Electrical properties of graphene nanoplatelets/ultra-high molecular weight polyethylene composites

Graphene nanoplatelets (GNPs)/ultra-high molecular weight polyethylene (UHMWPE) composites with a segregated structure had been fabricated using ethanol-assisted dispersion and hot compression at 180 °C. A percolation threshold of 3.5 wt% was achieved because of the formation conductive network. The positive temperature coefficient (PTC) and the negative temperature coefficient (NTC) effects of GNPs/UHMWPE composites had been investigated. The PTC behavior enhanced with increasing GNPs content but this was not always the case. The maximum PTC effect was observed in GNPs/UHMWPE composites (GNPs, 3.8 wt%) with the relatively low room temperature resistivity and the relatively high peak resistivity. The structure for GNPs/UHMWPE composites was examined by the SEM. The fact revealed that the slight interaction between GNPs and UHMWPE matrix may be changed by thermal cycles, and this can explain why thermal cycles could increase PTC and NTC intensity.     

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%.     

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。     

导电聚苯胺纳米纤维对聚乙烯/炭黑复合体系电阻行为的影响

采用水溶液氧化聚合和热掺杂相结合的技术制备十二烷基苯磺酸掺杂的聚苯胺(PANI-DBSA)纳米纤维,并将PANI-DBSA纳米纤维与低密度聚乙烯(LDPE)和炭黑(CB)进行熔融共混制得PANI-DBSA/LDPE/CB导电复合材料,研究了PANI-DBSA纤维的引入对导电复合材料电阻行为的影响。结果表明,添加PANI-DBSA纳米纤维,复合材料的逾渗阀值移向较低炭黑含量,复合材料的PTC强度得到一定程度的提高,复合材料的电阻率-温度曲线的热循环稳定性得以改善。     

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。     

LDPE/EVA/MWCNTs/CF复合材料的电学及流变性能

用熔融共混法制备了低密度聚乙烯(LDPE)/乙烯-醋酸乙烯共聚物(EVA)/多壁碳纳米管(MWCNTs)/碳纤维(CF)复合材料。使用高阻计、扫描电子显微镜、旋转流变仪等研究了导电填料及基体组成对材料的电性能和流变性能的影响。发现MWCNTs与CF共同作为导电填料具有协效作用,使得材料其不仅具有渗滤阈值低的特点,并且当填料含量超过阈值时,材料的导电性能相比于纯MWCNTs填充的复合材料电阻率降低了2个数量级。流变测试发现MWCNTS相比于CF对基体分子链运动的限制更为明显,MWCNTs含量的增多会增加材料的黏度并使材料从"类液"的粘弹行为转变为"类固"的粘弹行为。     

凹凸棒粘土对炭黑/环氧复合材料电性能的影响

通过溶液混合法制备了凹凸棒(ATT)/炭黑(CB)/环氧树脂(EP)复合材料。使用紫外可见光光谱仪(UV-Vis)和Zeta电位测试仪对CB和(或)ATT在丙酮溶剂中的分散稳定性进行了研究。使用扫描电子显微镜(SEM)和电阻仪分别研究了不同填料比例以及含量对EP复合材料微观结构和电阻率的影响。结果表明,ATT的加入可以有效增强CB在溶剂中的分散稳定性并促进EP基体中导电网络的形成。当CB与ATT质量比为5∶1时,复合材料的电阻率比不添加ATT时下降了2个数量级;其渗流阈值(1%)(质量分数,下同)小于具有相同填料含量的CB/EP复合材料(1.8%)。最后探讨了ATT对CB/EP复合材料电性能影响的可能机理。     

Low temperature electrical conductivity of low-density polyethylene/carbon black composites

The study deals with the electrical characteristics of carbon black/low-density polyethylene (CB/LDPE) composites of various CB filler concentrations (10, 15, and 20 wt.%). The DC electrical conductivity was studied as a function of filler concentration in low temperature range 25–285 K. It was found that the composites exhibit negative temperature coefficient of resistivity (TCR) at low temperatures and high enhancement in the electrical conductivity with both temperature and carbon black concentration. The observed increase of conductivity with the filler concentration was interpreted through the percolation theory. The dependence of the electrical conductivity of the given composites on temperature (25–285 K) was analyzed in terms of a formula in consistence with Mott hopping mechanism.Visiting scientist from the Jordan University of Science and Technology, Irbid-Jordan.     

