HDPE/CB高分子导电复合体系的单轴形变与压阻行为

根据基体形变及其与渗流网络结构之间的关系,研究了高密度聚乙烯(HDPE)/炭黑(CB)复合材料压阻行为的发生机制及其影响稳定性的力学因素.结果表明,单轴压阻行为的产生源于材料受外力变形而导致的渗流网络微结构变化,且这种变化强烈依赖于填料含量.当填料含量较低时(渗流阈值附近),体系电阻率随压力升高而表现为电阻正压力系数行为;当填料含量较高时,体系电阻率随压力升高显现电阻负压力系数效应.完全卸载的零压力下,电阻基线随压缩循环随循环次数增大而发生漂移,这种漂移与轴向残余压缩应变有关,可以通过增加循环次数来加以稳定.交联可以减小残余压缩应变,并抑制高填充复合体系电阻基线的漂移.     

聚氯乙烯/炭黑导电复合体系的压阻行为

研究了聚氯乙烯/炭黑(PVC/CB)导电复合体系在单轴压力作用下的压阻行为,发现CB含量对电阻-机械响应具有显著的影响.当CB含量低于渗流阈值时,PVC/CB复合材料呈现PPC效应;而高于渗流阈值时,呈现NPC效应.在渗流阈值附近,单轴压缩可诱导NPC效应的出现,或者抑制PPC效应.     

纤维状填料/HDPE复合体系的导电渗流与流变渗流行为的关系

研究了纤维状导电材料不锈钢纤维(SSF)填充高密度聚乙烯(HDPE)导电复合体系的导电渗流与流变渗流行为之间的关系,并与颗粒状导电颗粒炭黑(CB)/HDPE导电复合体系进行了比较.发现当SSF含量极低(0.3vol%)时,SSF/HDPE体系即发生导电渗流现象,且导电渗流转变区域极窄;而仅当SSF含量达到4.8vol%时,该复合体系才表现出流变渗流现象,这一结果与CB/HDPE体系及纳米级导电纤维填充体系截然不同.此外,通过正温度系数效应的研究发现SSF形成的导电通路稳定性高于CB/HDPE体系.我们认为,SSF/HDPE体系呈现的这些特点均与SSF较大的直径及长径比且其导电通路及流变渗流网络的形成机理不同有关.     

CB/HDPE导电复合体系中Kerner-Nielson方程修正及电渗流与粘弹渗流的相关性

随着导电填料含量的增加,聚合物导电复合材料的电导率呈现非连续的递增.当填料含量达到渗流阈值并导致渗流现象出现时,导电填料相互聚集并形成网络,体系电导率急剧增大,关于此类电渗流现象已有很多报道^[1～4].填充类导电复合材料的结构和性能与其粘弹性密切相关.近年来,由于炭黑填充使得许多光学方法失效,流变学方法受到了广泛重视.最新的研究发现,非均相结构的出现和演化对浓度的依赖性有着特征流变响应,是一种粘弹渗流现象^[5～7].     

粒子填充HDPE复合体系动态流变行为研究

研究了炭黑(CB)和石墨(GP)填充高密度聚乙烯(HDPE)复合体系的动态流变行为.发现高填料含量时出现似固体行为,并认为它归因于无机粒子网络逾渗结构的形成.在相同聚合物基体条件下,粒子种类和粒子几何参数(粒子形状、大小、粒径分布)对低频区域流变行为、流变参数的逾渗行为和逾渗阈值(φ_c)有决定性影响,且种类的影响相比于粒子几何参数更为显著.此外,高表面活性及高比表面积(大径厚比、小尺寸)粒子填充体系具有较低的φ_c.     

多壁碳纳米管填充高密度聚乙烯复合材料的导电性和动态流变行为

对多壁碳纳米管/高密度聚乙烯(MWNTs/HDPE)复合材料的导电性和动态流变行为进行了研究.发现复合材料的复数粘度η*随MWNTs含量φ的增大而增大.当φ>3wt%时,η*发生突变,在低ω区域表现为非牛顿流体行为,出现强烈的剪切变稀现象.将其称为流变渗流现象,对应的填料含量即渗流阈值φc.在动态储能模量(G′)、损耗模量(G″)与频率(ω)关系曲线上,随φ增加出现“第二平台”,第二平台的出现表明MWNTs与MWNTs之间、MWNTs与聚合物之间存在相互缠结形成网络的结构.同时发现,在tanδ~ω曲线上的低ω区出现凹谷.认为这是由于MWNTs长链结构在低ω时伸长/收缩,MWNTs与MWNTs相互接触形成了次级网络造成的.经过不同时间热处理后的ω扫描以及动态间扫描的结果证实了这种结构的存在.研究结果表明复合材料的流变渗流阈值与电渗流阈值相一致(均在3%~5%之间),动态流变行为与导电性存在一定的相关性.     

