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。     

高转变温度聚合物PTC材料的研究

研究了以尼龙12（PA12）为基体树脂，炭黑（CB）为导电填料的高转变温度聚合物正温度系数（P11C）材料。采用熔融共混方法制备了PA12/CB聚合物PTC复合材料，研究了炭黑种类、炭黑含量、炭黑表面改性等因素对PA12/CB复合材料PTC性能的影响。结果表明：Vxc305炭黑填充的PA12复合材料，当炭黑含量为30％时，PTC强度可达到105；炭黑表面改性能够抑制材料的NrC效应。     

炭黑改性对炭黑/高密度聚乙烯体系电性能稳定性的影响

采用熔体共混法制备了炭黑（CB）/高密度聚乙烯（HDPE）导电复合材料。研究了硝酸氧化对CB/HDPE导电复合材料正温度系数（PTC）、负温度系数（NTC）效应和电性能稳定性的影响。结果表明,填充氧化炭黑（CB-O）提高了CB-O/HDPE体系的电性能稳定性和PTC强度,部分消除或降低了复合材料的NTC效应。而CB-O/HDPE体系的室温电阻率比CB/HDPE体系只增加了0.3个数量级,但比经过交联处理的CB/HDPE（CB/crosslinked-HDPE）体系降低了1个数量级。CB-O/HDPE复合材料性能的改善主要是由于CB经氧化后,表面羧基、羟基等极性基团含量增加,抑制了CB粒子高温时的自团聚作用,减弱了体系的NTC效应;同时CB表面微晶晶界处导电性较差区域的减少,提高了CB的导电性,,并且CB-O表面大量孔洞和裂缝的形成,增强了CB-O与HDPE的物理吸附作用,提高了复合材料的电性能稳定性。      

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。     

HDPE/CB-GP复合材料体系电性质的研究

当HDPE含量46％（质量分数，以下同）、其它添加剂（如抗氧剂、阻燃剂、交联剂和润滑剂等辅助填料）的含量11％，两种导电填料石墨（GP）和碳黑（CB）的总含量为43％时，研究结果表明石墨含量的变化对HDPE/CB-GP复合材料室温电阻率、阴C强度和后NTC强度有显著的影响．HDPE/CB-GP复合材料中GP的含量〈8．6％时，样品的室温电阻率〈30Ω·m，PTC强度〉7、后NTC强度〈1．3；电阻率．温度曲线经过17次冷热循环后重现性好，复合材料具有实际应用价值；GP在复合材料中为层片状结构。     

高比表面积炭黑/聚丙烯导电复合材料

研究了高比表面积炭黑(Ketjen black, KB)填充聚丙烯复合材料(KB/PP)的导电性能及体积电阻率-温度特性。结果表明, 当KB填充含量达到0.5%~1.5%(体积分数)时, KB/PP复合材料出现电渗流行为, 表现出优异的室温导电性能。同时, KB/PP复合材料的体积电阻率-温度特性曲线呈现出特殊的负温度系数-正温度系数-负温度系数(NTC-PTC-NTC)三阶段特征, 体积电阻率随温度的上升, 先出现下降产生第一个NTC效应, 然后出现PTC效应及第二个NTC效应。在相对低温范围内, 第一个NTC效应具有良好的稳定性和重复性。KB表面的电子跃迁导电、基体体积膨胀两种效应的叠加是造成KB/PP复合材料出现三阶段特征的原因。     

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。     

导电炭黑填充PP-EAA复合材料的形态及电性能

以聚丙烯(PP) 和乙烯-丙烯酸共聚物( EAA) 的共混物为基体材料, 以导电炭黑为填料, 通过熔融共混的方法制备了导电复合材料。探讨了导电炭黑在两相基体中的分散情况以及聚丙烯结晶度对复合体系导电性能的影响。扫描电镜测试结果表明, 在共混物中炭黑粒子选择性分散在极性EAA 树脂中, 同时EAA 树脂在聚丙烯基体中形成连续网络结构, 从而显著降低了复合体系的渗滤阈值。电性能测试结果表明, 材料在相同导电炭黑含量下的体积电阻率相对于单基体体系有7～8 个数量级的降低, 并且结晶度较高的PP 更有利于降低复合体系的体积电阻率。此外, 炭黑/ PP-EAA 复合材料的拉伸强度相对于炭黑/ PP 体系有所下降, 而断裂伸长率有所提高。      

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.     

