Performance stabilization of conductive polymer composites

Conductive polymer composites used as candidates for positive temperature coefficient (PTC) materials are faced with performance decay characterized by gradually increased room‐temperature resistivity and decreased PTC intensity. Considering that deterioration of the properties is mainly related to the capability of conductive networks established by conductive fillers to recover from the effect of repeated expansion/contraction in a timely manner, the present work introduces chemical bonding into the filler/matrix interphase. The experimental results indicate that in the composites consisting of conductive carbon black (CB), low‐density polyethylene (LDPE), and ethylene–vinyl acetate copolymer, CB particles can be covalently connected with LDPE through melt grafting of acrylic acid. As a result, the composites are provided with reduced room‐temperature resistivity and significantly increased PTC intensity. Compared with the composites filled with untreated CB, the present composites possess reproducible PTC behavior and demonstrate stable electrothermal output in association with negligible contact resistance at the composites/metallic electrodes contacts. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2438–2445, 2003     

环氧树脂基导电复合材料的PTC特性研究进展

介绍了聚合物基正温度系数（PTC）材料的导电机理;综述了国内外对环氧树脂基PTC复合材料的研究现状;分析了影响环氧树脂基导电复合材料PTC特性的因素,包括导电填料、环氧基体、第三基体组分、固化剂和固化温度、加工工艺等;并对该材料的应用和发展方向进行了讨论。     

Influences of dielectric and conductive fillers on dielectric and mechanical properties of solid silicone rubber composites

Dielectric elastomers are materials being used for electromechanical transduction applications. Their electromechanical response depends on permittivity, Young’s modulus and electric breakdown strength. A factor that limits its application is high operating voltages that can be reduced through improvement in permittivity. One of the methods is by incorporating high permittivity fillers into polymer matrix to obtain dielectric–dielectric composites (DDC).These composites show high permittivity at the cost of reduced flexibility. An alternative solution is development of composites by incorporating organic or inorganic conductive fillers into polymer matrix. These composites show high permittivity with high dielectric loss and low breakdown strength. To overcome both the above limitations both dielectric and conductive fillers are incorporated into dielectric polymer matrix to obtain conductor–dielectric composites (CDC). In this study, high temperature vulcanized solid silicone rubber as matrix has been used to prepare DDC composites with barium titanate (BT) filler and CDC composites with both BT as dielectric and ketjenblack as conductive fillers, using Taguchi design of experiments. The effect of factors such as amount of fillers and curing agent, mixing time in roll mill and curing temperature on the dielectric and mechanical properties are reported. Lichtenecker model predicts the permittivity of the DDC composite more accurately. For the CDC composites permittivity increased by 390%, effective resistivity decreased by 80%, Young’s modulus increased by 368% and Shore A hardness increased by 90% as compared to those of reference matrix. Important interaction effects are observed among both the fillers that are uniformly dispersed without any aggregation.

     

Positive temperature coefficient behavior of polymer composites having a high melting temperature

The positive temperature coefficient (PTC) behavior of polymers having a high melting temperature, such as nylon, polyvinylidene fluoride, polyester, and polyacetal, was investigated. Carbon black and nickel powder were used to investigate the influence of their conductive fillers on PTC intensity. The polymer/filler composite was irradiated with gamma rays at dosages of 50, 100, and 150 kGy for the purpose of reducing the negative temperature coefficient (NTC) of a conductive composite. It was found that the PTC temperature depended on the melting point of the polymer matrix. The crosslinking structure enhanced the electrical stability and decreased the NTC effect of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 394–401, 2004     

CTBN对CB/EP基导电复合材料电性能的影响

以低结构CB(炭黑)为导电填料、EP(环氧树脂)为基体、CTBN(端羧基液体丁腈橡胶)为改性剂和2,4-EMI(2-乙基-4-甲基咪唑)为固化剂,采用超声分散法制备CB/EP基导电复合材料.研究结果表明:CB/EP基导电复合材料具有明显的导电渗流行为,其渗流阈值为w(CB)=7.1％;当w(CTBN)=12％时,含CT...     