HDPE氧化交联与动态流变行为

研究了高密度聚乙烯(HDPE)熔体在200℃的动态流变行为,比较了空气、氮气及加入抗氧剂B215情况下体系动态粘弹行为的差异.研究表明,在空气环境中,HDPE在低频区域出现特征粘弹行为.随着测试前热处理时间的延长,动态储能模量(G')明显增加,在低频率(ω)区域lgG'～lgω关系呈现平台特征.同时损耗角tanδ变小并出现极大值.在氮气环境中,上述特征粘弹行为存在但不明显.在加入抗氧剂的条件下,特征粘弹行为完全消失.这些现象归因于高温下HDPE的氧化导致其发生交联.     

电子束辐照交联CB/HDPE凝胶复合物的阻温特性

对电子束辐照交联并经溶剂抽提得到的炭黑/高密度聚乙烯(CB/HDPE)凝胶复合物的阻温特性进行了研究.结果表明,凝胶复合物与未抽提的交联试样和未交联试样相比,其PTC强度显著增大,并伴有明显的NTC现象.经热冷循环后,表现出很好的阻温特性稳定性,并且NTC现象消失.表明阻温特性的稳定性及NTC现象的消除强烈依赖于CB/HDPE导电复合材料凝聚态结构的稳定性     

加工工艺对气相生长碳纤维填充聚苯乙烯复合体系导电逾渗与动态流变特性的影响

研究了加工工艺对气相生长碳纤维(VGCF)填充聚苯乙烯(PS)复合体系导电逾渗与动态流变特性的影响.结果表明,低转速、短时间混合有利于VGCF形成较为完善的逾渗网络结构,其复合体系逾渗阈值低、导电性能好.使用作者提出的两相模型描述VGCF/PS复合体系的流变特性,发现低转速、短时间(30 r/min、5 min)混合条...     

HDPE/PA6反应增容体系的形态演化与黏弹行为

采用扫描电子显微镜(SEM)与先进流变扩展系统(ARES),研究了马来酸酐接枝高密度聚乙烯(HDPE-g-MAH)对高密度聚乙烯/尼龙6(HDPE/PA6)共混体系形态结构和黏弹行为的影响.发现HDPE-g-MAH的加入可原位生成尼龙6-高密度聚乙烯接枝共聚物(HDPE-g-PA6),使基体与分散相间的相容性显著改善,且随其添加量的增加两者相容性更好,导致HDPE/PA6体系形态结构变化.研究结果表明,由ARES获得的体系黏弹行为参数随HDPE-g-MAH含量的变化可与由SEM所观察到的微观形貌演化很好关联,动态流变学方法可敏感表征增容剂的加入所引起的HDPE/PA6界面性质变化,且能够反映分子链间相互作用的变化及由此导致的分散相颗粒网络的形成.     

Resistivity-Temperature Behavior of CB-Filled HDPE Foaming Composites

High-density polyethylene/carbon black foaming conductive composites were prepared from acetylene black（ACEY） and super conductive carbon black（HG-1P） as conductive filler, low-density polyethylene（LDPE） as the second component, ethylene-vinyl acetate（EVA） and ethylene propylene rubber（EPR） as the third component, azobisformamide（AC） as foamer, and dicumyl peroxide（DCP） as cross-linker. The structure and resistivity-temperature behavior of high-density polyethylene（HDPE）/CB foaming conductive composites were investigated. Influences of carbon black, LDPE, EVA, EPR, AC, and DCP on the foaming performance and resistivity-temperature behavior of HDPE/CB foaming conductive composites were also studied. The results reveal that HDPE/CB foaming conductive composite exhibits better switching characteristic; ACET-filled HDPE foaming conductive composite displays better positive temperature coefficient（PYC） effect; whereas super conductive carbon black（HG-1P）-filled HDPE foaming conductive composite shows better negative temperature coefficient（NTC） effect.     

