Development of an additive equation for predicting the electrical conductivity of carbon‐filled composites

The electrical conductivity of polymeric materials can be increased by the addition of carbon fillers. The resulting composites can be used in applications such as electrostatic dissipation and interference shielding. Electrical conductivity models are often proposed to predict the conductivity behavior of these materials. The electrical conductivity of carbon‐filled polymers was studied here by the addition of three single fillers to nylon 6,6 and polycarbonate in increasing concentrations. The fillers used in this project were carbon black, synthetic‐graphite particles, and milled pitch‐based carbon fibers. Materials were extruded and injection‐molded into test specimens, and then the electrical conductivity was measured. Additional material characterization tests included optical microscopy for determining the filler aspect ratio and orientation. The filler and matrix surface energies were also determined. An updated model developed by Mamunya and others and a new additive model (including the constituent conductivities, filler volume fraction, percolation threshold, constituent surface energies, filler aspect ratio, and filler orientation) fit the electrical conductivity results well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2280–2299, 2003     

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     

Effects of multiple carbon fillers on the rheology of polycarbonate‐based composites

Adding conductive carbon fillers to insulating thermoplastic polymers increases the electrical conductivity of the resulting composite, which could allow them to be used in electrostatic dissipative and semiconductive applications. Adding fillers often increases viscosity, which can make the material more difficult to process. In this study, three different carbon fillers [carbon black (CB), carbon nanotubes (CNT), and exfoliated graphite nanoplatelets (GNP)] were studied via three different combinations of two different fillers (CB/CNT, CB/GNP, and CNT/GNP). These filler combinations were studied via three 3² factorial designs, which considered the following loading levels: CB: 0, 2, and 5 wt%; CNT: 0, 1, and 5 wt%; and GNP: 0, 2, and 5 wt%. These composites were compounded, injection molded, and tested for electrical conductivity and steady shear viscosity. CB and GNP exhibited classic filler behavior, increasing the composite viscosity with increased filler loading. CNT acted differently, lowering the composite viscosity with increased filler loading. When CB and GNP were combined, the viscosity increase was additive. When CNT was combined with either CB or GNP, the resultant composite had a lower viscosity than the corresponding single filler composite with equivalent loadings of CB or GNP. This viscosity lowering effect of CNT, even at loadings as low as 1 wt%, allows for increased filler loadings of CB or GNP with little impact on processability. Five different formulations (four containing two filler combinations) could be used for electrostatic dissipative applications and seven different formulations (six containing two filler combinations) may be used for semiconductive applications. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Thermoset/graphene polymer composites—A review of processing and properties

Polymer-carbon nanocomposites incorporate the exceptional properties of both the polymer matrices, such as low cost and simple processing, with the distinctive features of the carbon-based fillers, such as high electrical and thermal conductivities, and excellent mechanical properties. Various fillers like carbon black (CB), graphite, expanded graphite (EG), and carbon nanotubes (CNTs) are being used to produce materials with advanced properties. However, at high filler loading, these filler materials have some major challenges such as filler agglomeration. Recently, graphene has gained increased interest as an alternative filler to produce polymer nanocomposites with advanced characteristics. Thermosetting polymer composites with graphene fillers are being considered for multiple applications and are a subject of interest for researchers because of enhanced properties like excellent corrosion resistance and low density. This review outlines studies to improve the mechanical, electrical, and thermal properties of thermoset/graphene composites.     

复合填料/聚丙烯酸酯导电压敏胶的制备与性能

针对导电胶黏剂（ECA）在实用中所遇到填料组分单一、易团聚、对基体力学性能影响较大等问题,本文利用不同组分填料间的架桥、插层等“协同”效应,将一定比例的碳黑（CB）、碳纤维（CF）、碳纳米管（CNTs）、纳米石墨微片（NanoG）复合作为导电填料加入到聚丙烯酸酯压敏胶（PSA）中,采用溶液共混法超声分散,得到填料添加量小、导电性能和力学性能良好的导电PSA。运用多种检测手段对导电PSA的电学性质、微观结构、热稳定性和力学性能进行了分析。结果表明,复合填料组成为CF 3%、NanoG 5%、CNTs 5%（均为质量分数）时,导电PSA的电导率达到3.0×10?2S/cm,180°剥离强度为0.38kN/m。     

