Electrical,rheological, and mechanical properties copolymer/carbon black composites

This work aims to evaluate the electrical conductivity and the rheological and mechanical properties of copolymer/carbon black (CB) conductive polymer composites (CPCs). The copolymers, containing ethylene groups in their structure, used as matrix were polyethylene grafted with maleic anhydride (PEgMA), ethylene-methyl acrylate–glycidyl methacrylate (EMA-GMA), and ethylene-vinyl acetate (EVA). For comparison purposes, bio-based polyethylene (BioPE)/CB composites were also studied. The electrical conductivity results showed that the electrical percolation threshold of BioPE/CB composite was 0.36 volume fraction of CB, whereas the rheological percolation threshold was 0.25 volume fraction of CB. The most conductive CPC was BioPE/CB. Among the copolymer/CB CPCs, PEgMA/CB showed the highest conductivity, which can be attributed to the fact that the PEgMA copolymer had higher crystallinity. It also has a higher amount of ethylene groups in its structure. Torque rheometry analysis indicated that EMA-GMA copolymer may have reacted with CB. Rheological measurements under oscillatory shear flow indicated the formation of a percolated network in BioPE/CB and copolymer/CB composites. Morphology analysis by scanning electron microscopy (SEM) indicated the formation of a percolated network structure in BioPE/CB composite and finely dispersed CB particles within the PEgMA copolymer. Wetting of CB particles/agglomerates by the copolymer matrix was observed in EVA/CB and EMA-GMA/CB composites. Conductive CB acted as reinforcing filler as it increased the elastic modulus and tensile strength of BioPE and the copolymers.     

Electrical and mechanical behavior of carbon black–filled poly(vinyl acetate) latex–based composites

The electrical and mechanical behaviors of carbon black‐filled. Poly(vinyl acetate) latex‐based polymer composites were examined. These composites were found to exhibit percolation thresholds in electrical conductivity near 2 vol% carbon black due to their segregated microstructures. Storage modulus and ultimate tensile strength (UTS) both exhibited discontinuities at 10 vol% carbon black, corresponding to a critical pigment volume concentration. Drying composites at 60°C rather than room temperature produced a higher percolation threshold and better mechanical properties at carbon black loadings above 10 vol% carbon black. A figure of merit was proposed to assess the balance of electrical conductivity, storage modulus and UTS. The figure of merit exhibited a peak value at 10 vol% for composites dried at room temperature and was shifted to higher carbon black concentrations when composites were dried at 60°C.     

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     

Electrically conductive carbon black (CB) filled in situ microfibrillar poly(ethylene terephthalate) (PET)/polyethylene (PE) composite with a selective CB distribution

In the present study, it was attempted to fabricate a new conductive carbon black (CB) filled poly(ethylene terephthalate) (PET)/polyethylene (PE) in situ microfibrillar composite with a lower percolation threshold through selectively localizing CB particles in the surfaces of the PET microfibrils. The CB particles were first mixed with PE matrix, and then PET was added into CB/PE compound. Subsequently, the CB/PET/PE composite was subjected to a slit die extrusion, hot stretch and quenching process to generate in situ PET microfibrils, in which CB particles moved to the surfaces of the PET microfibrils simultaneously. The morphological observation showed that the PET phases formed well-defined microfibrils, and CB particles did overwhelmingly localize in the surfaces of the PET microfibrils, which led to a very low percolation threshold, i.e., 3.8 vol%, and a good conductivity. The conductive network was built by the contact and overlapping of the CB particles coated PET microfibrils. In addition, the CB particles remaining in the PE matrix also contributed to the conductive paths, especially for the high CB loading filled microfibrillar composites. Because of the complexity of the distribution of CB particles, a high critical resistance exponent t (t = 6.4) exists in this conductive composite. To reveal the possibility of the migration of CB particles from PE to PET, the morphology of the CB/PET/PE composite mixed for different times was examined. It was found that, depending on the mixing time, the CB particles gradually migrated from the PE matrix to the surfaces at first, and then to the center of the PET phases. The preferable distribution of CB particles was originated from several factors including interfacial tension, viscosity, molecule polarity, and mixing process. Furthermore, during the mixing process of the CB/PET/PE composite, the migration of CB particles to PET phase from PE matrix led to the increase of both the viscosity ratio of the dispersed phase to the matrix and the volume of the dispersed phases, thus resulting in larger dispersed CB/PET composite phase particles.     

