EG石墨烯化的目标。当EG质量分数在3%时,类石墨烯/PVC-CPE复合材料电导率呈指数上升,提高了8个数量级;当EG质量分数超过4%时,电导率再次激增,出现第2次逾渗现象;在5%时,电导率达0.22 s/m,表现出良好的导热、抗静电和电磁屏蔽功能。石墨烯/PVC-TPU纳米复合材料的电导率变化与类石墨烯/PVC-CPE复合材料类似,而且导...     

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。     

膨胀石墨-碳纤维/尼龙三元导热复合材料制备

以尼龙6（PA6）为基体,膨胀石墨（EG）和碳纤维（CF）作为导热填料,采用熔融共混法制备了EG/PA6、CF/PA6和CF-EG/PA6导热复合材料。重点研究当固定导热填料（CF和EG）填充量为40wt%时,CF与EG不同的填充比例对CF与EG的接触方式及CF-EG/PA6复合材料的导热性和力学性能的影响。结果表明,相比单一CF填充,EG的加入有利于CF-EG/PA6复合材料热导率的增加;CF:EG质量比是25:15时的EG-CF/PA6三元复合材料,热导率可以达到2.554 W/（m·K）,是PA6的8倍,拉伸强度提高了125.34%,弯曲强度提高了119.8%,同时具有优异的耐热性。SEM结果表明,纤维状CF与蠕虫状EG片层在适当的填充比例下可以形成"面接触"的三维网络结构,这种三维网络结构不仅显著增大EG-CF/PA6复合材料的热导率,而且明显提高了其力学性能和耐热性能。为研制填充型导热高分子材料提供了一条新思路。      

镀Ag玻璃微珠-膨胀石墨/聚氯乙烯导电复合材料的制备与表征

采用一种无Pd无SnCl₂化学镀Ag新工艺对空心玻璃微珠（HGB）表面进行化学镀Ag,然后通过熔融共混方法制备镀Ag玻璃微珠（Ag-GB）-膨胀石墨（EG）/聚氯乙烯（PVC）复合材料。借助SEM、EDS和XRD测试手段对Ag-GB镀层的表面形貌与结构进行了表征,研究了Ag-GB和EG作为复合填料对Ag-GB-EG/PVC复合材料导电和力学性能的影响。结果表明:预处理的HGB的表面更易于Ag层的沉积,镀覆的镀层更为均匀、致密;Ag-GB表面的Ag层质量分数为81.15%;固定Ag-GB的质量分数为15%,随着EG质量分数的增加,Ag-GB（15%）-EG/PVC复合材料的体积电阻率呈非线性降低趋势,当EG的质量分数达到逾渗阈值12%时,Ag-GB（15%）-EG/PVC复合材料的体积电阻率为2.18×103 Ω·cm,满足抗静电PVC材料的应用要求。添加质量分数为12%的EG,Ag-GB（15%）-EG/PVC复合材料的体积电阻率与单独填充质量分数为50%的Ag-GB时Ag-GB/PVC复合材料的体积电阻率相当,此时其拉伸强度达到最大值。      

Thermal characterization of expanded graphite and its composites

Using the guarded hot plate method, we have measured the thermal conductivity of compressed expanded graphite (EG) samples (densities from 0.4 to 1.95 g/cm³) along the compression direction (c axis) in the range 150–675 K and that of EG/epoxy composites (5–75 wt % EG) in the range 150–425 K. We also have measured the specific heat of EG samples at temperatures from 200 to 675 K. Their c-axis thermal diffusivity has been shown to decrease with increasing EG density. The thermal conductivity of the EG/epoxy composites and its variation with EG content are well represented by a rule of mixtures that takes into account the anisotropy in the thermal conductivity of the EG particles and their preferential alignment in the composites.     

石墨烯纳米片/(酚酞聚芳醚酮-环氧树脂)双逾渗导热复合材料的制备和性能

为在较低的导热填料含量下提高环氧树脂(EP)的热导率,通过溶液法制备了石墨烯纳米片/(酚酞聚芳醚酮-EP) (GNP/(PEK-C-EP))复合材料。基于接触角测量计算并预测了GNP的选择性分布,并通过SEM和激光闪光法研究了GNP和PEK-C含量对GNP/(PEK-C-EP)复合材料的微观结构和热导率的影响。结果表明,当PEK-C的含量为20wt%时,GNP选择性分布在PEK-C中,形成了双逾渗结构的GNP/(PEK-C-EP)复合材料,从而构建了连续导热通道。当GNP含量为1wt%时,GNP/EP复合材料导热率最高达0.375 W(m·K)?1。当GNP含量为0.5wt%时,GNP/(PEK-C-EP)复合材料导热率最高达0.371 W(m·K)?1,较GNP含量为0.5wt%的GNP/EP复合材料热导率高48%,与GNP含量为1wt%的GNP/EP复合材料的热导率基本相同。表明GNP/(PEK-C-EP)复合材料的填料量减少了50%,利用双逾渗效应可以有效减少导热填料用量。此外,比较了纯EP和GNP/(PEK-C-EP)复合材料的玻璃化转变温度、热稳定性和热膨胀系数,结果表明,GNP/(PEK-C-EP)复合材料的热性能优于纯EP。      

Electrical percolation phenomena in cement composites containing conductive fibres

Electrical conductivity measurements on cement composites containing carbon fibres or steel fibres were conducted. Percolation phenomena associated with electrical conductivity were observed. The conductivity of the systems studied increased by several orders of magnitude, at a specific concentration of conductive fibre, i.e. the percolation concentration. The percolation concentration is shown to be dependent on conductive fibre geometry instead of system composition. The results provide an important guide for the manufacture of conductive cement composites containing conductive fibres.     

