基体分子运动对聚偏氟乙烯/碳纤维复合材料的聚合物基正温度系数性能的影响

聚合物基正温度系数(PTC)材料中,基体分子在熔体状态下的运动能力可显著影响填料分布、PTC强度及稳定重复性等,明确其机理有利于高灵敏性且稳定可重复的PTC复合材料的设计与制备.通过探究基体熔体黏度不同的聚偏氟乙烯(PVDF)/碳纤维(CF)的电阻-温度响应行为,可以发现复合材料PTC转变温度区间仅取决于基体化学结构与结晶性,而PTC循环稳定性却受到基体分子运动能力的显著影响.当基体分子运动能力较强时,分子链极易黏附填料在CF表面形成包覆层,导致局部填料间距增大到隧穿距离以上,不利于复合材料导电网络的重建,导致随热循环次数增加,复合材料的室温电阻率有所升高,PTC可重复性略微降低.而对基体分子链缠结明显的PVDF/CF复合材料中,运动能力较弱的分子链不会包覆CF粒子,在多次升温-降温循环后导电通路能恢复到初始状态,复合材料呈现良好的PTC可重复性,将其应用于电路过热保护装置时,复合材料表现出灵敏的温度响应特性及可多次循环的开关特性.     

HDPE/HIPS/CB复合材料的制备及PTC性能

以高抗冲击聚苯乙烯(HIPS)和高密度聚乙烯(HDPE)为基体,炭黑(CB)为导电填料,采用熔融法制备聚合物基正电阻率温度系数效应(PTC)复合材料.通过扫描电子显微镜(SEM)研究了CB在复合材料两相基体中的选择分布,采用热敏电阻温度(RT)曲线测试仪研究复合材料PTC性能随CB含量的变化规律.结果表明,在HIPS/CB体系中加入HDPE后,复合材料的渗流阈值降低,PTC强度增强,耐电压强度有所提高.     

HDPE/EPDM/CB复合物的PTC效应

聚合物正温度系数 (PTC)材料 ,是由聚合物基体与炭黑、碳纤维、金属粉末等导电填料共混而成的一种功能导电复合材料 ,其特点是 :当温度升高时 ,在聚合物结晶熔点附近 ,材料的电阻率随温度升高急剧增加 ,可发生几个数量级的突跃 .聚合物 PTC材料可用作自限温加热器、过电流保护器、传感器等 ,有广阔的发展前景 .目前对聚合物 PTC材料的研究主要以聚乙烯 [1～ 5]、乙烯 -醋酸乙烯酯共聚物[6] 、偏氟乙烯 [7] 等单一组分聚合物作为基体材料 .本文研究了以高密度聚乙烯 (HDPE) /三元乙丙胶(EPDM)共混物为基体材料的炭黑 (CB)导电复合材…     

乙烯类聚合物-炭黑复合物的PTC效应

本文以低密度聚乙烯(LDPE)和乙烯-醋酸乙烯酯共聚物(EVA)为基材,炭黑(CB)为导电微粒,探讨了聚合物-炭黑复合物的结构对正温度系数效应(PTC)增强与减弱的影响和炭黑含量与PTC效应的关系以及交联结构对PTC现象的稳定作用.     

PVDF-HDPE双相PTC材料的制备、结构与性能

分别以聚偏氟乙烯(PVDF)、高密度聚乙烯(HDPE)为基体,炭黑(CB)为导电填料,采用两步熔融混合法,制备了PVDF-HDPE-CB导电复合材料。通过差示扫描量热(DSC)、溶剂抽提、扫描电子显微镜(SEM)等方法表征了复合材料的结构,采用电阻测试仪等仪器测试了复合材料的性能。研究了PVDF与HDPE体积比与复合材料结构的关系,以及对复合材料导电性、正温度系数(PTC)特性、耐电压性能的影响。结果表明,复合材料具有双相PTC材料结构,在复合材料中,HDPE易形成连续相,少量添加即可显著提高以PVDF为基体的PTC材料的导电性和耐电压性能。     