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     

Investigation of the conductivity of asphalt concrete containing conductive fillers

Carbon black, graphite and carbon fibre were employed to design and prepare electrically conductive asphalt mixtures containing single filler or mixed fillers of conductive powder plus carbon fibre. The effects of filler type, filler content and mixed fillers on the resistivity of asphalt concrete were investigated. Experimental results showed that the insulating-conductive percolation transition of the resistivity under the function of filler content appears in the single-filler composites and the percolation threshold is approximately 12%, 10%, and 5% by volume percentage of the binder phase for carbon black, graphite and carbon fibre respectively. The combination function of mixed fillers has appreciable advantages over single powder filler, but no obvious advantages over simple fiber in the conductivity improvement at the same total filler content. But the addition of small amounts of expensive fibers to larger amounts of cheaper CB or graphite can be a cost effective system. Scanning electron microscope images provide insight into the mechanisms of conductivity enhancement for mixed fillers. Conductive filler particles exhibit the short-range contacts or connections in asphalt concrete, whereas carbon fibres exhibit a long-range conductive bridging effect and short-circuit effect because of the high aspect ratio.     

Processing,structure, and properties of gel spun PAN and PAN/CNT fibers and gel spun PAN based carbon fibers

Polyacrylonitrile (PAN) and PAN/carbon nanotube (PAN/CNT) fibers were manufactured through dry‐jet wet spinning and gel spinning. Fiber coagulation occurred in a solvent‐free or solvent/nonsolvent coagulation bath mixture with temperatures ranging from ?50 to 25°C. The effect of fiber processing conditions was studied to understand their effect on the as‐spun fiber cross‐sectional shape, as well as the as‐spun fiber morphology. Increased coagulation bath temperature and a higher concentration of solvent in the coagulation bath medium resulted in more circular fibers and smoother fiber surface. as‐spun fibers were then drawn to investigate the relationship between as‐spun fiber processing conditions and the drawn precursor fiber structure and mechanical properties. PAN precursor fiber tows were then stabilized and carbonized in a continuous process for the manufacture of PAN based carbon fibers. Carbon fibers with tensile strengths as high as 5.8 GPa and tensile modulus as high as 375 GPa were produced. The highest strength PAN based carbon fibers were manufactured from as‐spun fibers with an irregular cross‐sectional shape produced using a ?50°C methanol coagulation bath, and exhibited a 61% increase in carbon fiber tensile strength as compared to the carbon fibers manufactured with a circular cross‐section. POLYM. ENG. SCI., 55:2603–2614, 2015. © 2015 Society of Plastics Engineers     

Effects of the coagulation temperature on the properties of wet‐spun poly(vinyl alcohol)–graphene oxide fibers

Graphene oxide (GO) as a positive reinforcement filler was dispersed into a poly(vinyl alcohol) (PVA) dope and wet‐spun into composite fibers. The effects of two EtOH coagulation baths maintained at ?5 and 25 °C, respectively, on the morphology, structure, and mechanical properties of the composite fibers were investigated. The results show that gel spinning at ?5 °C led to a relatively large shrinkage ratio, thin diameter, and low porosity of the as‐spun fibers. Simultaneously, the low coagulation temperature also greatly contributed to the formation and preservation of the liquid‐crystalline phase of the GO sheets and interrupted the crystalline zone of PVA less. As a result, either the tenacity or the elongation at break of the fibers spun at ?5 °C was higher than those of the fibers spun through a coagulation bath at 25 °C. In particular, 1 wt % GO showed the highest reinforcement effects among all of the wet‐spun composite fibers. Hence, controlling the gelling–demixing process at a low temperature will provide more instructive insights for tailoring functional industrial textiles with excellent mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45463.     