Hybrid electro-conductive composites with improved toughness, filled by carbon black

The influence of both carbon black (CB), and an ethylene-propylene copolymer grafted by maleic anhydride (EP-g-MA), on the static mechanical properties, impact strength, peel and shear strengths as well as on the electrical conductivity of composites based on high-density polyethylene (HDPE) matrix, was investigated in this paper. It was found that CB improves the stress at yield, the stress at break, and Young’s modulus, as well as the shear strength and peel strength, of the HDPE/CB composites. The percolation threshold was found at 4.5 vol.% of CB. The addition of EP-g-MA to the HDPE/CB composites improves their impact strength, the peel and shear strengths, and the electrical conductivity.     

Poly(1,3‐butylene adipate) plasticized poly(lactic acid)/carbon black as electrical conductive polymer composites

Poly(1,3‐butylene adipate) (PBA) as the plasticizer for poly(lactic acid) (PLA) and carbon black (CB) as conductive filler, electrically conductive polymer composites (CPC) with different CB and PBA contents were prepared. Fourier transform infrared revealed that the interaction existed between PLA/PBA matrix and CB filler, and PBA could improve this interaction. The rheology showed that CB could obviously improve the apparent viscosity and decrease the fluidity of the composites, but just the reverse for PBA. PLA/PBA/CB composites exhibited the low electrical percolation thresholds of 0.516, 1.20, 2.46, and 2.74 vol% CB at 30, 20, 10, and 0 wt% PBA. The conductivity of the composite containing 3.98 vol% CB and 30 wt% PBA reached 1.67 S/cm. Scanning electron microscopy revealed that the addition of PBA facilitated the dispersion of PLA/CB composites. PBA could dramatically increase the elongation at break of plasticized PLA. But high‐PBA content caused the lowering of tensile strength. With the increasing of CB contents, the enforcement effect on the plasticized PLA became more obvious. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Conductive polymer blends filled with carbon black: Positive temperature coefficient behavior

Electrical conductivity and positive temperature coefficient (PTC) behavior of carbon black (CB) filled incompatible polyblends of ethylene-vinyl acetate copolymer/low density polyethylene (EVA/LDPE) were investigated. In comparison with single polymer systems, more possibilities for tailoring composite performance were brought about with the employment of polymer blends as matrix resins in conductive composites. Based on the concepts of double percolation and two-step percolation, PTC-type composites with balanced performance, improved processability, and reproducibility can be made. Thermodynamical and kinetic factors including interfacial energy, melt viscosity, blending ratio, melt mixing time, sequence of blending as well as CB concentration were shown to be closely related to the ultimate properties obtained.     

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     

Tensile modulus modeling of carbon black/polycarbonate,carbon nanotube/polycarbonate,and exfoliated graphite nanoplatelet/polycarbonate composites