聚乙烯/碳纤维复合材料的PTC效应

近几年 ,由导电粒子 (如碳黑、碳纤维、金属和金属氧化物等 ) [1～ 3] 填充结晶或半结晶型聚合物的导电复合材料备受人们关注 ,并逐渐得到了开发与利用 .其中有一类功能材料 ,随温度的升高 ,相继呈现正温度系数 (PTC)和负温度系数 (NTC)效应[4～ 8] .这类材料广泛应用于发热体制造、抗静电、过电流保护和电磁屏蔽等领域 .长期以来 ,以碳黑填充聚合物的 PTC效应报道得较多 .近年来 ,以碳纤维为填料或部分填料的高聚物复合材料的 PTC效应 [9～ 11]开始引起了人们的兴趣和关注 .本文着重讨论了碳纤维的加入对聚合物结晶形态的影响以及γ射…     

碳纳米管-聚乙烯复合材料的介电性能

采用熔融共混及模压的方法制备了碳纳米管(CNT)-高密度聚乙烯(HDPE)复合材料,并用介电谱仪研究了逾渗值附近的导电填料对复合材料体系在不同温度、频率条件下的介电常数、介电损耗、交流电阻率的变化规律。结果表明:复合材料的介电常数、介电损耗均随CNT质量分数增加而逐渐增大;在频率为103~106 Hz,温度为40~130℃时,HDPE基体的介电常数随频率和温度的变化较小,而添加CNT填料的复合材料的介电常数随频率和温度的增加而略微降低。当w(CNT)0.5%时,复合材料的交流电阻率表现出对频率的强烈依赖性;而当w(CNT)0.5%时,在低频处表现出直流特性,在高频处显示出交流电阻率的降低。     

NiCF/ABS复合材料的制备及电磁屏蔽效能研究

探讨了碳纤维(CF)表面镍金属的化学镀工艺,制备了镀镍碳纤维(NiCF),采用密炼工艺制备了ABS基体复合材料,研究了CF和NiCF含量对复合材料的导电性能及电磁屏蔽效能的影响。结果表明:采用化学镀的方法在碳纤维表面镀覆了金属镍,所形成的镀层均匀致密;镀覆时间为5min时,镀镍后的碳纤维电阻率降低两个数量级;复合材料电阻率随CF、NiCF含量的增加而逐渐减小;复合材料电磁屏蔽效能随CF、NiCF含量的增加而逐渐增加,当NiCF含量为25%(wt)(约13.3vol%)时,电磁屏蔽效能最高可达51dB。     

聚乙烯/碳黑导电复合材料的导电性能

提出并验证了聚乙烯/碳黑(PE/CB)导电复合材料的网络导电性能和产生正温度系数(PTC)特性的原因,分析了加工过程、温度和辐射交联等后处理过程对其导电性能的影响.     

超高分子量聚乙烯基导电复合材料的电性能和自发热性能的研究

超高分子量聚乙烯(UHMWPE)具有优异的综合性能,本文采用凝胶结晶溶液方法制备了分别以碳纤维(CF)和镀镍碳纤维(NiCF)为导电填料,UHMWPE为基体的3个系列导电聚合物复合材料—UHMWPE/CF、UHMWPE/NiCF和UHMWPE/EMMA/CF复合体系,并分别对它们进行了室温伽马射线辐射处理,重点研究了这些材料的电性能和自发热性能,利用DSC、SEM、WAXS、DMA和体积膨胀等仪器进行了一系列测试表征。结果表明,NiCF作为导电填料时体系的逾渗阈值最低,为3vol%。伽马射线辐射处理不仅能有效提高材料的PTC效应,而且在合适的辐射剂量时也能有效提高材料的自发热性能。对材料介电性能的研究揭示了材料的交流电阻率与温度、频率的依赖关系。     

Enhanced Reproducibility of Positive Temperature Coefficient Effect of CB/HDPE/PVDF Composites with the Addition of Ionic Liquid

