Electrical conductivity and percolation threshold of hybrid carbon/polymer composites

The electrical conductivity and percolation threshold of single and hybrid carbon filled composites are experimentally investigated. Polystyrene, carbon fiber (CF) and carbon black (CB) at three CF/CB ratios of 1.67, 3.33, 6.67 were compounded in a twin screw extruder micro‐compounder and compression molded into sheets. The through‐plane and in‐plane electrical conductivity of the composites are measured by 2 and 4 probe techniques. The percolation threshold of the single filler and hybrid composites are determined from the experimental results using a percolation model. The hybrid composites have a higher value of electrical conductivity and lower percolation threshold than the single CF filler composite except for the CF/CB ratio of 6.67. The percolation threshold for the cases of single filler and hybrid composites are modeled. The hard core / soft shell model is used and it is assumed that the percolation in a particle filled system depends on the ratio of tunneling distance to particle diameter. This ratio is determined by modeling single filler composites using the experimental data and kept constant in the modeling of the hybrid system. Finite size scaling is used to determine the percolation threshold for the infinite size hybrid system containing (nanosize) particles and micron size fibers for three CF/CB ratios. The simulation results show that the percolations of hybrid composites have the same trends observed in the experimental results. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41744.     

Effect of carbon black structure on low‐strain conductivity of polypropylene and low‐density polyethylene composites

The influences of carbon black (CB) structure on the percolation threshold, mechanical properties, and strain‐resistivity response of polymer composites are studied. Low‐density polyethylene (LDPE) and polypropylene (PP) samples were blended with five different types of CB differing in structure. Relatively low strains were studied; the maximum strain was 10%. It was found that the CB concentration for maximum strain‐sensitivity of the electrical conductivity is higher for low structure carbon blacks but is essentially independent of the CB structure for medium‐ to high‐structure carbon blacks. However, the composite containing the largest particle size carbon black clearly showed the highest strain‐sensitivity to electrical conduction. The mechanical properties and sensitivity of electrical resistivity to tensile strain of the filled composites examined in the study are also presented and discussed. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Nylon 6 induced morphological developments and electrical conductivity improvements of polypropylene/carbon black composites

In this study, a polar conductive filler [carbon black (CB)], a nonpolar polymer [polypropylene (PP)], and a polar polymer [nylon 6 (PA6)] were chosen to fabricate electrically conductive polymer composites by melt blending and compression molding. The morphological developments of these composites were studied. Scanning electron microscopy results showed that in a CB‐filled PP/PA6 (CPA) composite, CB particles were selectively dispersed in PA6 phases and could make the dispersed particles exist as microfiber particles, which could greatly improve the electrical conductivity. The PA6 and CB contents both could affect the morphologies of these composites. The results of electrical resistivity measurements of these composites proved the formation of conductive networks. The resistivity–temperature behaviors of these composites were also studied. For CB‐filled PP (CP) composites, there were apparent positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects and an unrepeatable resistivity–temperature characteristic. However, for CPA composites, there were no PTC or NTC effects from room temperature to 180°C, and the resistivity–temperature behavior showed a repeatable characteristic; this proved that CB particles were selectively dispersed in the PA6 phase from another point of view. All experimental results indicated that the addition of PA6 to a CP composite could lead to an expected morphological structure and improve the electrical conductivity of the CP composite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Voltage–current characteristics of high-density polyethylene conductive composites

The high-density polyethylene (HDPE) conductive composites filled separately with carbon fibers (CFs), ethylene-vinyl acetate copolymer (EVA), and three kinds of carbon blacks (CBs) (including different diameter, BET specific area, and DBP value) were prepared, to investigate the influence of the property, size, and content of the conductive fillers on the nonlinear voltage–current characteristics of the HDPE conductive composites. The results showed that the relationship between the electric current density and the electric field intensity of the three HDPE/CB composites including the HDPE/CF composites, the HDPE/CB/CF composites, and the HDPE/EVA/CB composites was nonlinear. The nonlinear conductivity index of the HDPE/CF composites was kept a low level comparing to the HDPE/CB composites, the HDPE/CB/CF composites, and the HDPE/EVA/CB composites. Moreover, the nonlinear conductive behavior mechanisms were discussed.     

