橡胶/炭黑导电复合材料的压阻效应研究进展

综述了炭黑填充的压敏导电橡胶复合材料的压阻机理、压阻特性和压阻数学模型等方面的研究工作进展。讨论了加工工艺条件、填料性质、分散性等因素对压敏导电橡胶复合材料的压阻性能及压阻稳定性的影响。     

Pressure-sensitive electrically conductive nitrile rubber composites filled with particulate carbon black and short carbon fibre

The electrical conductivity of pressure-sensitive nitrile rubber composites, containing different loadings of particulate carbon black filler and short carbon fibre, have been studied. The conductivity of composites increases with increasing of filler concentration as well as with increased applied pressure up to a certain limit. The composites containing particulate fillers register low conductivity as compared to composites containing short carbon fibres, due to easy formation of an interconnecting network in the latter case. The effect of the orientation of short carbon fibre with respect to an applied electric field has also been studied. The pressure dependence of composites with transversely oriented carbon fibres with respect to electric fields is higher than that of composites with longitudinally oriented carbon fibres. The results are interpreted on the basis of the formation of interconnecting continuous conducting networks.     

基于炭黑填充导电橡胶的压力/温度传感器非线性特性

通过研究电阻率和电阻几何系数对"负电阻-压力系数"(NPCR)和"正电阻-温度系数"(PTCR)的影响,分析了炭黑填充导电橡胶(导电炭黑/橡胶)的压力/温度传感器的非线性特性。结果表明: 导电炭黑/橡胶的NPCR和PTCR效应产生非线性的主要原因为电阻率的非线性变化; 当炭黑体积分数接近渗流体积分数时,其电阻率对体积的变化敏感程度高,此时,导电炭黑/橡胶的NPCR和PTCR效应的非线性特性较强; 由于导电炭黑/橡胶的体压缩系数大于其热膨胀系数,且导电炭黑/橡胶在压力场和温度场下的形变过程不同,导电炭黑/橡胶NPCR效应的非线性强于PTCR效应的非线性。     

炭黑/聚氨酯泡沫导电复合材料的开发

制备了以聚氨酯软泡为基体的炭黑 /聚氨酯泡沫导电复合材料 ,研究了炭黑的用量及交联剂、扩链剂、偶联剂等助剂对复合材料电学及力学性能的影响。     

导电炭黑填充硅橡胶的电阻温度系数

以炭黑(CB3100)为导电相,硅橡胶为基质制备导电复合材料。研究导电橡胶中炭黑质量分数对电阻温度系数的影响,并用填料对电阻温度系数的影响。以隧道效应理论为基础,给出了导电炭黑填充橡胶的电阻温度系数计算模型,结合实验得到温度对导电炭黑/硅橡胶电阻温度系数的影响主要体现在对其电阻率的影响;基体的体积热膨胀提高复合材料的电阻率,提高了正电阻温度系数;炭黑粒子间的隧道效应降低复合材料的电阻率,增强了负电阻温度系数;在炭黑/硅橡胶中加入少量碳纳米管,利用碳纳米管和炭黑的协同补强效应,使复合材料的导电性和稳定性提高。     

炭黑填充导电橡胶的力敏传感器灵敏系数

以通用有效介质理论为基础, 给出了炭黑填充导电橡胶(炭黑/橡胶)的力敏传感器灵敏系数计算方程。采用该方程并结合应变和压阻效应对"负压力-电阻特性"(NPC)的影响程度, 分析了力敏导电炭黑/橡胶的灵敏系数和工作原理。结果表明: 炭黑体积分数在临界体积分数附近时, 力敏导电炭黑/橡胶的灵敏系数在2.5～13之间, 其工作原理主要为压阻效应。当炭黑体积分数在渗流区时, 灵敏系数在2.5～4.5之间, 其工作原理与接触压力的大小有关。压力较小时, 其工作原理主要为压阻效应; 压力较大时, 其工作原理主要为应变效应。炭黑体积分数在传导区时, 灵敏系数在2.0～2.5之间, 其工作原理主要为应变效应。      

基于炭黑填充导电橡胶的力敏传感器的灵敏度

以通用有效介质理论为基础, 给出了炭黑填充导电橡胶(炭黑/橡胶)的力敏传感器灵敏度计算方程。采用该方程并结合形变和压阻效应, 分析了影响力敏导电炭黑/橡胶的灵敏度的主要参数。结果表明: 炭黑体积分数是影响力敏导电炭黑/橡胶的灵敏度的主要参数。当炭黑体积分数在临界体积分数附近时, 力敏导电炭黑/橡胶的灵敏度为0.1～11.5 MPa^-1, 其敏感机制主要为压阻效应。当炭黑体积分数在渗流区时, 灵敏度为0.2～3.6 MPa^-1, 其敏感机制还与接触压力的大小有关, 压力较小时, 主要为压阻效应; 压力较大时, 主要为应变效应。若炭黑体积分数在传导区, 灵敏度为0.3～1.7 MPa^-1, 其敏感机制主要为应变效应。     

