Melt spinning of β‐phase poly(vinylidene fluoride) yarns with and without a conductive core

When poly(vinylidene fluoride) (PVDF) is to be used as a piezoelectric material, the processing must include the formation of polar β‐phase crystallites, as well as the application of electrically conducting charge collectors, that is, electrodes. In this article, results from the melt spinning of PVDF yarns and a novel bicomponent PVDF‐yarn with a conductive carbon black/polypropylene (CB/PP) core are presented. Melt spinning has been done under conditions typical for industrial large‐scale fiber production. The effects on the resulting crystalline structure of varying the spinning velocity, draw rate, and draw temperature are discussed. The results show that, for maximum α‐to‐β phase transformation, cold drawing should take place at a temperature between 70 and 90°C, and both the draw ratio and the draw rate should be as high as possible. It was observed that the cold drawing necessary to form β‐phase crystallinity simultaneously leads to a decrease in the core conductivity of the bicomponent yarns. In this work, the melt spinning of bicomponent fibers with high‐β‐phase PVDF in the sheath and a CB/PP core was successfully accomplished. The core material remained electrically conductive, paving the way for the use of a CB‐polymer compound as inner electrode in the melt spinning of piezoelectric bicomponent fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Conducting bicomponent fibers obtained by melt spinning of PA6 and polyolefins containing high amounts of carbonaceous fillers

Melt spinning of conductive polymer composites (CPCs) is coupled with some difficulties such as a decrease of conductivity upon drawing and a reduced spinnability with increasing filler concentration. Applying bicomponent technology may provide the possibility to produce fibers from CPCs with a high filler concentration. A pilot‐scale bicomponent melt spinning set‐up was used to produce core/sheath fibers with fiber titers between 13 and 47 dtex. The sheath material was polyamide 6 (PA6) or polypropylene (PP) and the core material was a CPC. Two CPCs were used, polypropylene (PP) with carbon black (CB), denoted by PP/CB, and polyethylene (PE) with multiwalled carbon nanotubes (MWNT), denoted by PE/MWNT. The results showed that both materials could be used with a filler concentration of 10 wt % to obtain melt draw ratios up to 195. The volumetric fraction of core material in the bicomponent structure was 28%. A heat treatment of PP/CB fibers restored the conductivity to the level of the undrawn material, corresponding to an increase in conductivity by a factor 5. The same heat treatment had a positive effect on the conductivity of PE/MWNT fibers although the conductivity was not restored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the morphology and temperature-resistivity effect of injection-molded iPP/HDPE/CB composites

The relationship between morphology and temperature-resistivity effect of injection-molded isotactic polypropylene/high density polyethylene/carbon black (iPP/HDPE/CB) composites with special orientation structure is investigated in detail. The morphological variation induced by melting, disorientation, crystallization and movement of CB particles is responsible for the change of electrical conductivity of the iPP/HDPE/CB composites during the heating and cooling. The room temperature volume resistivity of the composites reduces markedly after a round of heating and cooling because the network is improved through morphological changes and movement of particles during annealing. The continuity of HDPE/CB phase and the effective concentration of the CB particles in HDPE simultaneously determine the temperature-resistivity effects of the composites. Samples with iPP/HDPE mass ratio of 50/50 achieve a better balance of the two factors, which results in more stable conductive properties varying with temperature.     

Multiple percolation in a carbon‐filled polymer composites via foaming

This article describes an investigation into the effects of foaming on the electrical conductivity for a carbon‐filled cyclic olefin copolymer (COC) composite incorporating both chopped carbon fibers (cCF) and carbon black (CB). Foamed and solid samples were injection molded and then analyzed for cell size, fiber length, fiber orientation, and electrical conductivity. Foamed samples exhibited higher electrical conductivity in the through‐plane direction for materials containing only CB or composites containing both filler types, and reduced electrical conductivity in the cCF‐filled composites. The increased electrical property gained by foaming was attributed to multiple percolation with CB aggregates forming more effective conductive clusters and networks in the continuous polymer phase during growth of the gas domains. A mechanism for the phenomenon was proposed based on these experimental observations. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Insert injection molding of high‐density polyethylene single‐polymer composites