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.     

Ethylene–(vinyl acetate) copolymer/carbon fiber conductive composite: effect of polymer–filler interaction on its electrical properties

Ethylene–(vinyl acetate) (EVA)/carbon fibre (CF) composites were prepared by changing the content of CF in the composite. To investigate the effect of the interaction between EVA and CF on the electrical properties of the composite, the CF was treated in nitric acid. The interaction between EVA and CF was examined by a solvent-extraction method. It was found that the interaction of EVA with CF was enhanced due to the chemical absorption of EVA on CF. The correlation of CF content, electrical properties and the formation of polymer–filler gel for the composite with oxidized CF was studied. Although the composites filled with treated CF exhibit a slightly higher resistivity than those filled with untreated CF at room temperature, they show the improved electrical properties, including elimination of the negative-temperature-coefficient (NTC) effect, high electrical reproducibility after thermal cycles, and independence of the conductivity on time, which improves the practical applications of positive-temperature-coefficient (PTC) materials. Copyright © 2004 Society of Chemical Industry     

The effect of filler concentration on the electrical,thermal, and mechanical properties of carbon particle and carbon fiber‐reinforced poly(styrene‐co‐acrylonitrile) composites

Composite materials of poly (styrene‐co‐acrylonitrile) (luran) matrix with carbon fibers (CF)/carbon particles (CP) were prepared and their properties were evaluated. The mechanical and thermal properties of these composites were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Although, by increasing the filler concentration no significant difference was found in melting and crystallization temperatures of the luran. The storage and tensile modulus of the composites increased linearly with filler concentration up to 40 wt % that was approximately three times higher than that of the virgin luran. There is a shift in glass transition temperature of the composite with increasing the filler concentration and the damping peak became flatter that indicated the effectiveness of the filler–matrix interaction. The volume resistivity and thermal conductivity (TC) of the composites were also measured. At a given carbon filler content the CF–Luran composites have much less volume resistivity as compared to CP–Luran composites. The decreased percolation threshold and volume resistivity in case of CF–Luran composites indicated that conductive paths existed in the composites. The conductive pathways were probably formed through interconnection of the carbon fillers. The volume resistivity was also decreased as a function of temperature. The thermal conductivity was increased linearly as a function of temperature with increasing filler concentration up to 40% of CF and CP. This increase was more profound in case of CF–Luran as compared to CP–Luran composites. This was owing to greater thermal networks of fibers as compared to particles. POLYM. COMPOS., 28:186–197, 2007. © 2007 Society of Plastics Engineers     

Electrical and thermal conductivity and tensile and flexural properties: Comparison of carbon black/polycarbonate and carbon nanotube/polycarbonate resins

Adding conductive carbon fillers to thermoplastic polymers increases the resulting composite's electrical conductivity. Carbon black (CB) is very effective at increasing composite electrical conductivity at low loading levels. In this study, varying amounts (2 to 10 wt %) CB were added to polycarbonate (PC) and the resulting composites were tested for electrical conductivity (1/electrical resistivity), thermal conductivity, and tensile and flexural properties. These results were compared with prior work done for carbon nanotubes (CNT) in polycarbonate. The percolation threshold was ～ 2.3 vol % CB compared to between 0.7 and 1.4 vol % CNT. At 8 wt % filler, the CNT/PC composite had an electrical resistivity of 8 ohm‐cm compared to 122 ohm‐cm for the CB/PC composite. The addition of CB to polycarbonate increased the composite electrical and thermal conductivity and tensile and flexural modulus. The 8 wt % (5.5 vol %) CB in polycarbonate composite had a good combination of properties for semiconductive applications. Ductile tensile behavior is noted in pure polycarbonate and in samples containing up to 8 wt % CB. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

