Effect of Polyaniline Functionalized Carbon Nanotubes Addition on the Positive Temperature Coefficient Behavior of Carbon Black/High-Density Polyethylene Nanocomposites

The influence of addition of polyaniline functionalized multiwalled carbon nanotubes (PANI-MWNTs) on the positive temperature coefficient (PTC) characteristics of carbon black (CB) filled high-density polyethylene (HDPE) nanocomposite materials have been studied. Polymer nanocomposites were prepared by the combined solution and melt-mixing process. The experimental results showed that the PTC intensity and maximum resistivity of the hybrid nanocomposites were obviously influenced by the polyaniline functionalization of multiwalled carbon nanotubes (MWNTs). A noticeable PTC of resistivity was observed for PANI-MWNTs/CB/HDPE hybrid nanocomposites near the melting point of HDPE. This is due to the significant volume expansion near the melting point of the HDPE in presence of hybrid fillers and a sudden increase of the resistivity due to the disconnection of the conductive paths. The PTC effect of CB/HDPE composites can be effectively modified by the addition of PANI-MWNTs.     

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。     

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。      

正交设计确定模压条件对HDPE/CB复合材料PTC强度的影响

在塑炼方法和复合材料组成一定时,用统计学方法,设计了四因子三水平的正交实验以确定不同模压条件对HDPE/CB复合材料PTC强度的影响。结果发现,各设计因素对样品PTC强度的影响大小顺序为:冷却时间>模压温度>模压压力>模压时间。最优模压条件为:模压压力8 MPa,模压温度155℃,模压时间15 min,模压后的冷却时间40 min。在最佳模压成型工艺条件下得到的样品PTC强度为8.4,与统计学的预测结果一致,后NTC强度小于0.8。冷热循环实验结果表明HDPE/CB复合材料有良好的电阻率-温度稳定性。     

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...     

一种有机结晶物对丁腈橡胶/炭黑复合材料电性能的影响

将一种低分子量有机结晶物加入到丁腈橡胶/炭黑复合体系中制备导电复合材料。实验得出, 其电阻率随温度的变化呈不同强度的正温度系数(PTC) 效应。讨论了低分子量有机结晶物对复合材料室温电阻率及PTC 效应的影响。      

电子束辐照对高密度聚乙烯/炭黑导电复合材料电阻率的影响

研究了电子束辐照固态和熔融态高密度聚乙烯／炭黑（ＨＤＰＥ／ＣＢ）导电复合材料的电性能随辐照温度和辐照剂量的变化。结果表明,对固态或熔融态辐照材料而言,其电阻率均随温度的升而而增大。等剂量下,固态辐照材料的ＰＴＣ强度比熔嘈态辐照的要高,两各状态经高剂量辐后其材料ＮＴＣ效应消失,,ＤＳＣ测试证明电阻率的２与基体的结晶行为以及交联链的形成密切相关。     

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.     

电子束辐照对PVDF/CB导电复合体系性能的影响

在较宽的剂量范围内研究了辐照对发黑填充的聚偏氟乙烯（PVDF／CB）导电复合体系性能的影响。发现在所研究的剂量范围内辐照都能有效降低该体系的室温电阻率。通过DSC测试和X射线衍射实验发现,电子束辐照在一定剂量下能提高体系的结晶度,但不改变体系的晶型。室温电阻率的变化是结晶度、结晶完善程度、晶片厚度和辐照引起的CB与PVDF相容性和界面粘结的变化多重作用的结果。在一定剂量下电子束辐照能显著提高PVDF／CB导电复合体系的肌效应,消除NTC现象。     

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。     

HDPE/EVA/CB复合导电材料的研究

研究了HDPE/EVA/CB(炭黑)复合材料的导电性及正温度系数(PTC)特性,包括电阻-温度特性和电流-时间特性.发现在HDPE/CB复合材料中加入少量的EVA能降低室温电阻率、改善炭黑粒子的分散、增强PTC效应以及缩短材料的响应时间,并从基体的结晶性及炭黑在共混基体中分布的角度探讨了EVA组分对复合材料电性能影响的作用机理.     

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。      

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。     

Carbon black/high density polyethylene conducting composite materials: Part II The relationship between the positive temperature coefficient and the volume resistivity

Carbon black/polymer composites can be used in a variety of industrial applications, where a high conductivity is an important physical parameter. The relationship between the positive temperature coefficient (PTC) effect and the room temperature volume resistivity has been investigated. These are two of the more important operating parameters. Resistivity-temperature measurements were performed on a radiation crosslinked high structure (H) carbon black mixed at different concentrations in HDPE. The results obtained for composites with a range of carbon black properties showed that there was a linear relationship between log (R2/R1) and log R1, where R2=maximum resistivity and R1=room temperature volume resistivity. The relationship can be taken as a reference line for the assessment of the relative effect that modifying the carbon black structure and changing the mixing variables on the relative magnitude of the PTC effect and the room temperature volume resistivity. The high structure (H) carbon black structural characteristics were modified by both gas phase (carbon dioxide at 900°C) and liquid phase (nitric acid) treatments. The former treatment procedure resulted in a decrease, while the latter an increase in the volume resistivities of the final composites. These results are discussed in terms of the effect of surface functionality and carbon structural characteristics. This revised version was published online in November 2006 with corrections to the Cover Date.     

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.      

成核剂对聚乙烯/炭黑复合物的形态及PTC特性的影响

借助 WAXD、SAXS、DSC等手段研究了成核剂的引入对聚乙烯 /炭黑导电复合体系的结晶行为、聚集态结构的大尺寸效应及 PTC特性的影响。结果表明 ,成核剂的引入对结晶度的影响不大 ,但却使得基体的微晶尺寸、长周期等变小 ;从而改善了导电复合物的 PTC特性 ,提高了材料的开关性能 ,并改善了阻 -温曲线的重复稳定性。     

热处理对PVDF／CB导电复合体系结晶行为及PTC特性的影响

研究了在不同的热处理条件下，聚偏氟乙烯与炭黔地电复合体系结晶行为的变化及对ＰＴＣ效应的影响。借助于ＤＳＣ和ＷＡＸＤ为体系的结晶为进行了深入的研究。结果表明，热处理可以改善基体结晶行为，使结晶度提高，从而使导电复合体系的室温电阻率下降，ＰＴＣ强度提高。     

炭黑-丁腈橡胶涂层复合材料的导电性能

将导电炭黑与丁腈橡胶混合制备导电聚合物复合材料,这种材料的电阻率随温度的变化呈正温度系数（ Ｐ Ｔ Ｃ）效应。讨论了不同的掺入炭黑粒子浓度、混炼和硫化及成膜溶剂对室温电阻率及 Ｐ Ｔ Ｃ效应的影响。     

Direct current conductivity of carbon nanofiber-based conductive polymer composites: effects of temperature and electric field

Polymer composites based on high density polyethylene (HDPE) and carbon nanofiber (CNF) were fabricated by melt compounding. The dependences of electrical conductivity of HDPE-CNF composites on filler concentration, temperature, and applied electric field were investigated. The results showed that the conductivity of the HDPE-CNF composites follows the scaling law of percolation theory. Increasing temperature caused a sharp increase in the resistivity of HDPE-CNF composites near the melting temperature of HDPE, yielding a positive temperature coefficient (PTC) effect of resistance. The potential mechanisms involved in the PTC effect of such composites were analyzed. An investigation of the effect of electric field on the conductivity of HDPE-CNF composites revealed the presence of tunneling conduction. The tunneling conductivity increased with increasing filler content because of high tunneling frequency, and decreased with rising temperature as a result of gap widening between conducting CNF fillers.     

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。