A process for making high‐density polyethylene (HDPE) single‐polymer composites (SPCs) by insert injection molding was investigated. HDPE SPCs with relatively good tensile and interfacial properties were prepared within a short cycle time within a temperature range of 40°C. Melt‐spun HDPE fibers were made from the same resin as the matrix. The fibers were heat treated in silicone oil, with and without tension, to study the changes of fiber properties upon exposure to high temperature. HDPE SPCs containing about 30 wt% lab‐made HDPE fabric achieved a tensile strength of 50 MPa, 2.8 times that of neat HDPE. The peel strength of HDPE SPCs increased with increasing injection temperature and achieved a maximum value of 16.7 N/cm. Optical micrographs of polished transverse cross‐sections of the SPC samples showed that higher injection temperature is beneficial to the wetting and permeation properties of the matrix. Scanning electronic microscope photographs suggested good bonding and compatibility between the fibers and the matrix. POLYM. ENG. SCI., 55:2448–2456, 2015. © 2015 Society of Plastics Engineers     

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.     

Melt spinning of conductive textile fibers with hybridized graphite nanoplatelets and carbon black filler

In this study, two different carbon fillers: carbon black (CB) and graphite nanoplatelets (GNP) are studied as conductive fillers for the preparation of conductive polypropylene (PP) nanocomposites. In order to obtain a homogenous dispersion of GNP, GNP/PP composites were prepared by two different methods: solid state mixing (SSM) and traditional melt mixing (MM). The result shows that MM is more efficient in the dispersion of GNP particles compared to SSM method. PP nanocomposites containing only one conductive filler and two fillers were prepared at different filler concentrations. Based on the analysis of electrical and rheological properties of the prepared nanocomposites, it shows that a hybridized composite with equal amounts of GNP and CB has favorable processing properties. Conductive fibers with a core/sheath structure were produced on a bicomponent melt spinning line. The core materials of these fibers are the hybridized GNP/CB/PP nanocomposite and the sheath is pure polyamide. It was found that GNPs were separated during melt and cold drawing which results in the decrease of conductivity. However, the conductivity could partly be restored by the heat treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2579–2587, 2013     

Preparation and characterization of isotactic polypropylene/high‐density polyethylene/carbon black conductive films with strain‐sensing behavior

Novel conductive films with a unique strain (ε)‐sensing behavior and based on a blend of isotactic polypropylene (iPP), high‐density polyethylene (HDPE), and carbon black (CB) were fabricated by an extrusion casting method. The morphology and ε‐sensing behavior of the films were investigated. Scanning electron microscope images showed that the oriented lamellae with a growing direction perpendicular to the extrusion direction were obtained in the HDPE phase and were accompanied by a cocontinuous structure of the iPP phase and HDPE/CB phase. The conductive percolation threshold (m_c) and resistivity–ε behavior of the thin films are affected by the drawing ratio during the process of film preparation. The m_c and electrical resistance of the iPP/HDPE/CB composite films increased with the drawing ratio. The gauge factor of the films within the elastic region decreased with increasing drawing ratio. Furthermore, the result of iPP/(HDPE/CB) 40/60 with a high drawing ratio shows that a reversible conductivity was obtained during the cyclic tensile testing (ε = 10%), but an irreversible conductivity makes the film fail during use at the applied ε values of up to 15%. This makes them good piezoresistive candidates for ε‐sensing materials. Moreover, a simple structural model was proposed to describe the reversible and irreversible phenomena in the electrical resistance behavior of the iPP/HDPE/CB films under tensile loading. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40686.     

