Effects of layer‐multiplying process on conducting properties of multilayer composites consisting of alternating layers of carbon black/polypropylene and polyamide 6/polypropylene

Composite materials consisting of alternating layers of carbon black/polypropylene (PPCB) and polypropylene (PP) were fabricated by layer‐multiplying coextrusion. A negative effect of the layer‐multiplying process on the conducting percolation of CB in PPCB layers was revealed by electrical resistivity measurements. When polyamide 6 (PA6) was introduced into pure PP layers, the resistivity was less than that of a system without the nylon phase. Morphological and crystalline examinations demonstrated that with increasing the number of layers, PA6 was elongated along the extrusion direction and adhered to by some CB particles. This was considered to be beneficial for the formation of new conducting pathways that compensated for the negative effect of the layer‐multiplying process on conductivity. POLYM. ENG. SCI., 54:1471–1476, 2014. © 2013 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     

Characterization of carbon black‐filled immiscible polypropylene/polystyrene blends

The electrical and rheological behaviors of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) blends were investigated. The compounding sequence influences the phase morphology of the ternary CB/PP/PS composites and the distribution of CB aggregates. Simultaneous measurements of resistance and dynamic modulus were carried out to monitor the phase coalescence of the ternary composites and CB migration and agglomeration in the PS phase during annealing at temperatures above the melting point of PP. The variation of resistivity is mainly attributed to CB agglomeration in the PS phase and the interfacial region, while the variation of dynamic modulus is regarded as the superimposition of the phase coalescence and CB agglomeration in the PS phase. The ternary composites with the majority of CB particles distributed in the interfacial region show the lowest conductive percolation threshold and the most stable resistivity–temperature performance during heating–cooling cycles. Copyright © 2011 Society of Chemical Industry     

Temperature dependence of electrical resistivity for carbon black filled ultra-high molecular weight polyethylene composites prepared by hot compaction

In this article, the temperature dependence of electrical resistivity is studied for carbon black (CB)/ultra-high molecular weight polyethylene (UHMWPE) composites. A new positive temperature coefficient (PTC) material with a very low percolation threshold is produced by the hot compaction method. The very low percolation threshold can be attributed to the segregation of CB in the interfacial regions of UHMWPE particles. The percolation threshold decreases with the increase of the molecular weight of UHMWPE, and with the decrease of the particle size of CB. For CB filled lower molecular weight UHMWPE (145M) composites, the PTC temperature, at which a sharp increase in the resistivity of the composite occurs, decreases with the increase of CB size. However, for a higher molecular weight UHMWPE (630M) filled with CB, the second PTC effect is observed and the negative temperature coefficient (NTC) effect is eliminated. A mechanism is proposed to explain these phenomena based on the optical microscopy and TEM observations. It can be concluded that the degree of the intermixing between CB and UHMWPE particles plays an important role in determining the electrical properties of the composites.     

Special electrical conductivity of carbon black‐filled two‐phased thermoplastic vulcanizates

The electrical properties of carbon black (CB)‐filled two‐phased thermoplastic vulcanizates (based on ethylene‐propylene‐diene copolymer and polypropylene, TPV) were investigated in this article. The results showed that the composites had a singularity in electrical conductivity compared with CB‐filled polypropylene composites. Both the loading of CB and the concentration of rubber phase in TPV had the remarkable effect on electrical property of composites. The rubber particles in TPV presented unique and competitive effects in constructing CB electrical conducting network, namely exclusion and block effects. The percolation threshold value of composites apparently decreased with rubber phase content. However, percolation behavior of composites was weakened when rubber phase content was very high. The percolation behavior of composites with loading of CB is weakened apparently by rubber particles. When annealing the composites in the melt state, the resistance‐time dependence of composites was strongly affected by the pressure of mold annealing. Although air aging had a negligible effect on the electrical properties, the microstructure of the CB/TPV composites had changed during air aging. CB/TPV composite only exhibited the negative temperature coefficient behavior even though the temperature was in the melting region of polypropylene, which was mainly attributed to the exclusive effect brought by the thermal expansion of rubber particles. The special electrical properties of CB/TPV can find potential application in many fields. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrical properties and morphology of carbon black‐filled HDPE/EVA composites