Improvement of conductive network quality in carbon black‐filled polymer blends

Heat treatment of polymer‐based composites is critical for the enhancement of both stability and long‐term service life, especially when the materials function under an inconstant temperature environment. The present article discusses the effect of heat‐treatment conditions on the electrically conductive properties of carbon black (CB)‐filled low‐density polyethylene (LDPE) and ethylene–vinyl acetate copolymer (EVA) composites, which are candidates for positive temperature coefficient (PTC) materials. It was found that the dispersion mode of CB particles changes as a function of the matrix morphology. When the composites are irradiated to form crosslinked networks in the matrix for the elimination of negative temperature coefficient (NTC) behavior, some of the produced free radicals are also entrapped for quite a long time after the irradiation treatment. These residual radicals further enhance the interaction between CB and the matrix and further induce the crosslinking of the matrix so that the composites' conductivity changes with time as a result of the continuous variation in the contacts between the conductive fillers. To improve the quality of the conduction paths in the composites, appropriate post‐heat treatment should be carried out, which speeds up the formation of the above‐mentioned two kinds of crosslinked structures within a limited time. Annealing at 75°C for more than 10 h is believed to be an effective way. After the treatment, a balanced performance characterized by reduced room‐temperature resistivity and improved PTC intensity was obtained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2768–2775, 2002     

Conductive polymer blends filled with carbon black: Positive temperature coefficient behavior

Electrical conductivity and positive temperature coefficient (PTC) behavior of carbon black (CB) filled incompatible polyblends of ethylene-vinyl acetate copolymer/low density polyethylene (EVA/LDPE) were investigated. In comparison with single polymer systems, more possibilities for tailoring composite performance were brought about with the employment of polymer blends as matrix resins in conductive composites. Based on the concepts of double percolation and two-step percolation, PTC-type composites with balanced performance, improved processability, and reproducibility can be made. Thermodynamical and kinetic factors including interfacial energy, melt viscosity, blending ratio, melt mixing time, sequence of blending as well as CB concentration were shown to be closely related to the ultimate properties obtained.     

Thermally induced performance decay in conductive polymer composites

In the course of long-term service, electrically conductive polymer composites acting as positive temperature coefficient (PTC) materials are faced with performance decay characterized by gradually increased room temperature resistivity and decreased PTC intensity. To reveal the influencing factors and to find appropriate ways for solving the problems, thermal-cold cycling experiments (which simulate the extreme operating conditions of PTC type materials in a laboratory environment) and electrification tests are carried out in the current work. The results demonstrate that irreversible damage of partial conductive networks and, in particular, oxidation degradation induced crystallizability deterioration of the matrix polymer are responsible for the electrical performance decay. Additionally, an increase in the contact resistance formed at the metallic electrode/composite contacts exerts a negative influence on the service life of the composites. Polym. Compos. 25:270–279, 2004. © 2004 Society of Plastics Engineers.     

Thermal conductivity of silicone rubber filled with ZnO

Thermal conductivities of silicone rubber filled with ZnO in a wide volume range were measured in order to study the effect of formed conductive particle chains on thermal conductivities. With the increasing of content of ZnO particles in silicone rubber, the amount of formed conductive chains increases and the conductive chains tend linearly to increase the thermal conductivity of the composite. The experimental results obtained were also analyzed using the Nielsen and Agari models to explain the effect of ZnO filler on the formation of thermal conductive networks. Thermal conductivities of a polymer filled with high volume content of particles evidently increased with the adding of small size fillers. The scanning electron microscopy (SEM) showed that percolation threshold has been reached at 31.4 vol% ZnO filler loading, and the hybrid fillers are more densely packed than single fillers in the silicone rubber matrix. There occurs a positive temperature coefficient (PTC) phenomenon in thermal resistance in composites of silicone rubber filled with ZnO. POLYM. COMPOS., 28:125–130, 2007. © 2007 Society of Plastics Engineers     

Visualisation of conductive filler distributions in polymer composites using voltage and energy contrast imaging in SEM

Semiconductive composites have been examined using advanced scanning electron microscopy (SEM). For the first time, voltage contrast and energy contrast between the conductive filler and the polymer matrix have been revealed using a secondary electron detector placed inside the lens system and an energy selective backscattering detector respectively. Critical parameters, including loading level, distribution, dimension and shape of conductive fillers, correlating to the electrical conductivities of the composites, have been investigated and quantitatively determined. These parameters are essential for performance predictions, product quality control and new product development. The volume fractions of the conductive fillers in the two investigated composites were determined as 20.9% and 14.2% respectively. Higher frequency of distribution distance between the conductive filler aggregates within the ranges of 20–100 nm was revealed for the composite with volume fraction of 20.9%. The aggregates of conductive fillers showed mainly branched shapes. The information obtained provides further insight into the conductivity mechanism of conductive filler loaded polymer composite.     