Effect of the addition of milled carbon fiber as a secondary filler on the electrical conductivity of graphite/epoxy composites for electrical conductive material

In this work, carbon composite bipolar plates consisting of synthetic graphite and milled carbon fibers as a conductive filler and epoxy as a polymer matrix developed using compression molding is described. The highest electrical conductivity obtained from the described material is 69.8 S/cm for the in-plane conductivity and 50.34 S/cm for the through-plane conductivity for the composite containing 2 wt.% carbon fiber (CF) with 80 wt.% filler loading. This value is 30% greater than the electrical conductivity of a typical graphite/epoxy composite with 80 wt.% filler loading, which is 53 S/cm for the in-plane conductivity and 40 S/cm for the through-plane conductivity. The flexural strength is increased to 36.28 MPa compared to a single filler system, which is approximately 25.22 MPa. This study also found that the General Effective Media (GEM) model was able to predict the in-plane and through-plane electrical conductivities for single filler and multiple filler composites.     

Strain effects on percolation conduction in conductive particle filled composites

The effect of uniaxial and multiaxial mechanical strain on the electrical conductivity of particle filled polymer composites is investigated in the framework of concentration-driven percolation. For composites consisting of low aspect ratio, rigid conductive particles in a compliant polymer matrix, a simple argument leads to the conclusion that the effective volume fraction of conductive particles (the ratio of total particle volume to the total volume of the deformed composite) plays a dominant role, with conductivity remaining isotropic despite the directional bias of the strain state. As such, conductivity is expected to exhibit classical power, law-dependence on concentration, which in this case takes the form of a strain-dependent effective volume fraction. Consideration of deformation effects on particle agglomerates suggest, however, that particle-to-particle network connections are likely to be affected most significantly along directions experiencing the most severe strains, introducing a directional bias in network connectivity at a higher length scale. To assess the importance of this possible directional bias, random resistor network models are used to study the conductivity of uniaxially strained composites. For conservative assumptions on the severity of the bias in bond probabilities, network conductivities exhibit approximately isotropic, concentration-driven behavior for moderate strains, supporting the predictive utility of the simple percolation conduction-effective volume fraction approach. Further corroboration is provided by experiments in the literature on silicone-graphite composites subjected to uniaxial compressive strain, where good agreement is obtained through moderate strains for the theoretically correct value of the conduction exponent in concentration-driven percolation.     

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%.     

Microstructural image analysis and structure–electrical conductivity relationship of single- and multiple-filler conductive composites

The electrical conductivity of polypropylene/graphite (PP/G) composites and polypropylene/graphite/carbon black (PP/G/CB) was investigated in this paper. The conductivity experimental data of PP/G composites was correlated to theoretical models, which exist in the literature, and the results showed higher values of the exponent t compared to the expected typical values. Moreover, these analytical models were unable to describe the electrical behaviour for multiple-filler conductive composites such as PP/G/CB composites. A 2D computer simulation to numerically compute the electrical conductivity based on digital image analysis was found to be somewhat useful to describe the mechanism of conduction in PP/G/CB composites and to determine the critical factors in developing high electrically conductive composites.     

Microstructure of carbon nanotubes/PET conductive composites fibers and their properties

Poly(ethylene terephthalate) (PET) resin has been compounded with carbon nanotubes (CNTs) using a twin-screw extruder. The composites of 4 wt% CNTs in PET had a volume electrical resistance of 10³ Ω cm, which was 12 orders lower than pure PET. The volume electrical conductivity of CNTs/PET composites with different CNTs containing followed a percolation scaling law of the form σ = κ(ρ − ρ_c)^t well. Scanning electron microscopy (SEM) micrograph showed that CNTs had been well dispersed in PET matrix. Optical microscopy micrograph showed that discontinuity of conductive phase existed in some segments of composite fiber. Rheological behavior of CNTs/PET composites showed that the viscosity of CNTs/PET composites containing high nanotube loadings exhibited a large decrease with increasing shear frequency. Crystallization behavior of CNTs/PET composites was studied by differential scanning calorimetry (DSC) and the nucleating effect of CNTs in the cooling crystallization process of PET was confirmed. Composite fiber was prepared using the conductive CNTs/PET composites and pure PET resin by composite spinning process. Furthermore, cloth was woven by the composite fiber and common terylene with the ratio 1:3. The cloth had excellent anti-static electricity property and its charge surface density was only 0.25 μC/m².