The sensitive effect of weight ratio of the high‐density polyethylene (HDPE)/ethylene‐vinylacetate copolymer (EVA) on the electrical properties of HDPE/EVA/carbon black (CB) composites was investigated. With the EVA content increasing from 0 wt % to 100 wt %, an obvious change of positive temperature coefficient (PTC) curve was observed, and a U‐shaped insulator‐conductor‐insulator transition in HDPE/EVA/CB composites with a CB concentration nearby the percolation threshold was found. The selective location of CB particles in HDPE/EVA blend was analyzed by means of theoretical method and scanning electron micrograph (SEM) in order to explain the U‐shaped insulator‐conductor‐insulator transition, a phenomenon different from double percolation in this composite. The first significant change of the resistivity, an insulator‐conductor transition, occurred when the conductive networks diffused into the whole matrix due to the forming of the conductive networks and the continuous EVA phase. The second time significant change of the resistivity, a conductor‐insulator transition, appeared when the amorphous phase is too large for CB particles to form the conductive networks throughout the whole matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ductile tear behavior of multilayered polypropylene homopolymer/ethylene 1‐octene copolymer sheets

The tear resistance of the polypropylene homopolymer (HPP)/ethylene 1‐octene copolymer (POE) alternating multilayered sheets, which were prepared through multilayered coextrusion, was evaluated. Polarized optical microscope (POM) photographs revealed that HPP and POE layers aligned alternately vertical to the interfaces and continuously parallel to the extrusion direction. Tear results demonstrated the conventional blends had less tear‐resistant than the multilayered samples. Large plastic deformation of HPP layer occurred in the multilayered structure during the stable crack growth, causing the tear energy to increase with the number of layers increasing. The measurements of PCMW2D IR and WAXD revealed that the large plastic deformation had a direct relationship with the crystal structure and termination of micro‐cracks by interface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43298.     

Low percolation threshold and high conductivity in carbon black filled polyethylene and polypropylene composites

High electrically conductive composites have been manufactured using twin and single screw extruders from carbon black with polyolefin. High density, low density polyethylene, polypropylene, polyethylene/polypropylene copolymer, and maleic anhydrite grafted polypropylene have been compounded with three carbon blacks (CBs), i.e., Black Pearl, Printex, and Ketjen, respectively. The lowest percolation threshold (0.8 vol %) for conductive composite was obtained using Ketjen CB blended with high density polyethylene (HD3690, MFI = 36 g/10 min). Polypropylene composites also achieved low percolation thresholds of 1.5 vol % when compounded with Printex or Ketjen CB. Decreasing melt viscosity of polymer matrix resulted in decreasing resistivity of composites. Ketjen CB showed the best conductive behavior for both polyethylene and polypropylene composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Evaluation of the fracture behaviors of multilayered propylene–ethylene copolymer/polypropylene homopolymer composites with the essential work of fracture

As one of the most appropriate techniques for evaluating the fracture behavior, the essential work of fracture (EWF) was introduced to investigate the fracture toughness of multilayered composites. Propylene–ethylene copolymer (CPP)/polypropylene homopolymer (HPP) alternating multilayered composites with 2–128 layers were prepared though multilayered coextrusion. Polarized optical microscopy photographs revealed that the CPP and HPP layers aligned alternately vertical to the interfaces and continuously parallel to the extrusion direction. The dichroic Fourier transform infrared spectroscopy results showed that the coextrusion sheet had a preferential orientation parallel to the melt flow direction (MD); this caused crack propagation along the blunted MD and the necking ligament section. After heat treatment, the orientation parallel to the MD could been largely eliminated, and the crack propagated in a stable manner. The specific essential work of fracture (w_e) of the multilayered composite was higher than that of the blend; this indicated a higher resistance of crack propagation. The number of layers had little effect on the toughness of the multilayered composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40574.     