基于炭黑填充导电橡胶的力敏传感器的灵敏度

以通用有效介质理论为基础,给出了,炭黑填充导电橡胶(炭黑/橡胶)的力敏传感器灵敏度计算方程.采用该方程并结合形变和压阻效应,分析了影响力敏导电炭黑/橡胶的灵敏度的主要参数.结果表明:炭黑体积分数是影响力敏导电炭黑/橡胶的灵敏度的主要参数.当炭黑体积分数在临界体积分数附近时,力敏导电炭黑/橡胶的灵敏度为0.1～11.5 MPa-1,其敏感机制主要为压阻效应.当炭黑体积分数在渗流区时,灵敏度为0.2～3.6 MPa-1,其敏感机制还与接触压力的大小有关,压力较小时,主要为压阻效应;压力较大时,主要为应变效应.若炭黑体积分数在传导区,灵敏度为0.3～1.7 MPa-1,其敏感机制主要为应变效应.     

炭黑填充导电橡胶的温度传感器灵敏系数

以通用有效介质理论为基础,给出了炭黑填充导电橡胶(导电炭黑/橡胶)的温度传感器电阻-温度计算模型。利用该模型得出材料的灵敏系数计算公式,并结合形变和电阻率的变化对正电阻-温度特性(PTCR)的影响分析材料的灵敏系数特性。结果表明:在炭黑分布均匀、体积分数在渗流体积分数附近等条件下,电阻-温度计算模型与实验吻合,表现出一致的PTCR变化规律。导电炭黑/橡胶的PTCR效应主要源于基体膨胀导致炭黑体积分数的稀释作用,若炭黑体积分数在渗流区,导电炭黑/橡胶的灵敏系数为280~420;当炭黑体积分数在传导区时,其灵敏系数为32.5~62.0。导电炭黑/橡胶的PTCR效应是热-形变与形变-电导过程的乘积效应,导电炭黑/橡胶的灵敏系数高,但其体积膨胀系数低,使材料的电阻温度系数较低。     

石墨/炭黑/改性树脂导电复合材料的电学性能研究

以改性环氧树脂为基体、石墨\炭黑为混合导电填料制备了导电复合材料。分析了材料的导电机理,研究导电填料含量与电阻率之间的关系。结果表明:当石墨为15%、炭黑20%时制备的复合材料具有良好的导电性,电阻率为16.4Ω.cm。同时测试了复合材料的伏安特性曲线,发现其呈现非线性欧姆关系,具有正温度系数效应(PTC)。     

碳纳米管/聚乙烯/聚苯乙烯多相复合材料的制备及导电性能研究

用熔融共混的方法分别制备了两相复合材料MWNT(多壁碳纳米管)/LDPE、MWNT/PS和多相复合材料MWNT/LDPE/PS,以上3种复合材料的导电渗滤阈值分别为8%(wt,下同)、6%和4%.SEM观察发现,MWNT选择性的分布于MWNT/LDPE/PS复合材料的LDPE相中.当LDPE/PS的质量比为50/50时,聚合物基体形成双连续结构,由于双重渗滤的作用,复合材料的渗滤阈值降低到4%.     

导电炭黑Super-P对混凝土性能的影响

采用低成本和高稳定性的纳米导电炭黑Super-P (CBSP)作为水泥混凝土的添加剂。通过设置不同的水灰比和不同的CBSP掺量,研究了CBSP的加入对混凝土各方面性能的影响(即坍落度、力学性能、抗渗性能、导电性能和温敏性能)。通过SEM对混凝土微观形貌进行分析。实验结果显示,掺入纳米材料CBSP使混凝土坍落度不断降低。随着CBSP的掺入量不断增大,混凝土的力学性能先提升后降低且各龄期变化趋势相似,当CBSP的掺入量为0.75wt%时力学性能达到最大。同时混凝土的力学性能随水灰比的增加而降低。混凝土的抗渗性能随着CBSP掺量的增加而先提高后降低,且当水灰比较大时抗渗性能有所降低。当CBSP掺入量为0.75wt%～2wt%时,混凝土电阻率迅速降低。标准养护条件比室内干燥养护的混凝土电阻率低。不同水灰比混凝土之间电阻率相差较小。SEM显示了CBSP的填充孔隙和隧道导电作用。通过实验证明CBSP的加入可以改善混凝土的各项性能。     

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。     

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.     

