Influence of morphology on positive temperature coefficient effect for conductive polymer composites with carbon black dispersed at interface

Selective localization of carbon black (CB) at the interface of polymer blends was achieved by the method that EBA‐g‐MAH was first reacted with CB, and then blended with poly(ethylene‐co‐butyl acrylate)/nylon6 (EBA/PA6). In CB‐filled EBA/PA6 blends, EBA and PA6 phases formed cocontinuous morphology and CB was localized in PA6 phase. The percolation threshold was 5 wt%. A single PTC (positive temperature coefficient) effect was observed in this composite. The appearance of PTC effect was originated from the thermal expansion of EBA phase. In the EBA‐g‐MAH filled EBA/PA6 blends, TEM results showed that CB particles were induced by EBA‐g‐MAH to localize at the interface, resulting that the percolation threshold was much lower than that of EBA/PA6/CB. Influence of morphology on PTC effect of EBA/PA6/EBA‐g‐MAH/CB composites was studied. In the composites with sea‐island morphology, the conductive network was fabricated by dispersed phase and CB at the interface. Thermal expansion of matrix interrupted the contact of dispersed phases and conductive network formed by CB particles at the interface, resulting in the double PTC effect. The composites with co‐continuous morphology exhibited single PTC effect due to the fact that conductive network was only fabricated by CB localized at the interface. POLYM. ENG. SCI., 53:2640–2649, 2013. © 2013 Society of Plastics Engineers     

Economical conductive graphite-filled polymer composites via adjustable segregated structures: Construction,low percolation threshold,and positive temperature coefficient effect

The economical graphite-filled thermoplastic urethane/ultra-high molecular weight polyethylene (TPU/UHMWPE) composites with the segregated structure were constructed by the combination of mechanical crushing and melt blending method. The low percolation threshold of 1.89 wt% graphite in the adjustable segregated composites was obtained and high electrical conductivity was about 10⁻¹ S m⁻¹ at 10 wt% graphite loadings owing to the formation of three-dimensional conductive networks. Moreover, when the graphite loadings were over the percolation threshold, the remarkable positive temperature coefficient (PTC) effect of electrical resistivity for TPU/UHMWPE-Graphite composites were achieved, originating from the combined thermal motion of TPU and UHMWPE. Meanwhile, the outstanding repeatability of PTC effects was obtained after 5-time cycles. Therefore, economical conductive polymer composites were still the promising field in the practical application of PTC materials.     

Designs of conductive polymer composites with exceptional reproducibility of positive temperature coefficient effect: A review

Conductive polymer composites with positive temperature coefficient (PTC) effect have gained intensive attention for the potential application in the smart heating field. The PTC reproducibility is significantly essential to guarantee the security and utility of PTC composites. Regrettably, during the repeated temperature cycles, the irreversible self-aggregation of conductive filler and the random reconstruction of conductive network lead to unsatisfactory performance of PTC reproducibility. Extensive efforts have been conducted to address this issue by strategies, including modification of fillers, cross-linking of a polymer matrix, hybrids of fillers, and application of binary polymer matrix. Nevertheless, there are very limited reviews about this issue. In this review, the recent advances in fabricating PTC composites with the enhanced PTC reproducibility have been systematically summarized. Meanwhile, the current challenges and future prospects of PTC composite are also presented. We hope that this review will provide some inspirations for designing PTC materials of long-term performance for commercial applications.     

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.     

The positive temperature coefficient phenomenon of vinyl polymer/CB composites

In this paper, the results of a systematic study of carbon black (CB)-filled conducting polymer positive and negative temperature coefficient (PTC/NTC) effects are report. The conductivity of the composites jumps by several orders of magnitude at the critical value of carbon black. This critical value, ø_c, decreases with the increase of melt index and degree of crystallinity of the polymer. The crystalline lamellae just “modify” the distribution of carbon black and make the dispersion heterogeneous. Radiation cross-linking enhances the PTC intensity and decreases the NTC effect of the materials. The electrical reproducibility of compounds is improved by the cross-linking structure that reduces the freedom of carbon black movement at high temperature. The NTC phenomenon is related to the carbon black coagulation that facilitates electrical conduction at high temperature. The larger the melt index, the more easily carbon black coagulates. A new model was set up to explain the results successfully. © 1993 John Wiley & Sons, Inc.     