Developing an effective method for improving the reproducibility of positive temperature coefficient(PTC) effect is of great significance for large-scale application of polymer based PTC composites, owing to its contribution to the security and reliability. Herein, we developed a carbon black(CB)/high density polyethylene(HDPE)/poly(vinylidene fluoride)(PVDF) composite with outstanding PTC reproducibility, by incorporating 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([OMIm][NTf_2]) into the composite. After multiple repeated temperature cycles, the PTC performance of as-prepared material keeps almost unchanged and the varition of resistance at room temperature is less than 7%. Our studies revealed that [OMIm][NTf2] contributes to the improvement of PTC reproducibility in two ways:(i)it acts as an efficient plasticizer for refining the co-continuous phase morphology of HDPE/PVDE blends;(ii) it inhibits the crystallization of PVDF through the dilution effect, leading to more overlaps of the volume shrinkage process of HDPE and PVDF melt which results in the decrease of interface gap between HDPE and PVDF. This study demonstrated that ionic liquids as the multifunctional agents have great potential for improving the reproducibility in the application of the binary polymer based PTC composites.     

PTC/NTC Behavior of PVDF Composites Filled with GF and CF

Conductive polyvinylidene fluoride（PVDF）matrix composites filled with graphited fiber（GF）or carbon fiber（CF）were prepared by the melt-mixing method.The breakage and length distribution of the fibers in the polymer matrix were studied by scanning electron microscope（SEM）and optical microscope（OM）observations,respectively. The differences in the positive temperature coefficient（PTC）effects of the composites were mainly attributed to inter-fiber contact ability.The elimination of the negative temperature coefficient（NTC）effect for CF/PVDF composite was because of an increase in the viscosity of the polymer matrix.With the same filler content,CF could be more effective,to eliminate the NTC effect when compared with GF.Addition of 2%CF（mass fraction）in the PVDF composite with 7%GF（mass fraction）could effectively eliminate the NTC phenomenon of the composite.     

Positive Temperature Coefficient Characteristics of Multi-walled Carbon Nanotube Filled Polyvinylidene Fluoride Nanocomposites

Composites of polyvinylidene fluoride (PVDF) and multi-wall carbon nanotubes (MWNT) were prepared by a melt mixing process. Temperature dependence of electrical properties of the nanocomposites was investigated for composites containing different amounts of MWNT. An obvious positive temperature coefficient was observed. It was found that resistivity of the composites was decreased with increasing MWNT content and the electrical percolation threshold was formed at 3 wt% MWNT, which were caused by the formation of conductive chains in the composites. The mechanism of the positive temperature coefficient behavior of the nanocomposites is discussed. The rheological results showed that the materials experience a fluid–solid transition at the composition of 2 wt%, beyond which a continuous MWNT network forms throughout the matrix leading to a percolated network structure, which further indictes the nanotubes were dispersed uniformaly, in the PVDF matrix.     

Effects of heat treatment on electrical conductivity of HDPE/CB composites

The influence of heat treatment on the electrical conductive behavior of carbon black (CB) filled high density polyethylene (HDPE) composites was investigated. The results showed that the effects of annealing temperature on the resistivity and the PTC intensity of the HDPE/CB composites were significant; the resistivity and the PTC intensity of the composites varied with increasing number of thermal cycles; while the variation became small after the third thermal cycle. Furthermore, the variation of the resistivity was 1.7 times higher than that of the composites without annealing, and the variation of the PTC intensity of the composites was 0.22, which were smaller than those of the specimens without heat treatment. A suitable annealing heat treatment could reduce the resistivity and enhance the PTC intensity of the composites; it was also helpful to improve the stability of the properties of the composites and the repeatability of the PTC effect.     

热处理对聚乙烯／炭黑导电复合体系形态结构及PTC特性的影响

借助ＷＡＸＤ、ＳＡＸＤ和ＤＳＣ等手段研究了炭黑与聚乙烯复合体系在不同热处理条件下的结晶行为及聚集态结构的大尺寸效应对ＰＴＣ特性的影响。由此提出，不仅结晶度大小，而且聚集大尺寸效应性能对ＰＴＣ行性有重要影响的新观点。     

Morphology and electrical conductivity of ultrahigh-molecular-weight polyethylene–low-molecular-weight polyethylene–carbon black composites prepared by gelation /crystallization from solutions