导电复合橡胶用导电填料的应用研究进展

对导电复合橡胶用导电填料如炭系、金属系、颗粒表面镀金属等的种类、性质等因素对复合橡胶材料导电率的影响及应用进行了综述。也对采用新型的填料即本征导电聚合物主要是聚苯胺填充制备导电复合橡胶的研究进展进行了综述。炭系是目前制备导电复合橡胶主要的导电填料,但有污染,不适合制备有颜色要求的导电材料,金属系、颗粒表面镀金属的比重大,在聚合物中分散较困难,也不太适合于有比重要求的制品。本征导电聚合物导电填充填料是制备导电复合橡胶发展的一个重要方向,可以解决不熔难溶造成的在聚合物中分散性差的问题。     

In situ melt grafting in carbon black/polyolefin composites and its influence on conductive performance

To improve the conductive properties of carbon‐black‐filled low‐density polyethylene, in situ grafting of certain monomers was applied during the melt compounding process. The experimental data obtained demonstrated that chemical bonding could thus be established between the fillers and the matrix polymer. The degree of enhancement of the filler/matrix interfacial interactions in the composites prepared in this way depends on the species of the grafting monomers being employed. When compared with the untreated carbon black composites, the composites manufactured through in situ melt grafting exhibited reduced room temperature resistivities and greatly increased positive temperature coefficient intensities, as well as favorable performance reproducibility. This proposed technical route has several advantages, including simplicity, low cost and easy control. Copyright © 2004 Society of Chemical Industry     

Enhanced positive temperature coefficient in amorphous PS/CSPE-MWCNT composites with low percolation threshold

In this work, amorphous polystyrene/chlorosulfonated polyethylene composites doped with multiwalled carbon nanotubes (PS/CSPE-MWCNT) were constructed by in situ polymerization to form semi-interpenetrating networks. The MWCNTs showed excellent dispersion and selective location in the PS regions. High electrical conductivity and low percolation threshold (0.89 wt %) for the composites were achieved. An enhanced positive temperature coefficient (PTC) behavior for amorphous PS/CSPE-MWCNT composites was first reported, nearly without a negative temperature coefficient (NTC) effect when the conductive fillers were beyond the percolation threshold, similar to those of crystalline polymer composites. Moreover, a PTC intensity of more than five orders of magnitude and excellent repeatability of the PTC effect were achieved. This study offers new insight into the development of novel PTC materials with low percolation threshold. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47053.     

Improved stability of volume resistivity in carbon black/ethylene-vinyl acetate copolymer composites by employing multi-walled carbon nanotubes as second filler

Semiconductive polymer shielding layers of power cable require stable volume resistivity to protect the insulation layer from stress enhancements when carbon black (CB)/polymer composite undergoes thermal cycles. For the CB-filled polymer composites, CB would often re-aggregate when temperature is close to the melting point of polymer matrix, so that the conductive network would be destroyed. Re-distribution of CB and re-formation of conductive CB network under thermal cycles might be the main reason for the instability of volume resistivity. In this work, the re-aggregation of CB in the CB/polymer composites was disclosed. Besides, a small amount of multi-walled carbon nanotubes (MWNTs) was employed as cofiller with CB to improve the stability of volume resistivity of the polymer composites under thermal cycles. The total weight fraction of conductive fillers (CB or CB cofilled with MWNTs) was set as 35 wt%. Compared with the polymer composites loaded with CB solely, the volume resistivity of the composites filled with CB-MWNTs was much more stable with changing temperature. This can be attributed to the enhancement of conductive networks when the MWNTs are employed as second conductive filler.     

炭黑填充聚合物基PTC导电复合材料及制品的研究进展

介绍了PTC效应的几种主要机理,讨论了不同基体、填充物和加工工艺对此类复合材料PTC效应的影响,NTC效应产生的主要原因以及减缓或推迟NTC效应的方法,并对其商业推广应用进行了较为深入的探讨.     