抗静电软质聚氯乙烯材料的研究

采用表面电阻测试和扫描电镜，分析研究了软质聚氯乙烯(PVC)树脂与炭黑(CB)复合体系的抗静电性与炭黑含量、分布形态、PVC树脂型号及混炼塑化工艺之间的关系。结果表明：在炭黑临界添加量18％时，较短的混炼时问内，不同型号的PVC树脂基体中均能形成导电网络，体系的导电性能迅速提高，可达到抗静电的目的。相同混合和成型条件下，与SG-3树脂相比，炭黑在相对分子质量较大的SG-2基体树脂中更易形成均匀分布形态，破坏导电网络，导致电性能随混炼时间迅速下降。力学性能测试表明：炭黑的加入使复合体系的拉伸强度和断裂伸长率降低。     

Hybrid particulate and fibrous injection molded composites: Carbon black/carbon fiber/polypropylene systems

The electrical properties of injection molded composite systems based on a polypropylene matrix and two types of carbonaceous fillers—carbon black (CB) and carbon fibers (CF)—were investigated. In addition to conductivity as a function of system compositions, conductivity profiles were studied. Inhomogeneous spatial distribution of CB particles in moldings containing either CB as a single filler or in combination with CF was found. Furthermore, unexpected fiber orientation transverse to the melt flow direction and disappearance of skin‐core orientation pattern, typical for injection molded fiber filled composites, were observed in the two filler samples. An amplification of the shear‐thinning behavior, characteristic for the polypropylene (PP) matrix, imposed by the inhomogeneity of the CB distribution resulting in flattening of the advancing melt front and velocity profile is suggested as underlying the observed phenomena. POLYM. COMPOS., 26:454–464, 2005. © 2005 Society of Plastics Engineers     

Effect of a coupling agent on the electromagnetic and mechanical properties of carbon black/acrylonitrile–butadiene–styrene composites

Titanate coupling agent (TCA) is widely used as a plasticizer in filled polymer processes. In this study, the effect of TCA with different contents (2 and 10 wt %) on the electrical conductivity, wave absorption, and mechanical properties of carbon black (CB)/acrylonitrile–butadiene–styrene (ABS) composites were investigated. The results indicate that with the addition of 2 wt % TCA to the filled CB, the electrical conductivity of CB/ABS composites improved greatly, but its wave absorption performance was weakened. In contrast, the addition of 10 wt % TCA to the filled CB improved the microwave absorption performance of the CB/ABS composites but led to poor electrical conductivity. However, TCA, regardless of the contents of 2 or 10 wt %, greatly improved the mechanical properties of the composites. The probable reasons for this are discussed on the basis of the fracture morphology of the sample, a chemical band between the filling and resin, and the physical coating between the filling and TCA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1839–1843, 2006     

Electrical conductivity of epoxy/silicone/carbon black composites: Effect of composite microstructure

The objective of this work is to study the effect of electrical conductivity and physical‐mechanical properties of carbon black (CB) filled polymer composites. This goal is achieved by synthesizing epoxy/silicon phase separated blend structure of composites filled with CB. The percolation threshold of epoxy/silicone/CB composites decreased and the total conductivity increased compared to the pure epoxy/CB composite. A threefold increase was obtained with tensile strength of epoxy/silicone/CB composite with 25 wt% of silicone and 5 wt% of CB in comparison with epoxy/CB systems. This composite has conductivity of about 10⁻⁶ S/cm, which is six orders of magnitude higher than for epoxy/CB composites at the same concentration of CB. POLYM. COMPOS., 35:2234–2240, 2014. © 2014 Society of Plastics Engineers     

Effect of plasticizer on the electrical,thermal, and morphological properties of carbon black filled poly(propylene)