多壁碳纳米管增强炭黑/聚丙烯导电复合材料导电行为

为了充分利用不同导电粒子的导电作用,在炭黑(CB)/聚丙烯(PP)导电复合体系中引入了多壁碳纳米管(CNTs)。研究发现：引入的CNTs分散在CB粒子间起到“桥梁”作用,使体系的导电性能得到明显改善,并且CB∶CNTs为19∶1时其协同导电效果最好,该复合体系出现逾渗现象,对应的导电填料体积分数明显降低。在导电填料总体积分数为4.76%时,少量CNTs的引入就可使复合体系的体积电阻率从109Ω·cm下降到105Ω·cm;同时少量的CNTs能明显抑制炭黑/聚丙烯导电复合材料的正温度效应(PTC),使PTC强度从6.10降低到1.48,PTC转变峰温度从166℃升高到174℃。少量的 CNTs可以使PP的结晶温度提高12℃,对PP结晶的成核作用比CB更加明显。复合体系力学性能随导电填料体积分数增加而明显降低,但因为体积电阻率一定时CB-CNTs/PP体系所需导电填料体积分数较CB/PP体系明显降低,因此少量CNTs的引入能够使复合体系的力学性能得到更大程度的保持。     

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。     

MWNTs/UHMWPE复合材料的导电行为

采用溶液混合、超声波分散的方法,制备了多壁碳纳米管（MWNTs）/超高分子量聚乙烯（UHMWPE）复合材料,并对其电学性能进行了研究。结果表明,该种方法可以使MWNTs比较好地分散于UHMWPE基体中,复合材料均表现出明显的渗流行为;长径比大的L.MWNTs-60100具有较小的渗流阈值,并且具有较小的正温度系数（PT...     

炭黑结构度对HDPE/CB导电复合材料导电网络形成与破坏的影响

采用熔融混合方法制备高密度聚乙烯/炭黑(HDPE/CB)导电复合材料,比较不同结构度CB填充体系的逾渗曲线和温度-电阻行为,并研究了不同含量、不同结构度CB填充的HDPE的结晶行为。实验结果表明,高结构度CB可使填充体系逾渗值显著下降(本研究中可降低为2.7%);低结构度CB填充体系的正温度系数(PTC)效应强度比高结构度CB填充体系高出约3;降温过程中,温度-电阻率曲线上出现电阻突变峰的强度随着CB结构度的降低而增强;差示扫描量热(DSC)和广角X射线衍射(WAXD)结果显示,CB粒子的加入对HDPE的结晶行为没有显著影响。     

熔融酯交换法原位合成炭黑/聚碳酸酯导电复合材料

利用原位聚合法合成具有导电性能的炭黑(CB)/聚碳酸酯(PC)复合材料。在聚合反应过程中, CB与PC在较低黏度下更好地混融, 而且通过负载催化剂连接CB和PC分子, 使CB参与PC链增长过程, 从而使CB有效分散。与传统的熔融共混法相比, 利用原位聚合法制备的CB/PC导电复合材料的渗滤阈值低, 当复合材料的体积电阻率为1.56×10⁶ Ω·mm时, CB的质量分数仅为4.32%。通过SEM观察发现, 原位法得到的样品中CB与PC充分混融, 形成导电网络更充分有效。利用原位聚合法得到的样品的正温度系数(PTC)的对数值达到4.69, 具有作为自控温材料的潜力。     

体积膨胀的稀释作用对聚合物基导电复合材料PTC效应的影响

聚合物基PTC复合材料中,导电填料的体积分数是一个绝缘体-导体的转换开关。理论分析表明,PTC转变区的电阻率突变与渗流曲线在临界体积分数附近的电阻率突变在导电机制上是同一的,聚合物基体体积膨胀的稀释作用对PTC效应有重要影响,在一定的温度范围内(小于PTC/NTC的转变温度),存在着定量的炭黑浓度稀释。      

Positive temperature coefficient characteristic and structure of graphite nanofibers reinforced high density polyethylene/carbon black nanocomposites

Graphite nanofibers (GNF) and carbon black (CB) filled high density polyethylene (HDPE) hybrid composites were fabricated using a melt mixing method. The effects of the CB and GNF content on the room temperature resistivity and positive temperature coefficient (PTC) behavior of the nanocomposites were examined. The room temperature resistivity of the composites decreased significantly with increasing GNF content, but this was not always the case with the PTC intensity. The incorporation of a small amount of GNF into the HDPE/CB composites significantly improved the PTC intensity and reproducibility of the hybrid nanocomposites. The maximum PTC effect, whose log intensity was approximately 7.2, was observed in the HDPE/CB/GNF (80/20/0.25 wt%) nanocomposite with relatively low room temperature resistivity. The mechanism for the effects of GNF in HDPE/CB/GNF hybrid composites were examined using differential scanning calorimetry, transmission scanning electron microscopy and X-ray diffraction.     