Effect of carbon nanoparticle type,content, and stress on piezoresistive polyethylene nanocomposites

This study examines the piezoresistive behavior of polyethylene (PE) composites containing different types of carbon nanoparticle fillers. The fillers investigated are single‐wall carbon nanotube (SWCNT), multi‐wall carbon nanotube (MWCNT), and graphene nanoplatelets (GNP), which were dispersed in PE through melt blending in concentrations ranging between 0.5 and 10 wt%. The dispersion and nanocomposite morphology were investigated using scanning electron microscopy and X‐ray diffraction with strong evidence found for shear‐induced orientation of GNP nanoparticles during the compression molding process. The conductivity and permittivity of the composite materials was investigated using impedance spectroscopy and the lowest percolation threshold and highest electrical conductivity was observed for SWCNT composites, followed by MWCNT and GNP. The compressive piezoresistance of the nanocomposites was measured and the initial, elastic, and plastic deformation regions were all identifiable by the resistance measurements. The main finding of this study is that the piezoresistance of MWCNT nanocomposites is more sensitive to the effects of varying stress and composition than SWCNT nanocomposites. This indicates an evolving filler network in the case for MWCNT, while a static network for SWCNT, which is explained by the higher aspect ratio and surface area of the latter. POLYM. ENG. SCI., 55:1643–1651, 2015. © 2014 Society of Plastics Engineers     

Synergistic effect of carbon fillers in electrically conductive nylon 6,6 and polycarbonate based resins

The electrical conductivity of polymeric materials can be increased by the addition of carbon fillers, such as carbon fibers, carbon black, and synthetic graphite. The resulting composites could be used in applications such as electromagnetic and radio frequency interference shielding and electrostatic dissipation. A significant amount of work has been conducted varying the amount of single conductive fillers in a composite material. In contrast, very limited work has been conducted concerning the effect of combinations of various types of conductive fillers. In this study, three different carbon fillers were used: carbon black, synthetic graphite pareticles, and pitch based carbon fiber. Two different polymers were used: nylon 6,6 and polycarbonate. The goal of this project was to determine the effect of each filler and combinations of different fillers on the electrical conductivity of conductive resins. A 2³ factorial design was analyzed to determine the effects of the three different carbon fillers in nylon 6,6 and polycarbonate. The results showed that carbon black caused the largest increase in composite electrical conductivity. The factorial design analysis also showed that combinations of different carbon fillers do have a positive synergistic effect, thereby increasing the composite electrical conductivity.     

Mechanochemical Routes to Functionalized Graphene Nanofillers Tuned for Lightweight Carbon/Hydrocarbon Composites

Graphite exfoliation by shear‐induced dry and wet processes and especially mechanochemistry represent attractive routes to carbon nanofillers. Dry ball‐milling of graphite in a planetary mill under gas pressure is a scalable and environmentally benign one‐step process, which requires neither hazardous solvents nor tedious separate functionalization and purification steps. Gas type, pressure, and milling duration govern average particle size, shape, and functionalization. Ball‐milling under Ar yields hydroxylated spherical carbon particle agglomerates, whereas ball‐milling under CO₂ affords functionalized nanoplatelets without encountering agglomeration problems and highly exothermic post‐milling reactions with air. The carboxylation of graphene nanoplatelets enhances their dispersibility in various media including polypropylene (PP) even in the absence of compatibilizers. Large amounts of carboxylated nanoplatelets are dispersed in PP without massive viscosity build‐up. Functionalized carbon nanoplatelet fillers enable tailoring of recyclable lightweight carbon/hydrocarbon composites exhibiting an improved balance of stiffness, strength, toughness, electrical, and thermal conductivity.     

Electrical conductivity of carbon‐filled polypropylene‐based resins

Adding conductive carbon fillers to insulating thermoplastic resins increases composite electrical conductivity. Often, as much of a single type of carbon filler is added to achieve the desired conductivity and still allow the material to be molded into a bipolar plate for a fuel cell. In this study, various amounts of three different carbons (carbon black, synthetic graphite particles, and carbon nanotubes) were added to polypropylene resin. The resulting single‐filler composites were tested for electrical resistivity (1/electrical conductivity). The effects of single fillers and combinations of the different carbon fillers were studied via a factorial design. The percolation threshold was 1.4 vol % for the composites containing only carbon black, 2.1 vol % for those containing only carbon nanotubes, and 13 vol % for those containing only synthetic graphite particles. The factorial results indicate that the composites containing only single fillers (synthetic graphite followed closely by carbon nanotubes and then carbon black) caused a statistically significant decrease in composite electrical resistivity. All of the composites containing combinations of different fillers had a statistically significant effect that increased the electrical resistivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hybridized reinforcement of natural rubber with silane‐modified short cellulose fibers and silica