Poly(propylene) (PP)/carbon black (CB) composites are melt‐blended in a Brabender mixer with varying CB content. With the special‐grade conductive CB, the surface resistivity of PP/CB composite was reduced by 13 orders of magnitudes by increasing the CB content from 0 to 15 wt%. The plasticizer poly(ethylene glycol) di‐methyl ether (PEGDME) is used (0–5 wt%) to improve the dispersion of the CB in the polymer matrix and to reduce the surface resistivity of the composites. But the PEGDME plasticizer used here has no positive effect on the surface resistivity of the composites; in fact, it enhances the surface resistivity value by one order of magnitude at higher concentration (5 wt%). The scanning electron microscopy (SEM) pictures indicate that the presence of foreign material (plasticizer) especially at higher concentration disrupts the continuous carbon network inversely affecting the conductivity values. Finally, the optimization of the input variables (CB and PEGDME loading) is done using the design of experiment approach. POLYM. COMPOS., 38:2472–2479, 2017. © 2015 Society of Plastics Engineers     

High‐density polyethylene/carbon black conductive composites. I. Effect of CB surface modification on its resistivity–temperature behavior

The effect of the interaction between a polymeric matrix and conductive particles of carbon black (CB), especially the interaction enhanced by oxidizing CB (o‐CB), on the resistivity–temperature behavior of its composites was studied. The results reveal that the interaction between ethylene‐vinyl‐acetate and CB is stronger than that between high‐density polyethylene and CB. The room temperature resistivity of the o‐CB filled system subsequent to thermal cycles increases to a lower extent in comparison with those filled with virgin CB. Moreover, the resistivity decrease of composites filled with o‐CB needs a longer time than that of the virgin CB filled system during isothermal annealing, meaning that the resistivity–temperature behavior of the former is much more stable than that of the latter. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3112–3116, 2002; DOI 10.1002/app.10049     

Effects of strain and temperature on the electrical properties of carbon black‐filled alternating copolymer of ethylene‐tetrafluoroethylene composites

Carbon black (CB)‐filled alternating copolymers of ethylene‐tetrafluoroethylene (ETFE) composites were prepared by the melt‐mixing method. The effects of strain and temperature on the electrical resistivity of the composites were elucidated in detail. Our results indicated that the CB content and CB particle size are the two main factors that influence the electrical resistance of the composites when they are subjected to strain. The large particle size CB‐filled ETFE composites with a low CB content show a significant increase in electrical resistivity as a function of strain. A linear relationship between the logarithm of the electrical resistivity of the composites and strain was observed, indicating that tunneling conduction plays an important role when the composites are subjected to strain. The tensile testing results indicated that the CB‐filled ETFE composites have reasonably good tensile properties.     

Resistivity relaxation behavior of carbon black filled high‐density polyethylene conductive composites

The variation of resistivity for high‐density polyethylene (HDPE) conductive composites filled with carbon black (CB) with time was investigated under the excitation of different temperature field. The movement of CB particles in the HDPE matrix was not a momentary equilibrium process, but a relaxation process. The relaxation of resistivity of the composites was monotonic, and it could be described by an exponential form above melting temperature. However, the relaxation of resistivity was nonmonotonic below melting temperature, herein a parameter t₀ which was the beginning time of the resistivity attenuation could be introduced into the exponential equation. The attenuation of resistivity at constant temperature was limited for the composites with certain content of CB. The resistivity of the composites would incline to a constant value with the prolongation of time no matter what the heat treatment temperature was. Heating rate had influence on the relaxation of resistivity of the composites, and the lower heating velocity resulted in less time to approach to the equilibrium resistivity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Kinetic and thermodynamic control in conductive PP/PMMA/EAA carbon black composites