Thermomechanical and shape memory properties of SCF/SBS/LLDPE composites

A thermally triggered shape memory polymer composite was prepared by blending short carbon fiber (SCF) into a blend of poly(styrene-b-butadiene-b-styrene) triblock copolymer (SBS)/linear low density polyethylene (LLDPE) prior to curing. These composites have excellent processability compared with other thermosets. The dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were investigated to assess the thermomechanical properties of the SCF/SBS/LLDPE composite. Scanning electron microscope (SEM) imaging of the samples was performed to show the distribution of the SCF in the composite. The study specifically focused on the effect of SCF on the shape memory behavior of the SCF/SBS/LLDPE composite. The results indicated that the large amount of SCF significantly improved the mechanical property of the polymer composites while not damaging the shape memory performance. The SCF/SBS/LLDPE composites exhibited excellent shape memory behavior when the SCF content was less than 15.0 wt%. Moreover, the shape fixity ratio and shape recovery time of the SCF/SBS/LLDPE composites increased with the SCF content.     

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.     

两种碳材料混合填充聚合物复合材料的导电特性及渗流阈值的计算模型

介绍了用碳纳米管与炭黑（或石墨）混合填充的聚合物复合材料的导电特性;阐述了混合填充聚合物体系的导电机理;介绍了基于线性混合规则和已占体积理论的渗流阈值的计算模型;分析了模型计算值与实验值的差异。利用已占体积理论,重新推导了混合填充体系渗流阈值的计算公式,并与文献公式做了比较。新公式表明：混合填充聚合物复合材料的渗流阈值...     

多壁碳纳米管/聚乙烯复合材料的制备及其导电行为

多壁碳纳米管/聚乙烯复合材料的制备及其导电行为;碳纳米管;高密度聚乙烯;渗流阈值;导电行为;V-PTC特性     

超细颗粒填充高密度聚乙烯复合体的导电和流变学性质

制备了多壁碳纳米管、石墨和碳黑填充高密度聚乙烯(HDPE)复合体,研究了复合体的导电和流变学性质.利用隧道逾渗模型对关键指数分别为4.4、6.4和2.9的三种复合体的非普适性导电行为进行了解释.与此同时,考察了颗粒类型和含量,以及剪切速率对复合体流变学性质的影响.结果表明,复合体系的储能模量在低频区出现第二平台,而复合黏度则表现出强烈的剪切变稀行为,标志着颗粒在聚合物内部发生聚集形成了网络结构.与石墨和碳黑填充复合体相比,具有更高纵横比的多壁碳纳米管填充复合体具有更高的储能模量和复合黏度.基于Guth-Smallwood理论结合有效介近似的G′r分析结果表明,填充HDPE复合体系的流变学逾渗阈值和导电逾渗阈值吻合良好.     

Electrochemical Behavior and Determination of Uric Acid at Single-Walled Carbon Nanotube Modified Gold Electrodes

The voltammetric behavior of uric acid was studied at a single-walled carbon nanotube (SWNT) modified gold electrode. Uric acid can effectively accumulate at this electrode and produce an anodic peak at about 0.45 V (vs. SCE) in pH 5.0 sodium acetate buffer solutions (HAc-NaAc). The experimental parameters, such as solution pH, accumulation time, and amount of SWNT, were optimized for determination. Under the optimum conditions, the anodic peak current is linear to the uric acid concentration over the range of 1.0×10⁻⁷ M to 2.5×10⁻⁵ M with a correlation coefficient of 0.998. The detection limit was 5.0×10⁻⁸ M for 60 s accumulation. The electrode could be easily regenerated and exhibited good stability. A 5.0×10⁻⁶ M uric acid solution was measured ten times using the same electrode, and the relative standard deviation of the peak current was 1.3%. This method was successfully applied to the determination of uric acid in human urine samples, and the recovery was 97–99%. The feasibility for simultaneous determination of xanthine, ascorbic acid and uric acid was discussed. These species did not interfere with each other in a certain concentration range. The influence of some surfactants on the anodic peak was also examined.     

碳纤维表面酰氯化及其与尼龙6的接枝Ⅱ、碳纤维接枝复合材料CF/PA6的等温结晶和熔融行为

碳纤维表面酰氯化及其与尼龙6的接枝Ⅰ、碳纤维接枝复合材料CF/PA6的等温结晶和熔融行为;阴离子接枝;碳纤维/尼龙6复合材料