Conductive fillers are often added to thermoplastic polymers to increase the resulting composite's electrical conductivity (EC) which would enable them to be used in electrostatic dissipative and semiconductive applications. The resulting composite also exhibits increased tensile modulus. The filler aspect ratio plays an important role in modeling composite EC, and tensile modulus. It is difficult to measure the filler aspect ratio after the manufacturing process (often extrusion followed by injection molding) in the composite, especially when nanomaterials are used. The EC percolation threshold is a function of the filler aspect ratio; hence, knowledge of this percolation threshold provides a means to extract the filler aspect ratio. In this study, the percolation threshold of the composite was determined from EC measurements and modeling, which in turn was used to determine the filler aspect ratio for tensile modulus modeling. Per the authors' knowledge, this approach has not been previously reported in the open literature. The fillers; carbon black (CB: 2–10 wt %), multiwalled carbon nanotubes (CNT: 0.5–8 wt %), or exfoliated graphite nanoplatelets (GNP: 2–12 wt %); were added to polycarbonate (PC) and the resulting composites were tested for EC and tensile modulus. With the filler aspect ratio determined from EC values for CNT/PC and GNP/PC composites, the three‐dimensional randomly oriented fiber Halpin‐Tsai model accurately estimates the tensile modulus for the CNT/PC composites and the Nielsen model predicts the tensile modulus well for the CB/PC and GNP/PC composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrical conductivity and self-temperature-control heating properties of carbon nanotubes filled polyethylene films

Electrical properties of polyethylene and carbon nanotube composite films were investigated, when the composite films were set in heating box or under electric field at constant voltage. The composite films were prepared by gelation/crystallization from dilute solution. The mixture of ultra-high molecular weight polyethylene (UHMWPE) and branched low molecular weight polyethylene (LMWPE) was used as matrix, and multi-walled carbon nanotubes (MWNTs) were used as fillers. The filler content was chosen to be 10 wt% (ca. 5.25 vol%) which is a relatively higher loading than the percolation threshold to ensure to act as heating element in plane heater of composite film. The focus was concentrated on the temperature dependences of electric conductivity by external heating and by exothermic effect concerning self-temperature-control heating properties which were measured for the three kinds of UHMWPE-LMWPE composites with the same content of MWNTs in the composites. When a certain voltage was applied to the composite, the surface temperature of film reaches the equilibrium value within less than 100 s. The maximum surface temperature as the equilibrium state of the resultant composite film can be easily controlled by adjusting the composite ratio represented as UHMWPE/LMWPE. The high efficiency of heating and wide adjustability of stable temperature suggested its good application in high efficient plane heater.     

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     

High-dielectric constant percolative composite of P(VDF-TrFE) and modified multi-walled carbon-nanotubes

To develop a high-dielectric constant composite of poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] and multi-walled carbon-nanotubes (MWCNTs) with desirable homogeneity, MWCNTs were treated with a nitro-sulfuric acid by ultrasonication. The chemically modified MWCNTs (a-MWCNTs) were characterized by Fourier transform infrared spectroscopy and a back-titration procedure. Improvement of the dispersibility of a-MWCNTs in polymer matrix, in comparison with unmodified MWCNTs in P(VDF-TrFE), was confirmed by field emission scanning electron microscopy. Electric behavior of the composites with different volume fraction of dispersed carbon nanotubes can be described by percolation theory, as well as the Maxwell–Wagner–Sillars mechanism. The percolation threshold (f _c ) of composites with a-MWCNTs (f _c  = 0.0308) is larger than that of composites with MWCNTs (f _c  = 0.0216) due to better dispersion of a-MWCNTs in matrix and the reduction of aspect ratio of a-MWCNTs occurred in the modification procedure. The composite with 2.98 vol% (close to the percolation threshold) of a-MWCNTs has a dielectric constant of 592 at 100 Hz and room temperature.     

Electrical and mechanical properties of polyimide-carbon nanotubes composites fabricated by in situ polymerization

Polyimide (PI)-carbon nanotubes composites were fabricated by in situ polymerization using multi wall carbon nanotubes (MWNT) as fillers. It suggested that in situ polymerization is an ideal technique to make a perfect dispersion of carbon nanotubes into matrixes. Besides it, the pre-treatment of carbon nanotubes in solvent to make the networks untied enough and to let solvent percolated into the networks is very important for forming uniform entanglements between carbon nanotubes and polymer molecular chains. The results imply that the percolation threshold for the electric conductivity of the resultant PI-MWNT composites was ca. 0.15 vol%. The electrical conductivity has been increased by more than 11 orders of magnitude to 10⁻⁴ S/cm at the percolation threshold. The mechanical properties of the polyimide composite were not improved significantly by addition of carbon nanotubes.     