Natural‐rubber‐based hybrid composites were prepared by the mixture of short cellulose fibers and silica of different relative contents with a 20‐phr filler loading with a laboratory two‐roll mill. The processability and tensile properties of the hybrid composites were analyzed. The tensile modulus improved, but the tensile strength and elongation at break decreased with increasing cellulose fiber content. The scorch safety improved with the addition of 5‐phr cellulose fiber in the composites. The Mooney viscosity significantly decreased with increasing cellulose fiber content. To modify the surface properties of the cellulose fiber and silica fillers, a silane coupling agent [bis(triethoxysilylpropyl)tetrasulfide, or Si69] was used. The effects of Si69 treatment on the processing and tensile properties of the hybrid composites were assessed. We found that the silane treatment of both fillers had significant benefits on the processability but little benefit on the rubber reinforcement. The strength of the treated hybrid composite was comparable to that of silica‐reinforced natural rubber. Furthermore, to investigate the filler surface modification and to determine the mixing effects, infrared spectroscopic and various microscopic techniques, respectively, were used. From these results, we concluded that the fillers were better dispersed in the composites, and the compatibility of the fillers and natural rubber increased with silane treatment. In conclusion, the hybridized use of short cellulose fibers from a renewable resource and silica with Si69 presented in this article offers practical benefits for the production of rubber‐based composites having greater processability and more environmental compatibility than conventional silica‐filler‐reinforced rubber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reinforcement of acrylonitrile butadiene rubber using pristine few layer graphene and its hybrid fillers

Unfunctionalized few layer graphene (FLG) nanoplatelets were mixed with acrylonitrile butadiene rubber (NBR) by melt mixing and the properties were compared with composites containing carbon black alone and a 1:1 mixture of FLG and carbon black. Incorporation of a very small amount of FLG significantly improved the cure characteristics of NBR. Compared to graphene, similar loading of carbon black gave higher rheometer torque at the expense of scorch safety whereas hybrid filler gave optimum cure characteristics. There was more than 190% improvement in tensile strength when 5 phr FLG was added to the matrix. On the other hand, to achieve the same strength, five times more of carbon black was needed compared to FLG. In contrast to carbon black, FLG increased the compression set of the rubber. The compositions containing 1:1 mixture of the fillers displayed compression set values in between those containing FLG or carbon black alone. The storage modulus was also found to be optimum for the composites containing equal amounts of FLG and carbon black. FLG loaded composites displayed significant reduction in the creep compliance. Additionally, the helium leak rate of the composites was decreased in presence of FLG due to its platelet structure.     

Novel electrospun polymer electrolytes incorporated with Keggin‐type hetero polyoxometalate fillers as solvent‐free electrolytes for lithium ion batteries

In this study, solvent‐free nanofibrous electrolytes were fabricated through an electrospinning method. Polyethylene oxide (PEO), lithium perchlorate and ethylene carbonate were used as polymer matrix, salt and plasticizer respectively in the electrolyte structures. Keggin‐type hetero polyoxometalate (Cu‐POM@Ru‐rGO, Ni‐POM@Ru‐rGO and Co‐POM@Ru‐rGO (POM, polyoxometalate; rGO, reduced graphene oxide)) nanoparticles were synthesized and inserted into the PEO‐based nanofibrous electrolytes. TEM and SEM analyses were carried out for further evaluation of the synthesized filler structures and the electrospun nanofibre morphologies. The fractions of free ions and crystalline phases of the as‐spun electrolytes were estimated by obtaining Fourier transform infrared and XRD spectra, respectively. The results showed a significant improvement in the ionic conductivity of the nanofibrous electrolytes by increasing filler concentrations. The highest ionic conductivity of 0.28 mS cm^?1 was obtained by the introduction of 0.49 wt% Co‐POM@Ru‐rGO into the electrospun electrolyte at ambient temperature. Compared with solution‐cast polymeric electrolytes, the electrospun electrolytes present superior ionic conductivity. Moreover, the cycle stability of the as‐spun electrolytes was clearly improved by the addition of fillers. Furthermore, the mechanical strength was enhanced with the insertion of 0.07 wt% fillers to the electrospun electrolytes. The results implied that the prepared nanofibres are good candidates as solvent‐free electrolytes for lithium ion batteries. © 2020 Society of Chemical Industry     