特殊形态结构导电高分子复合材料的电学性能

先使聚丙烯接枝马来酸酐(PP-g-MAH)与炭黑(CB)反应,再与聚丙烯/尼龙6(PP/PA6)共混制备出CB位于两相界面处的PP/PA6/PP-g-MAH/CB导电高分子复合材料,研究了材料的特殊结构和电学性能。结果表明,在PP/PA6/CB体系中CB粒子分布在PA6相,体系的逾渗阈值为2%;而在PP/PA6/PP-g-MAH/CB体系中,CB被PP-g-MAH诱导分布在两相界面处。PP/PA6两相为海岛结构时,PP/PA6/PP-g-MAH/CB体系仍可导电。PP/PA6/PP-g-MAH/CB体系的逾渗阈值降至1.6%,低于PP/PA6/CB体系。体系的正温度效应(PTC)强度远高于PP/PA6/CB体系,在90-135℃范围内不出现负温度效应(NTC)。PP/PA6/PP-g-MAH/CB体系的电学性能归结于其特殊的界面形态结构:导电通道由位于共混物界面处的PP-g-MAH和CB构建而成。     

双逾渗PTC材料的制备研究

以CB为导电填料,HDPE和PC为聚合物基,采用两种工艺制备HDPE／PC／CB三元复合材料。研究表明CB在单一聚合物HDPE中的逾渗阈值约为20％。母料共混制备的HDPE／PC／CB三元复合材料的PTC行为及重复性优于直接共混制备的试样。在母料共混制备的HDPE／PC／CB三元复合体系中形成了双逾渗行为,当HDPE／PC-40／60时,复合材料具有较好的PTC效应及PTC效应重复性。     

DC electrical conductivity of poly(methyl methacrylate)/carbon black composites at low temperatures

The study deals with the dc electrical conduction of poly(methyl methacrylate)/carbon black composites of different carbon black (CB) filler concentrations (2, 6, 12 wt%). The dc electrical conductivity was studied as a function of filler concentration, and temperature in the range (20–290 K). It was found that the composites exhibit negative temperature coefficient of resistivity (NTCR) at low temperatures and enhancement in the dc electrical conductivity with both temperature and CB concentration. The observed increase of conductivity with CB concentration was interpreted through the percolation theory. The dependence of the electrical conductivity of the composites in low temperatures was analyzed in term of a formula in consistence with Mott variable rang hopping (VRH) mechanism. The observed overall mechanism of electrical conduction has been related to the transfer of electrons through the carbon black aggregations distributed in the polymer matrix.     

炭黑碳纤维填充双组分聚合物体系的导电网络及其阻温特性

以2种不同形态尺寸的导电填料炭黑(CB)、 碳纤维(CF)填充双组分聚合物体系高密度聚乙烯(HDPE)聚丙烯(PP), 制备了四元导电复合材料。研究了导电网络的结构形态及其对材料阻温特性的影响。光学显微镜及SEM 观察表明: 炭黑选择性地分布于HDPE中, 体系中HDPE与PP呈双连续相分布, 形成双渗流导电网络结构。而具有较高长径比的碳纤维在两相基体中均匀分布并贯通多个相区, HDPE导电相区的碳纤维相互桥接形成导电网络。电性能测试结果表明: 体系的体积电阻率与CB/HDPEPP及CBCF/HDPE三元复合体系相比下降了1~5个数量级。同时, 双渗流导电网络的存在也有效抑制了负温度系数(NTC)效应, 提高了循环稳定性。与CBCF/HDPE体系相比, CBCF/HDPEPP体系的NTC效应从2个数量级下降到0.6个数量级, 电阻特征弛豫时间从951s增加到了2370s。      

炭黑填充聚偏氟乙烯复合材料的PTC效应

以聚偏氟乙烯（PVDF）为基体,经与炭黑等混合后挤出成型辐照。研究了两种不同类型导电炭黑（CB）对复合物导电性和正电阻温度系数（PTC）的影响,辐射剂量对PTC性能的影响,以及HDPE/PVDF配比对复合物PTC性能的影响。通过CB在HDPE/PVDF中配比不同时分布的扫描电镜（SEM）观测,随着PVDF含量的增加,C...