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     

Bridged double percolation in conductive polymer composites: an electrical conductivity, morphology and mechanical property study

Conductive polymer composites are ubiquitous in technological applications and constitute an ongoing topic of tremendous commercial interest. Strategies developed to improve the level of electrical conductivity achieved at a given filler concentration have relied on double-percolated networks induced by immiscible polymer blends, as well as mixtures of fillers in a single polymer matrix, to enhance interparticle connectivity. In this work, we combine these two strategies by examining quaternary composites consisting of high-density polyethylene (HDPE), ultrahigh molecular weight polyethylene (UHMWPE), graphite (G) and carbon fiber (CF). On the basis of our previous findings, we examine the electrical conductivity, morphology, thermal signature and mechanical properties of HDPE/UHMWPE/G systems that show evidence of double percolation. Upon addition of CF, tremendous increases in conductivity are realized. The mechanism by which this increase occurs is termed bridged double percolation to reflect the role of CF in spanning non-conductive regions and enhancing the continuity of conductive pathways. At CF concentrations above the percolation threshold concentration, addition of G promotes increases in conductivity and dynamic storage modulus in which the conductivity increases exponentially with increasing modulus.     

Improvement of polyimide/polysulfone composites filled with conductive carbon black as positive temperature coefficient materials

In this study, polyimide (PI)/polysulfone (PSF) blends filled with carbon black (CB) were developed for the use as positive temperature coefficient (PTC) materials in order to achieve the volume resistivity as lower than 10⁴ Ω.cm at room temperature. The weight ratios of PI/PSF were various from 100/0 to 10/90 with CB varied from 0 to 20 wt%. The use of conductive filler was reduced when PSF was blended with PI; the blends clearly possessed a percolation threshold decreased by 90%. The electrical conductivity of the CB-filled blends was higher than those of CB-filled pure PI. The transition temperature for PTC material was reported in the range of 180 to 210 °C. The preferential location of CB filler in PI domains could be observed using the optical microscope. In addition, the composites met the standards for the obtained mechanical and thermal properties, exhibiting the potential use as PTC materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48482.     

Electrical behavior and positive temperature coefficient effect of graphene/polyvinylidene fluoride composites containing silver nanowires

Polyvinylidene fluoride (PVDF) composites filled with in situ thermally reduced graphene oxide (TRG) and silver nanowire (AgNW) were prepared using solution mixing followed by coagulation and thermal hot pressing. Binary TRG/PVDF nanocomposites exhibited small percolation threshold of 0.12 vol % and low electrical conductivity of approximately 10^-7 S/cm. Hybridization of TRGs with AgNWs led to a significant improvement in electrical conductivity due to their synergistic effect in conductivity. The bulk conductivity of hybrids was higher than a combined total conductivity of TRG/PVDF and AgNW/PVDF composites at the same filler loading. Furthermore, the resistivity of hybrid composites increased with increasing temperature, giving rise to a positive temperature coefficient (PTC) effect at the melting temperature of PVDF. The 0.04 vol % TRG/1 vol % AgNW/PVDF hybrid exhibited pronounced PTC behavior, rendering this composite an attractive material for making current limiting devices and temperature sensors.     

Lowering the percolation threshold of conductive composites using particulate polymer microstructure

The percolation thresholds of carbon black–polymer composites have been successfully lowered using particulate polymer starting materials (i.e., latex and water‐dispersible powder). Composites prepared using carbon black (CB) and commercial poly(vinyl acetate) (PVAc) latex exhibit a percolation threshold near 2.5 vol % CB. This threshold value is significantly lower than that of a comparable reference composite made from poly(N‐vinylpyrrolidone) (PNVP) solution and the same CB, which exhibits a sharp rise in electrical conductivity near 15 vol % CB. This dramatic difference in critical CB concentration results from the segregated microstructure induced by the latex during composite film formation. Carbon black particles are forced into conductive pathways at low concentration because of their inability to occupy volume already claimed by the much larger latex particles. There appears to be good qualitative agreement between experimental findings and current models dealing with conductive behavior of composites with segregated microstructures. Lack of quantitative agreement with the models is attributed to the polydispersity of the polymer particles in the latex. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 692–705, 2001     

Room temperature resistance relaxation behavior for carbon black filled conductive polymer composites