Improvements in methods for measuring the volume conductivity of electrically conductive carbon powders

Electrically conductive carbon powders are commonly used as filler materials in polymers to create electrically semi-conductive composite materials for use in battery electrodes and anti-static applications. Current methods for characterizing the conductivity of these powders use two pistons to compress the powders. Two-piston methods are known to underestimate conductivity. This study develops a guard-electrode method based on ASTM D257 to better characterize the bulk conductivity and impedance spectra of electrically conductive powders. The conductivity and impedance spectra of a highly conductive powder (copper powder) and a low conductivity powder (cellulose) were used to bound the conductivity of carbon black, graphite, and biochar. Powders were measured through a full range of compression with both the two-piston and the guard-electrode method. In all cases, measurements using the guard-electrode method have higher conductivity and lower impedance than the same powders measured using the two-piston method. The grain conductivity of the particles is obtained through fitting the relationship of conductivity versus packing fraction using the GEM equation. The guard-electrode method is shown to be more similar to established conductivity values as measured via a four-probe technique for copper and graphite then the two-piston method.     

炭黑填充型导电橡胶的压力/温度特性研究

分析了导电橡胶的压阻效应和温度效应,实验制备了导电橡胶试样,并研究了试样添加不同导电粒子后的压阻特性和温度特性。研究表明,导电橡胶添加不同导电材料时呈现出不同的温度特性,随温度的升高,单独添加乙炔炭黑的导电橡胶在30～70℃之间呈现负温度效应,在70～120℃之间呈现正温度效应;乙炔炭黑与N472并用的导电橡胶随温度的升高呈现正温度效应;添加纳米Al2O3的导电橡胶随温度的升高呈现正温度效应和负温度效应。探讨了压力变化时电阻率与温度的相关性,分析了产生不同温度特性的主要原因。     

Transparent conductive thin film synthesis based on single-walled carbon nanotubes dispersion containing polymethylmethacrylate binder

Transparent conductive hybrid thin films of single-walled carbon nanotubes (SWNTs) and polymethyl methacrylate (PMMA) are fabricated using dispersions containing SWNTs and water-borne PMMA binder. The polymer binder was used as adhesion promoter between the SWNTs and the substrate. The polymer binder content in the SWNTs dispersion is varied to obtain the optimum optical transmittance, electrical conductivity, and mechanical adhesion. The PMMA and SWNT network formed the composite over substrate. The fabricated SWNTs/PMMA hybrid films are immersed in nitric acid (HNO3) and thionyl chloride (SOCl2) to improve electrical conductivity. SWNTs films with 0.2-0.6 mg/ml polymer binder have sheet resistance of 80-140 ohms/sq at a transmittance of about 80% and a strong adhesion on glass substrate. Furthermore, the electrical stability of the films is improved via the PMMA addition. This results indicates that the SWNTs/PMMA hybrid films fabricated by this method can be used as an alternative of indium tin oxide (ITO) film on flexible substrate.     

Mechanical and electrical properties of nanocomposites containing hybrid fillers of disk-like copper and conductive carbon black

Electrically conductive rubber (ECR) was prepared through conventional rubber mixing techniques on a two-roll mill, which the conductive filler was polymer-coated Cu nano-disk and conductive carbon black (CCB). The effect of Cu nanoparticles content on the mechanical and electrical resistivity properties of ECR was further investigated. The obtained results of six different compositions for ECR with 0, 5, 10, 15, 20 and 25 per hundred of rubber (phr) of Cu nanoparticles loading were compared. It was found that ECR has lower volume resistivity and high tensile strength, compared with rubber containing commercial Cu particles. These results suggest that when the Cu particles are nano-disk and surface modified, the mechanical and stability properties of the rubber can be synchronously improved.     

Influence of annealing on rheological and conductive behaviors of high-density polyethylene/carbon black composites

A simultaneous measurement on dynamic viscoelastic and conductive behaviors was carried out to investigate the effect of high temperature annealing on the properties of carbon black (CB) filled high-density polyethylene composites. The results showed that dynamic storage and loss moduli of the composites increased significantly with increasing annealing time, and there existed a liquid- to solid-like transition at a critical time (t _c) which is dependent on temperature and CB content. Accompanying with the variation in dynamic moduli, electrical resistance (R) decreased sharply with time. What’s more, the increase of R could be observed in the long time region. The activation energy determined from t _c as a function of reciprocal temperature was found to be irrespective of CB content. The evolutions of moduli and R induced by thermal treatment were discussed on the base of the concept of filler flocculation in the melt.