Multiphase polymer blends provide unique morphologies to reduce the percolation concentration and increase conductivity of carbon‐based polymer composites via selective distribution of the conductive filler. In this work, the kinetic and thermodynamic effects on a series of multiphase conductive polymer composites were investigated. The electrical conductivity of carbon black (CB)‐filled conductive polymer blend composites comprising polypropylene, poly(methyl methacrylate), and ethylene–acrylic acid were determined as a function of compounding sequence and annealing time. Kinetic and thermodynamic parameters were found to influence the conductivity. Phase morphology and conductivity at short annealing times were influenced by the compounding sequence where the CB was added after being premixed with one of the polymer components or directly added to the three‐component polymer melt. However, they were thermodynamically driven at longer annealing times; the resistivity was found to decrease by a statistically significant amount to similar levels for all the composite systems with increasing annealing time. The increase in conductivity at longer annealing times was determined to be the result of changes in the phase morphology from sea‐island, dispersed microstructure to a tri‐continuous morphology rather than change in localization of CB, given that the CB was found to be entirely located in the EAA phase even at short annealing times (and independent of compounding sequence), where the conductivity was not measurable. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42134.     

炭黑/环氧树脂复合材料导电行为的研究

分别采用不同的混合分散方法制备炭黑/环氧树脂(CB/EP)复合材料(CB牌号为F101、XE2,EP牌号为E-54、E-51和E-44),研究了制备工艺、CB用量和CB结构等对复合材料导电性能的影响。结果表明:不同方法制得的复合材料体积电阻率的大小依次为机械混炼法离心混合法超声分散法;CB/EP复合材料的导电性能随CB用量增加而显著提高,并且F101/E-54、XE2/E-54复合材料体系均表现出明显的导电渗流行为;CB结构对复合材料的导电性能影响较大,F101/E-54、XE2/E-54复合材料体系的导电渗流阈值分别为3.85%、0.47%。     

Dynamic percolation phenomenon of poly(methyl methacrylate)/surface fluorinated carbon black composite

The electrical resistivity of polymer filled with conductive filler, such as carbon black (CB) particles, is greatly decreased by incorporating the conductive filler. This is called the percolation phenomenon and the critical CB concentration is called the percolation threshold concentration (Φ*). For CB particle–filled insulating polymer composite at lower than Φ*, the conductive CB network is constructed in the polymer matrix when the composite is maintained at a temperature higher than the glass‐transition temperature or the melting temperature of the polymer matrix. This phenomenon is called dynamic percolation and the time to reach the substantial decrease in resistivity is called percolation time (t_p). To investigate the relationship between the dynamic percolation process and the surface state of CB particles, we used three kinds of carbon black particles such as original carbon black (CB0) and fluorinated carbon black (FCB010 and FCB025)–filled poly(methyl methacrylate) (PMMA). It was observed that the dynamic percolation curves for CB0‐filled PMMA and FCB‐filled PMMA composites shifted to a shorter percolation time with increases in both the annealing temperature and the filler concentration. However, the dynamic percolation curves of FCB‐filled PMMA showed a gradually decreasing trend compared to that of CB0‐filled PMMA composites. The activation energy calculated from an Arrhenius plot of the t_p against the inverse of the annealing temperature was decreased by surface fluorine treatment. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1151–1155, 2003     

Effect of axial stretching on electrical resistivity of short carbon fibre and carbon black filled conductive rubber composites

The variation of electrical resistivity of carbon black and short carbon fibre (SCF) filled rubber composites was studied against the degree of strain at constant strain rate. It was found that both the degree of strain and strain rate affect the electrical resistivity of the composites. The change in resistivity against the strain and strain rate depends both on the concentration and the type of conductive filler. The incorporation of short carbon fibres (SCF) imparts higher conductivity to the composite than carbon black at the same level of loading. Composites filled with carbon black exhibit better mechanical properties than SCF filled composites. Electrical setting, ie a permanent change in electrical resistivity, was observed during extension–retraction cycles. A good correlation was found between the mechanical response and the electrical response towards strain sensitivity. The results of different experiments are discussed in the light of breakdown and formation of conductive networks in the filled rubber composites. © 2002 Society of Chemical Industry