Carbonaceous fillers for shape memory actuation of polyurethane composites by resistive heating

The effectiveness of carbonaceous, electrically conductive fillers in shape memory actuation of polyurethane composites by resistive heating was evaluated. Specifically, the dependence of electrical resistivity on specimen temperature and imposed tensile strains encountered in shape memory test cycles was determined for shape memory polyurethane (SMPU) composites of carbon nanofiber (CNF), oxidized carbon nanofiber (ox-CNF), and carbon black (CB). The SMPU composites with crystalline soft segments were synthesized from diphenylmethane di-isocyanate, 1,4-butanediol, and poly(caprolactone)diol in a low-shear chaotic mixer and in an internal mixer. The materials synthesized in the chaotic mixer showed higher soft segment crystallinity and lower electrical percolation threshold. A reduction in soft segment crystallinity was observed in the presence of CNF and ox-CNF; the reduction was smaller in the case of ox-CNF. Only the composites of CB showed pronounced positive temperature coefficient (PTC) effects. The observed PTC effects bore a close relationship with non-linear thermal expansion during heating. The composites of CNF and ox-CNF did not show PTC effects due to low levels of soft segment crystallinity. The resistivity of composites of CB increased by several orders of magnitude with imposed tensile strain while composites of CNF and ox-CNF showed weak dependence on strain.     

Electrical behavior and structure of polypropylene/ultrahigh molecular weight polyethylene/carbon black immiscible blends

This study investigates the electrical behavior, which is the positive temperature coefficient/negative temperature coefficient (PTC/NTC), and structure of polypropylene (PP)/ultrahigh molecular weight polyethylene (UHMWPE)/carbon black (CB) and PP/γ irradiated UHMWPE (XL‐UHMWPE)/CB blends. As‐received UHMWPE or XL‐UHMWPE particles are chosen as the dispersed phase because of their unusual structural and rheological properties (extremely high viscosity), which practically prevent CB particles penetration. Because of their stronger affinity to PE, CB particles initially form conductive networks in the UHMWPE phase, followed by distribution in the PP matrix, thus interconnecting the CB‐covered UHMWPE particles. This unusual CB distribution results in a reduced electrical percolation threshold and also a double‐PTC effect. The blends are also investigated as filaments for the effect of shear rate and processing temperature on their electrical properties using a capillary rheometer. Because of the different morphologies of the as‐received and XL‐UHMWPE particles in the filaments, the UHMWPE containing blends exhibit unpredictable resistivities with increasing shear rates, while their XL‐UHMWPE containing counterparts depict more stable trends. The different electrical properties of the produced filaments are also related to differences in the rheological behavior of PP/UHMWPE/CB and PP/XL‐UHMWPE/CB blends. Although the flow mechanism of the former blend is attributed to polymer viscous flow, the latter is attributed to particle slippage effects. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 104–115, 2001     

填充型多相聚合物导电复合材料的PTC效应

以聚丙烯和低密度聚乙烯共混物为基体,用碳黑为填充材料制备了复合导电材料,导电性能的测试表明多相复合体系的渗滤阈值低于两相复合体系的渗滤阈值。对复合材料PTC效应的分析以及对材料的热性能测试结果表明碳黑在共混体系中的分布。同时探讨了体系碳黑含量的变化对PTC效应的影响。     

Electrical properties and morphology of polypropylene/epoxy/glass fiber composites filled with carbon black

The volume resistivity and percolation thresholds of carbon black (CB) filled polypropylene (PP), PP/epoxy, and PP/epoxy/glass fiber (GF) composites were measured. The morphology of these conductive polymer composites was studied with scanning electron microscopy (SEM). The effects of the GF and epoxy contents on the volume resistivity were also investigated. The PP/epoxy/GF/CB composite exhibited a reduced percolation threshold, in comparison with that of the PP/CB and PP/epoxy/CB composites. At a given CB content, the PP/epoxy/GF/CB composite had a lower volume resistivity than the PP/CB and PP/epoxy/CB composites. SEM micrographs showed that CB aggregates formed chainlike structures and dispersed homogeneously within the PP matrix. The addition of the epoxy resin to PP resulted in the preferential location of CB in epoxy, whereas in the PP/epoxy/GF multiphase blends, because of the good affinity of CB to epoxy and of epoxy to GF, CB particles were located in the epoxy phase coated on GF. The decreased percolation threshold and volume resistivity indicated that conductive paths existed in the PP/epoxy/GF/CB composite. The conductive paths were probably formed through the interconnection of GF. Appropriate amounts of GF and epoxy should be used to decrease the volume resistivity and provide sufficient epoxy coating. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1142–1149, 2005     

Morphology and electrical properties of carbon black/poly(ethylene terephthalate)/polypropylene composite