Mechanical and thermo‐physical properties of high‐density polyethylene modified with talc

The aim of this study was to examine the physical, mechanical, and thermo‐physical properties of high‐density polyethylene (HDPE) modified with talc. Different weight fractions of talc (up to 35 wt %) were compounded with an HDPE matrix containing 2.5 wt % of carbon black (CB) in a twin‐screw compounder. The composites were then processed by injection moulding to obtain specimens for testing. The results indicate that CB causes a significant decrease in the toughness, while talc not only enhances the thermal conductivity and thermo‐physical properties of the composites but can also play a role in compensating for the negative effects of CB on impact resistance. The experimental data show that the presence of CB reduces the impact resistance of HDPE by up to 34%, while addition of up to 8 wt % talc can return this value to close to that of pure HDPE. No significant effect on the composite tensile yield and fracture strength was observed for either component at all concentrations. The thermal conductivity, thermal diffusivity, and specific density values of the composites increased almost linearly, but the increase in moisture absorption in the long term showed nonlinear behavior in the concentration range of the experiment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electric self‐heating behavior of acetylene carbon black filled high‐density polyethylene composites

The electric self‐heating behavior of carbon black (CB) filled high‐density polyethylene (HDPE) was studied in relation to the time‐dependent current and surface temperature under various voltages and to the voltage‐dependent surface temperature at electric–thermal equilibrium. The resistance increase due to self‐heating restricts the current flow through the sample and thus stabilizes the electric power and the self‐heating temperature to their saturation values, which vary with the voltage. A simple phenomenological model shows that self‐heating at electric‐thermal equilibrium is involved in the initial resistance, the electric field induced positive temperature coefficient (PTC) transition and the heat dissipation. The influences of annealing and irradiation crosslinking on the self‐heating behavior are discussed. Copyright © 2004 Society of Chemical Industry     

Improvement of melt spinning properties and conductivity of immiscible polypropylene/polystyrene blends containing carbon black by addition of styrene‐ethylene‐butene‐styrene block copolymer

Conducting polymeric materials prepared from immiscible blends, such as polypropylene (PP)/polystyrene (PS), together with carbon black (CB), are known to have a relatively high electrical conductivity, because of a selective distribution of CB (double percolation). Melt spinning of immiscible blends containing CB has, however, not been extensively reported on previously. An immiscible 1:1 blend of PP and PS to which 4 wt% CB was added exhibited a very low melt draw‐down ratio at rupture compared wit PP with the same content of CB. By adding 5 wt% SEBS (styrene‐ethylene‐butene‐styrene block copolymer), the ultimate melt draw‐down ratio increased about 10 times, which made the material more suitable for melt spinning. As‐extruded samples of the immiscible blends (with CB) did not have higher electrical conductivities than PP/CB. A heat treatment increased the conductivity of immiscible PP/PS/CB composites, and longer treatment times and higher temperatures promoted the conductivity. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

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     

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     

Investigation of electrically conductive acrylonitrile‐butadiene rubber

Electrically conductive acrylonitrile‐butadiene rubbers (NBRs) containing carbon black (CB) as conductive filler were prepared in order to investigate their electrical and mechanical properties. The effects of conductive CB loading, temperature, acrylonitrile content, crosslinking density of vulcanizates, and plasticizer on conductivity were studied. The change in electrical conductivity of NBRs with different amounts of CB showed that there is a certain critical point (percolation threshold) where a significant decrease in electrical resistivity (increase in conductivity) is observed. Mechanical properties such as tensile strength, elongation to break, and surface hardness of vulcanized NBRs were measured. It was found that the percolation threshold was 5 phr of CB for the NBR/CB composites. J. VINYL ADDIT. TECHNOL., 13:71–75, 2007. © 2007 Society of Plastics Engineers.     

HDPE/CB复合体系PTC行为的工艺研究

采用高结构导电炭黑(CB)Vxc—72与半晶聚合物高密度聚乙烯(HDPE)进行熔融共混，制备复合型导电高分子材料。研究了该复合体系中偶联处理、混炼时间、辐射及退火处理等工艺因素对其PTC(电阻—温度效应)性能的影响。结果表明，当辐照剂量为140—160kGy、炭黑非均匀分散且进行退火处理时复合体系具有最佳的PTC性能，但混炼时间过长、偶联处理均会使复合体系PTC强度降低。     