Room temperature resistance relaxation was studied with respect to carbon black (CB) volume fraction, the type of polymer matrix, and the environment. It was found that resistance of CB filled poly(methylvinylsiloxane) and polypropylene (PP) conductive composites changed at room temperature with different directions and amplitudes, depending on the filler volume fraction and the environment. The room temperature resistance relaxation was ascribed to the local Joule heat at the tunneling junction or the swelling effect of the solvents. On the other hand, CB filled immiscible PP/Nylon 1212 blends exhibited a stable electrical conduction due to the selective distribution of CB aggregates along the interface between polymer matrices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Control of carbon nanotubes at the interface of a co-continuous immiscible polymer blend to fabricate conductive composites with ultralow percolation thresholds

The concept of “double percolation”, i.e., conductive fillers are selectively located in one phase of a co-continuous polymer blend to form a percolated network in the selected phase, is widely used to reduce the percolation thresholds of conductive polymer composites to a fraction of their original values. However, it is expected that the percolation threshold can be significantly reduced further if the conductive fillers are only selectively distributed at the continuous interface of the co-continuous polymer blend, where only a very small amount of fillers are needed to build up the conductive percolated network. Multiwalled carbon nanotubes (MWCNTs) with very high aspect ratio (ca. 1000) are selectively distributed at a continuous interface of a co-continuous immiscible poly(lactic acid)/poly(ε-caprolactone) (PLA/PCL) blend at a weight ratio of 50/50 by controlling the migration process of MWCNTs from the unfavorable PLA to the favorable PCL phase. Compared to the PLA/PCL/MWCNTs composites by the traditional double percolation method (percolation threshold is ca. 0.97 wt%), the percolation threshold of PLA/MWCNTs/PCL composites (ca. 0.025 wt%) drops 2 orders of magnitude due to controlling the MWCNTs at the continuous interface between the PLA and PCL phases.     

丙烯酸树脂基导电油墨正/负升温系数协同效应的研究

采用乳液聚合的方法,利用Fox方程进行设计合成了玻璃化温度可控型聚(甲基丙烯酸甲酯-丙烯酸丁酯)[P(MMA-BA)]。借助激光粒度分布仪得到了控制乳液的粒径分布与大小的工艺条件;利用差热扫描量热仪(DSC)测定了聚合物的玻璃化温度(Tg)。实验发现所测的Tg与实验设计值有一定的偏差,为此对Fox公式进行了适用性的修正,理论设计和实测结果达到了很好的吻合。重点探讨了丙烯酸粘结料树脂玻璃化温度与导电填料的配比对电热膜电阻值稳定性的影响。利用扫描电子显微镜观察分析导电网络。结果表明,非晶态丙烯酸高聚物的PTC效应显著,消除了导电填料在温度升高过程中的NTC效应。     

Positive temperature coefficient effect and mechanism of compatible LLDPE/HDPE composites doping conductive graphite powders

Linear low density polyethylene (LLDPE)/high density polyethylene (HDPE) blends doped conductive graphite powders were constructed by the traditional melt‐blending method to acquire the conductive compatible polymer composites, and corresponding positive temperature coefficient (PTC) effect of electrical resistivity was investigated. The results indicated that the room‐temperature resistivity gradually decreased and PTC effects were remarkably enhanced by regulating the graphite contents or LLDPE/HDPE ratios. Especially, with increasing graphite contents, the polymer‐fixed composites showed the notable double PTC effects, originating from the volume expansion of the co‐crystallization or their fraction. Whereas, with increasing the LLDPE/HDPE ratio, the PTC effects of the graphite‐fixed composites occurred at the lower temperature, even far below the melting points of the co‐crystallization. Therefore, the regulation of co‐crystallization morphology of compatible polymer matrices was a new idea in the improvement of PTC materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46453.     

炭黑/碳纳米管/环氧树脂复合材料的导电渗流行为研究

采用超声分散溶液混合法制备炭黑/碳纳米管/环氧树脂(CB/CNTs/EP)复合材料,研究了不同几何结构的炭系填料的导电作用,并且通过体积电阻率测试和扫描电镜等手段分别对其电性能和微观形貌进行了表征与分析。结果表明,在CB/CNTs/EP复合材料中,CB和CNTs按质量比4:1填充复合体系的渗流阈值为3.8%,介于两种填料单独使用时的两个渗流阈值之间。不同结构纳米材料(CB和CNTs)的混用会在环氧树脂体系中形成更稳定的导电网络,提高了复合材料的导电性。     