This work attempts to develop a carbon black (CB) filled conductive polymer composite based on poly(ethylene terephthalate) (PET) and polypropylene (PP). The process follows by localizing the CB particles in the minor phase (PET), and then the conductive masterbatch was elongated to form conductive microfibrils in PP matrix during melt extrusion process. After compression molding, a fine conductive three‐dimensional microfibrillar network is constructed. For comparison purpose, CB, PET, and PP are mixed using different pattern. The morphology and the volume resistivity of the obtained composites are evaluated. Electrical conductivity investigation shows that the percolation threshold and resistivity values are dependent on the CB concentration. The best morphological observation shows that the PET phases forms well‐defined microfibrils, and CB particles overwhelmingly localize in the surfaces of the PET microfibrils, which led to a very low percolation threshold, i.e., 4.5 phr, and a reasonable conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of some service conditions on the electrical resistivity of conductive styrene–butadiene rubber–carbon black composites

Conductive polymer composites were prepared using vulcanized styrene–butadiene rubber as a matrix and conductive carbon black as a filler. The filler loading was varied from 10 to 60 phr. The volume resistivity was measured against the loading of the carbon black to verify the percolation limit. The electrical conductivity of filled polymer composites is attributed to the formation of some continuous conductive networks in the polymer matrix. These conductive networks involve specific arrangements of conductive elements (carbon black aggregates) so that the electrical paths are formed for free movement of electrons. The effects of temperature and pressure on the volume resistivity of the composites were studied. The volume resistivity of all the composites increased with increase in temperature, and the rate of increase in the resistivity against temperature depended on the loading of carbon black. The change in volume resistivity during the heating and cooling cycle did not follow the same route, leading to the phenomena of electrical hysteresis and electrical set. It was found that the composites with 40 and 60 phr carbon black become more conductive after undergoing the heat treatment. Generally, all the composites showed a positive temperature coefficient of resistivity. The volume resistivity of all the composites decreased with increase in pressure. The relaxation characteristic of the volume resistivity of the composites was studied with respect to time under a constant load. It was found that the volume resistivity of the compressed specimen of the composites decreased exponentially with time. It was observed that initially a faster relaxation process and later a slower relaxation process occurred in these composites. Some mechanical properties of these composites were also measured to confirm the efficacy of these composites for practical applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2179–2188, 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...     

制备工艺对PTC复合材料阻温特性的影响

研究了密炼工艺对聚乙烯／炭黑复合材料室温电阻率及ＰＴＣ强度的影响,针对一定配方找到了最佳密炼工艺条件。电子束辐照交联能有效消除ＮＴＣ现象和提高材料的电性能循环稳定性,有助于制备低电阻率、高ＰＴＣ强度并具有较好电性能循环稳定及热敏开关特性和电路保护元件。     

Factors influencing the resistivity–temperature behavior of carbon black filled isotactic polypropylene/high density polyethylene composites

The relationship between morphology and resistivity–temperature behavior of carbon black (CB) filled isotactic polypropylene/high density polyethylene (iPP/HDPE) composites was investigated. The positive temperature coefficient intensity for all composites studied in this paper was lower than one and the negative temperature coefficient (NTC) effect was obvious. The factors influencing resistivity–temperature behavior include the CB contents, types of the polymer matrices and their composition, which determine the phase morphology and thus the conductive network. The types of iPP and HDPE influenced the NTC effect, while the morphology of the composites mainly influenced the initial volume resistivity of the composites.     

Deformation mechanisms of polypropylene/polystyrene multilayered films

Multilayered composites of polypropylene (PP) and polystyrene (PS) fabricated by a layer‐multiplying coextrusion technique are described. The aim of this investigation was to find a correlation between the morphology and the mechanical and micromechanical deformation behavior. The multilayered films had primarily continuous layers, exhibiting only few defects in layer construction and turning into an irregularly layered system when the calculated layer thickness was only 5 nm. The morphology and layer thickness of both the PP and PS layers affected the mechanical and the micromechanical behavior, which was brittle for the films having PS layers thicker than 75 nm and ductile when the PS layers were 50 nm and thinner. Transmission electron microscopy showed crazes in the thicker PS layers and homogeneous deformation in the thinner ones. The molecular orientation during deformation of the ductile films was calculated from rheo‐optical measurements with Fourier transform infrared spectroscopy. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012