复合型PE自限温发热材料的形态及电热特性

研究了炭黑的含量对复合型聚乙烯自限温发热材料发热行为的影响,发现发热温度最高的发热材料的炭黑含量即为导电渗流区上限的含量。采用透射电子显微镜、扫描电子显微镜分别表征了炭黑的微观形态及其发热材料的微观网状结构。将材料的渗滤行为、发热特性以及特定的网状结构形态进行了关联。结果表明,这种由颗粒构成的网状结构既具有优异的导电性,又保持了良好的力学性能,     

Synergistic effect of boron nitride and tetrapod‐shaped zinc oxide whisker hybrid fillers on filler networks in thermal conductive HDPE composites

In this paper, in order to investigate and predict the synergistic effect of the tetra‐needle‐shaped zinc oxide whisker (T‐ZnO) and boron nitride (BN) hybrid fillers in the thermal conductive high‐density polyethylene (HDPE) composites, the filler networks were studied through dynamic rheological measurement. Moreover, the crystallinity of the HDPE in the composites, and the thermal and electrical conductivity of the composites were also investigated. It was found that when the ratio of the BN and T‐ZnO in hybrid fillers was 20:10, the HDPE/hybrid fillers composite not only had the highest thermal conductivity but also can maintain the electrically insulating. Furthermore, the gel point of the HDPE/hybrid fillers composites was 11.2 wt%, and it was close to the 10 wt%. Therefore, the synergistic effect of the T‐ZnO and BN hybrid fillers in the HDPE/hybrid fillers composites can be successfully predicted through dynamic rheology date. Simultaneously, the Scanning electron microscope results showed that the T‐ZnO and BN particles can contact each other to form the thermal conductive paths so that the thermal conductivity of the HDPE can be enhanced through addition of the hybrid fillers. In addition, it was also found that the improved thermal conductivity of the HDPE/hybrid fillers composites was not because of a change in the crystallinity of the HDPE in the HDPE/hybrid fillers composites. POLYM. COMPOS., 38:1902–1909, 2017. © 2015 Society of Plastics Engineers     

Dispersion and resistivity optimization of conductive carbon black in environment‐friendly conductive coating based on acrylic resin

A designated chemical structure, determined through the analysis of elements and groups on the surface of conductive carbon black (CB), alcohol‐soluble acrylic resin used for dispersion of conductive CB was successfully prepared based on the principles of similar structure complex well. The content of acrylic acid, glass transition temperature (T_g), molecular weight (M_w), self‐crosslinking degree, and N‐hydroxymethyl acrylamide content were investigated to optimize the electrical conductivity and dispersion effect of conductive CB in coating. The composites of acrylic resin and conductive CB were characterized by X‐ray photoelectron spectroscopy for surface chemical structure on CB, scanning electron microscopy for morphology of conductive coating, Fourier transform infrared for groups in acrylic resin, and digital multimeter techniques for surface resistivity of conductive coating. The optimum surface resistivity of the acquired conductive coating could reach 600 ohm/sq, showing an excellent conductive property. Moreover, the conductive coating still maintained a lower resistivity after salt spray and weather resistance test. POLYM. COMPOS. 36:467–474, 2015. © 2014 Society of Plastics Engineers     

Effect of the carbon black structure on the stability and efficiency of the conductive network in polyethylene composites

Composites of high‐density polyethylene (HDPE) with different kinds of carbon black (CB) were prepared through melt blending. The influence of the CB structure on the stability and efficiency of the conductive network in HDPE/CB composites were mainly investigated. Scanning electron microscopy was used to observe the morphology of the CB primary aggregates. The relationship between the temperature‐resistivity behaviors of the composites and the crystallization behaviors of the matrix were also investigated. High‐structure CB built an effective conductive network at a low filler content compared to the low‐structure one because of its branched morphology. Therefore, the composite containing high‐structure CB revealed a lower percolation threshold. The composite containing low‐structure CB obtained a stronger positive temperature coefficient (PTC) intensity because the cluster network was fragile and easily damaged during matrix melting. The reproducibility of the results of PTC effect of the composite containing high‐structure CB was better than that of the composite containing a low‐structure one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013