Melt spinning of conducting polymeric composites containing carbonaceous fillers

Fibers produced by melt spinning of conductive polymer composites are attractive for several applications; the main drawback is however reduced processability at high filler concentrations. Carbon nanotubes (CNTs) are considered suitable fillers for conductive polymer composites, replacing conductive grades of carbon black (CB). In this study, the fiber‐forming properties of conductive polymer composites based on a conductive grade of CB and two masterbatches with CNT in a polyethylene matrix were investigated. The CB was also used in a polypropylene matrix for comparison. The rheological properties of the filler‐containing melts in shear and their extensional behavior were evaluated. A piston‐driven device was used to extrude the molten materials through a capillary; different capillary geometries were tested. Fibers were produced at various draw ratios, and their conductivity was determined. To assess the ultimate extensibility, a modified Rheotens method was used. The results showed that a conductive CB grade can have a lower percolation threshold and higher conductivity than a material with CNT. Conductivity decreased with increasing melt draw ratio for both types of fillers. The spinnability of the materials decreased with increasing concentration of filler material and correlations were found between spinnability and melt elasticity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Studies on the comprehensive performance of graphite and additives filled high density polyethylene composites

The comprehensive performance of graphite and additives filled high‐density polyethylene (HDPE) composites is studied in this article. Four graphites with different particle diameters are used as conductive fillers in HDPE/graphite. Plasticizer, nucleator, and certain particle diameter graphite are employed to prepare HDPE composite. The behavior of crystallization and the distribution of graphite are also studied by means of SEM. An orthogonal design experiment is taken to optimize the content of the filler. The experimental results indicate that the positive temperature coefficient (PTC) effect is related to the particle diameter of graphite. And the bending strength of HDPE/graphite composite with the plasticizer and nucleator is two times less than that of HDPE‐graphite blends. Meanwhile, the high PTC intensity (the ratio of peak resistivity to room temperature resistivity) is also preserved. An excellent comprehensive performance conductive composite is prepared. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Progress on the morphological control of conductive network in conductive polymer composites and the use as electroactive multifunctional materials

Since the emergence of large aspect ratio and multifunctional conductive fillers, such as carbon nanotubes, graphene nanoplates, etc., conductive polymer composites (CPCs) have attracted increasing attention. Although the morphological control of conductive networks in CPCs has been extensively investigated as an important issue for the preparation of high performance CPCs, recent extensive progress has not been systematically addressed in any review. It has been observed that the morphological control of conductive networks during the preparation of CPCs has crucial influence on the electrical properties of these composites. Several methods have been shown to be able to control the network structure, and thus, tune the electrical properties of CPCs, including the use of shear, polymer blends, thermal annealing, mixed filler, latex particle etc. Moreover, many novel and exciting applications have been extensively investigated for CPCs, such as stretchable conductor, electroactive sensors, shape memory materials and thermoelectric materials, etc. Therefore, the morphological control of conductive network in CPCs is reviewed here. Issues regarding morphology characterization methods, morphological control methods, resulted network morphology and electrical properties are discussed. Furthermore, the use of CPCs as electroactive multifunctional materials is also reviewed.     

Recent Progress on Fabrication and Performance of Polymer Composites with Highly Thermal Conductivity

The rise of miniaturized, integrated, and functional electronic devices has intensified the need for heat dissipation. To address this challenge, it is necessary to develop novel thermally conductive polymer composites as packaging materials. In this paper, a number of factors for the construction and design of thermally conductive polymers are concluded. Special attention is focused on the analysis and comparison of the thermally conductive composites prepared by various fillers or strategies to provide guidelines and references for future design of composite materials. The current commonly used preparation strategies of thermally conductive polymer are summarized, such as using a variety of fillers, vacuum filtration, template method, and so on. The challenges of thermally conductive polymer composites are finally sketched. This review can inspire the design of polymer composites with brilliant thermal conductivity.     

Properties and thermo-switch behaviour of LDPE mixed with carbon black,zinc metal and paraffin wax

This paper reports on the presence of wax and radiation-induced crosslinking on the morphology, thermal and mechanical properties, as well as electrical conductivity and thermo-switch properties of LDPE containing different amounts of carbon black (CB) or carbon black plus zinc metal as filler. Although the filler was generally well dispersed in the polymer or polymer/wax blend, there were clear indications of the formation of conductive pathways. Different combinations of polymer, wax, CB and zinc filler and radiation induced crosslinking gave rise to different extents of crystallinity and/or chain immobilization, which had an influence on the mechanical and thermo-mechanical properties, and on the electrical conductivity and thermo-switch behaviour. Most importantly, the presence of wax, and CB and CB/Zn fillers, gave rise to increased electrical conductivity. The thermal expansion in the composites did not seem to play a significant role in obtaining larger values of the positive temperature coefficient of resistivity (PTC). We found that the presence of a small amount of paraffin wax significantly increased the PTC coefficients of the LDPE based conductive composites, and that γ-radiation induced crosslinking provided the thermo-mechanical stability of the amorphous regions in LDPE needed to obtain a high PTC intensity, which would provide a cheap material with good thermo-switch functionality, which is something not observed before.