The correlativity of positive temperature coefficient effects in conductive silicone rubber

A thorough study on the positive temperature coefficient (PTC) effects of conductive silicone rubber was made. Various conductive silicone rubbers with apparent differences in PTC anomalies (defined as the ratio of peak resistivity to room temperature resistivity) were chosen. The correlation between the size of the PTC anomaly and both the thermal expansion coefficient of conductive silicone rubber and the interaction between silicone rubber and carbon black (CB) were found. The effects of cross‐linking on the temperature effect of resistivity of conductive silicone rubber were also studied. The results testify the important role of the interaction between silicone rubber and CBs in the temperature effect of resistivity of conductive silicone rubber. Copyright © 2005 Society of Chemical Industry     

Effect of coefficient of thermal expansion on positive temperature coefficient of resistivity behavior of HDPE–Cu composites

Positive temperature coefficient of resistivity (PTCR) characteristics of (high density polyethylene) HDPE–Cu composites has been investigated with reference to the conventional HDPE–CB (carbon black) composites. Plot of resistivity against temperature of HDPE–CB composites showed a sudden rise in resistivity (PTC trip) at 127°C, close to the melting temperature of HDPE. However, the PTC trip temperature (98°C) for HDPE–Cu composites was appeared well below the melting temperature of HDPE. Addition of 1 phr nanoclay in the composites resulted in an increase in PTC trip temperature of HDPE–Cu composites, whereas no significant effect of nanoclay on PTC trip temperature was evident in case of HDPE–CB–clay composites. We proposed that the PTC trip temperature in HDPE–Cu composites was governed by the difference in coefficient of thermal expansion (CTE) of HDPE and Cu. The room temperature resistivity and PTC trip temperature of HDPE–Cu composites were very much stable upon thermal cycling. DMA results showed higher storage modulus of HDPE–Cu composites than the HDPE–CB composites. Thermal stability of HDPE–Cu composites was also improved compared to that of HDPE–CB composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of thermal ageing treatment and antioxidants on the positive temperature coefficient characteristics of carbon black/polyethylene conductive composites

Polyethylene (PE)‐filled with carbon black (CB) is a prototypical composite that displays resistance switching. These materials can exhibit either a positive temperature coefficient (PTC) or negative temperature coefficient (NTC). The CB‐filled semicrystalline polymer composites ideally need antioxidants, which stabilize the composites against thermooxidative degradation, because they should be resistant to the severe conditions of high temperature. The characterization of PTC materials is affected by the crystallinity of the polymer, and the crystallinity of the polymer is changed with thermal ageing treatment. Thermal ageing of PTC samples was conducted in an oven in the range 50–140°C, in air. The composites, containing 0.5–3% (by weight) Irganox 1076 (Ciba‐Geigy), were irradiated under nitrogen at room temperature with different doses of gamma rays from a ⁶⁰Co source. The resulting composites were analyzed by differential scanning calorimetry, gel fractionation, X‐ray diffraction, and dynamic mechanical analysis. The conductivity of the composites depended on the amounts of antioxidants and the duration of the thermal ageing treatment. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2316–2322, 2003     

Electrically conductive polymer composites and blends

Increasing utilization of the electrical properties of polymeric blends and composites has prompted our renewed interest in developing a general working relationship which can explain the electrical properties of polymer composites and blends in terms of processing characteristics, morphology, and compositions. Here, we restrict our attention to the following two-component systems: (1) two component systems with conductive particulate inclusions (e.g. carbon black) embedded in a continuous polymeric matrix, and (2) two component polymer blend systems with one conductive polymer (e.g., polyether copolymer) dispersed in another continuous polymeric matrix. The following processing aspects related to the electrical property of particulate filled composites are discussed: (1) critical concentration of rigid conductive fillers, ?_c, and (2) redistribution of conductive fillers upon processing. An equation based on the crowding factor of concentrated suspension rheology and Janzen's particle contacts percolation is proposed to describe the relationship between ?_c, and the maximum packing fraction of conductive fillers. The relationship is used to explain the influence of particle morphology on conductivity, and the conductivity difference in the high shear and the low shear region of a processed polymer composite part. Furthermore, some qualitative guidelines for blending a low conductivity polyether copolymer to achieve an overall balance of antistatic and mechanical properties of polymer blends are also discussed.