HDPE／CB—MWNTs复合材料体系PTC效应

研究了高密度聚乙烯/碳黑-多壁碳纳米管复合材料的正温度系数效应(PTC).结果发现,HDPE/CB-MWNTs复合材料中MWNTs的含量为1%.(质量分数,下同)时复合材料的PTC强度达8.3,室温电阻率仅为1.2Ω·m;而当MWNTs的含量为3%.时复合材料的PTC强度迅速减小到小于3,室温电阻率则变化不大.SEM研究表明导电填料CB或者MWNTs在复合材料中分布均匀.对HDPE/CB-MWNTs复合材料的PTC效应随MWNTs含量的变化原因进行了探讨.     

Percolation threshold and morphology of composites of conducting carbon black/polypropylene/EVA

Conducting carbon black (CB), one of the intrinsic semi-conductors, was added into matrix polypropylene (PP) to prepare conducting composites by means of the melt processing method. Another component EVA was mixed into the composites in order to lower the percolation threshold. The percolation threshold of the ternary CB/PP/EVA composites was merely 3.8 vol%, while it was up to 7.8 vol% for the binary CB/PP composites without EVA. The conductivity of the ternary CB/PP/EVA composites was up to 10^–2 S/cm when the CB percentage was 5 vol%, while that of the binary CB/PP was lower than 10^–2 S/cm when the CB percentage was up to 10 vol%. DSC thermograms of the CB/PP/EVA composites showed that the melting peak shifted to low temperature with increasing CB content. The addition of CB and EVA resulted in the decrease of the crystallinity of PP in the ternary composites. The mechanical properties are also discussed. SEM and TEM were employed to study the morphology of the blend system. The results indicated that CB existed in the form of aggregations in the blend system. The smallest unit that formed a percolation network was grape-like aggregates with some small branches, which consisted of some CB particles, rather than the individual particles. This distribution was very valuable for forming conducting paths and for lowering the percolation value.     

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。     

Lowering the percolation threshold of polymer matrix composite by using raspberry-like carbon black/polystyrene composite particles

Our previous studies of raspberry-like carbon black/polystyrene (CB/PS) composite particles suggested that their morphologies could be tailored as the coverage degree of CB on PS microspheres. Morphologies of these composite particles were investigated by scanning electron microscope. The CB/PS composites prepared by using raspberry-like CB/PS particles had lower percolation threshold than that of general CB/PS composites. Optical microscopy photographs indicated that hierarchical structure of composite particles enabled CB particles to form more effective networks within the matrix. Raspberry-like structure dispersed CB particles in the interfaces between polycarbonate (PC) and PS when CB/PS particles were introduced into PC as additives. The effects of concentration of PS, coverage degree of CB, and concentration of CB on electrical properties of CB/PS/PC composite were investigated. The results showed that the percolation threshold of CB/PS/PC composite was improved when PS concentration was at the range of 20–80% and coverage degree of CB was more than 5% simultaneously.     

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 Effect of Polypropylene/Carbon Nanotube/Montmorillonite Hybrid Nanocomposites

Ternary polypropylene/multiwalled carbon nanotube/montmorillonite (PP/MWNT/MMT) nanocomposites were prepared by melt compounding of a ball-milled MWNT and MMT mixture in a Haake mixer at a screw rotation rate of 200 r/$hbox{min}$. The electrical conducting behavior of such hybrid composites was examined. The results showed that the conducting behaviors of PP/MWNT/MMT nanocomposites were strongly dependent on the MWNT and MMT contents. The percolation concentration of such hybrid nanocomposites was 1.0 wt% MWNT. Furthermore, percolating PP/1.0 wt% MWNT/MMT nanocomposites exhibited a positive temperature coefficient (PTC) effect. The PTC transition temperature can be regulated over a broader temperature range by varying the MMT contents. Hybridization of nanofillers provides a facile methodology to fabricate conducting polymer nanocomposites with tunable PTC transition temperatures.      

Electrical properties and morphology of carbon black filled PP/EPDM blends: effect of selective distribution of fillers induced by dynamic vulcanization

The roles of dynamic vulcanization process in the electrical properties, morphology, and rheology of carbon black (CB)-filled polypropylene (PP)/ethylene–propylene-diene rubber (EPDM) blends have been investigated. With the addition of CB, the uncross-linked (TPE) and dynamically vulcanized (TPV) composites showed a notable difference in the electrical properties, which is mainly caused by different distributions of CB particles resulting from the dynamic vulcanization process. Particularly, it was found that the CB particles in the TPE composites tended to distribute in EPDM phase, whereas the CB particles in the TPV composites were almost located in the PP matrix. The rheological behavior of the TPE and TPV composites was significantly changed with the incorporation of CB particles. Due to the selective distribution caused by the dynamic vulcanization process, the formation of the conductive network for the TPE composites is caused by the double percolation effect, while for the TPV composite, the formation of the conductive network is caused by the excluded volume effect.