Composite materials based on ultrahigh-molecular-weight polyethylene (UHMWPE)–low- molecular-weight polyethylene (LMWPE) and carbon black (CB) particles were prepared by a gelation/crystallization process from dilute solution. The method was developed to obtain composite materials with an improved and reproducible positive temperature coefficient (PTC) effect. Drastic improvement of the PTC effect was achieved when specimens with a LMWPE/UHMWPE composition of 9/1 containing 13 wt% CB were treated at 170 °C without restraint before measurement. The maximum PTC intensity, defined as the ratio of the maximum resistivity to the resistivity at room temperature, was about 5 orders of magnitude, which equals that of the LMWPE-CB system prepared by a kneading method. Interestingly, electrical resistivity during the heating-cooling process showed good reproducibility in the temperature range 30–190 °C, but has never been reported before even for cross-linked LMWPE-CB compostie. Scanning electron micrographs revealed that CB particles were dispersed in the LMWPE matrix, but not on the UHMWPE fibrils. It turns out that the network structure of UHMWPE, with a very low melt index, plays an important role in removing the negative temperature coefficient effect usually observed for the LMWPE-CB system and in ensuring the quality and the reproducibility of the PTC effect. Received: 31 August 1998 Accepted in revised form: 4 January 1999     

Influences of Plasma Treatment and 60Co γ-Ray Radiation on the Over-Voltage Positive Temperature Coefficient of High Density Polyethylene/Carbon Black Nano Composites

Argon plasma-pretreated high-density polyethylene (PHDPE) was blended with the conductive nano carbon black (CB) and inorganic flame retardant (magnesium hydroxide, Mg(OH)₂) was added. Influences of the CB content, plasma treatment time, plasma treatment power, and dosage of ⁶⁰Co γ-ray radiation on positive temperature coefficient (PTC) behaviors of composite were studied. In addition, the over-voltage resistance behavior of the composites was also investigated. The free radical of PHDPE was measured by 1,1-diphenyl-2-picryhydrazyl (DPPH) method. The gel contents of composite were measured by solvent extraction method. The results showed that the room-temperature volume resistivity and PTC effect of composite were improved significantly with plasma treatment. The PHDPE composite with ⁶⁰Co γ-ray radiation eliminated the negative temperature coefficient (NTC) effect in the composites effectively, and the PTC intensity of composite was increased. With increasing of radiation dosage from 20 Mrads to 80 Mrads, the gel content of composites increased up to 83.84% and the response temperature of composites shifted to low temperature (127.5 °C to 114.8 °C). In this work, the composites also successfully passed the over-voltage resistance test, and possessed good reproducibility.     

Electrical and self‐heating properties of UHMWPE‐EMMA‐NiCF composite films

Conductive polymer composites (CPC) containing nickel‐coated carbon fiber (NiCF) as filler were prepared using ultra‐high molecular weight polyethylene (UHMWPE) or its mixture with ethylene‐methyl methacrylate (EMMA) as matrix by gelation/crystallization from dilute solution. The electrical conductivity, its temperature dependence, and self‐heating properties of the CPC films were investigated as a function of NiCF content and composition of matrix in details. This article reported the first successful result for getting a good positive temperature coefficient (PTC) effect with 9–10 orders of magnitude of PTC intensity for UHMWPE filled with NiCF fillers where the pure UHMWPE was used as matrix. At the same time, it was found that the drastic increase of resistivity occurred in temperature range of 120–200 °C, especially in the range of 180–200 °C, for the specimens with matrix ratio of UHMWPE and EMMA (UHMWPE/EMMA) of 1/0 and 1/1 (NiCF = 10 vol %). The SEM observation revealed to the difference between the surfaces of NiCF heated at 180 and 200 °C. Researches on the self‐heating properties of the composites indicated a very high heat transfer for this kind of CPCs. For the 1/1 composite film with 10 vol % NiCF, surface temperature (T_s) reached 125 °C within 40 s under direct electric field where the supplied voltage was only 2 V corresponding to the supplied power as 0.9 W. When the supplied voltage was enough high to make T_s beyond the melting point of UHMWPE component, the T_s and its stability of CPC films were greatly influenced by the PTC effect. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1253–1266, 2009