Effects of filler geometry on internal structure and physical properties of polycarbonate composites prepared with various carbon fillers

BACKGROUND: The effects of filler geometry are important for understanding the internal structure and physical properties of polymer composites. To investigate the effects of filler geometry on electrical conductivity as well as morphological and rheological properties, three types of polycarbonate (PC) composites were prepared by melt compounding with a twin‐screw extruder. RESULTS: The electrical conductivity of PC/carbon black (CB) and PC/graphite (carbon) nanofibre (CNF) composites did not show a percolation threshold through the entire filler loading ranges. However, PC‐blend‐carbon nanotube (CNT) composites showed a percolation electrical threshold for a filler loading of 1.0 to 3.0 wt% and their maximum electrical conductivity approached 10^?3 S m^?1. PC‐blend‐CB and PC‐blend‐CNF composites showed Newtonian behaviour like pure PC matrix, but PC‐blend‐CNT composites showed yield stress as well as increased storage modulus and strong shear thinning behaviour at low angular frequency and shear rate due to strong interactions generated between CNT–CNT particles as well as PC molecules and CNT particles on the nanometre scale. CONCLUSIONS: The electrical conductivity of the PC composites with different carbon constituents was well explained by the continuous network structure formed between filler particles. The network structure was confirmed by the good dispersion of fillers as well as by the yield stress and solid‐like behaviour observed in steady and dynamic shear flows. Copyright © 2009 Society of Chemical Industry     

Improving the thermal conductivity and shape-stabilization of phase change materials using nanographite additives

Improvements in the thermal conductivity and shape-stability of paraffin phase change materials (PCMs) by adding exfoliated graphite nanoplatelets (xGnP) or graphene were compared. The composite PCMs were fabricated by mixing paraffin with xGnP or graphene in hot toluene, followed by solvent evaporation and vacuum drying. A larger increase in thermal conductivity was observed for paraffin/xGnP, with a 10 wt.% xGnP loading producing a more than 10-fold increase. Graphene shows a lower electrical percolation threshold and offers a much larger increase in the electrical conductivity of paraffin than xGnP. However, its thermal conductivity increase is much lower. Despite the excellent thermal conductivity of single-flake graphene, the large density of nanointerfaces due to the small size of the graphene flakes significantly impedes heat transfer. We also found that graphene is much more effective than xGnP as a shape-stabilizing filler. At 2 wt.% graphene loading, paraffin maintains its shape up to 185.2 °C, well above the operating temperature range of paraffin PCMs, while the paraffin/xGnP counterpart is shape-stable up to 67.0 °C only. Small amounts of graphene and xGnP can be used in combination as a low-cost and effective improver for both the heat diffusion and shape-stabilization of paraffin PCMs.     

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     

Electrical and mechanical properties of melamine‐formaldehyde–based laminates with shungite filler

Processing issues and the electrical and mechanical properties of a novel combination of a natural carbonaceous filler, Karelian shungite, and a water soluble thermosetting polymer, melamine‐formaldehyde, were investigated. Two types of shungite with different carbon contents were investigated and compared to a commercial carbon black. The larger particle size and chemically more active surface of the shungites compared to carbon black leads to easy handling with little dusting and allows water to be used as dispersant. Laminates of melamine‐formaldehyde reinforced with random cellulose fibers and filler were prepared by film stacking. The layered structure results in anisotropic resistivities for the shungites with fairly low in‐plane percolation thresholds and a dissipative resistivity above the percolation transition. In comparison, carbon black had a lower percolation threshold and a low isotropic resistivity above the percolation transition. The mechanical properties of the composites were slightly deteriorated by all three fillers, indicating poor interfacial adhesion. The results of Fourier transform infrared (FTIR) measurements are interpreted as indicating hydrogen bonding and thus relatively weak adhesion between filler and polymer. Aqueous mixtures of melamine‐formaldehyde and shungite filler had lower viscosities than corresponding melamine‐formaldehyde and carbon black filler mixtures. POLYM. COMPOS., 26:552–562, 2005. © 2005 Society of Plastics Engineers