Conducting property of carbon black filled poly(ethylene glycol)/poly(methyl methacrylate) composites as gas‐sensing materials

To reveal the role of crystalline polymers in carbon black (CB) filled amorphous polymer composites and improve the mechanical properties of composite films, CB/poly(ethylene glycol) (PEG)/poly(methyl methacrylate) (PMMA) composites were synthesized by polymerization filling in this work. The electrical conductive property and response to organic solvent vapors of the composites were investigated. The composites, characterized by a relatively low percolation threshold (～ 2.1 wt %), had lower resistivity than CB/PMMA composites prepared with the same method because of the different dispersion status of CB particles in the matrix polymer. The concentration and molecular weight of PEG notably influenced the electrical response of the composites against organic vapors. The drastic increase in the electrical resistance of the composites in various organic vapors could be attributed mainly to the swelling of the amorphous polymer matrix in the solvent but not to that of the crystalline polymer. These findings could help us to understand the conductive mechanism and electrical response mechanism of the composites as promising gas‐sensing materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Influence of carbon black and carbon nanotubes on the conductivity,morphology, and rheology of conductive ternary polymer blends

The influence of carbon black (CB) and multiwall carbon nanotubes (CNT) with different colloidal properties on the phase morphology, electrical properties, and rheological behavior in a polypropylene (PP)/poly(methyl methacrylate) (PMMA)/ethylene acrylic acid copolymer (EAA) ternary polymer blend was studied. A PP/PMMA/(EAA‐CNT) system was compared to two different PP/PMMA/(EAA‐CB) systems. The relationship between the phase morphology, electrical percolation threshold, and rheological behavior was analyzed. The critical percolation threshold for the ternary system was found to be around 0.5 vol% for the PP/PMMA/(EAA‐CB1) and 0.2 vol% for the PP/PMMA/(EAA‐CB2) and PP/PMMA/(EAA‐CNT), which were more than 8 times lower than for the single phase systems. The rheological threshold coincided with the electrical resistivity percolation threshold inversion point. It was proposed that beyond a critical loading of conductive filler particles in the minor EAA phase, especially for high aspect ratio fillers such as the CB2 and CNT, phase separation is slowed significantly due to the aggregation of particles into a network formation within the EAA phase causing a significant increase in phase viscosity. The results are consistent with the hypothesis that the kinetics of phase separation and resulting formation of a tri‐continuous morphology are dictated by the viscosity of the minor phase relative to the two major phases. POLYM. ENG. SCI., 57:1329–1339, 2017. © 2017 Society of Plastics Engineers     

Low percolation threshold in single-walled carbon nanotube/high density polyethylene composites prepared by melt processing technique

A new method was developed to disperse carbon nanotubes (CNTs) in a matrix polymer and then to prepare composites by melt processing technique. Due to high surface energy and strong adsorptive states of nano-materials, single-walled carbon nanotubes (SWNTs) were adsorbed onto the surface of polymer powders by spraying SWNT aqueous suspected solution onto fine high density polyethylene (HDPE) powders. The dried SWNTs/powders were blended in a twin-screw mixture, and the resulting composites exhibited a uniformly dispersion of SWNTs in the matrix polymer. The electrical conductivity and the rheological behavior of these composites were investigated. At low frequencies, complex viscosities become almost independent of the frequency as nanotubes loading being more than 1.5 wt%, suggesting an onset of solid-like behavior and hence a rheological percolation threshold at the loading level. However, the electrical percolation threshold is ∼4 wt% of nanotube loading. This difference in the percolation thresholds is understood in terms of the smaller nanotube-nanotube distance required for electrical conductivity as compared to that required to impede polymer mobility. The measurements of mechanical properties indicate that this processing method can obviously improve the tensile strength and the modulus of the composites.     

High-yield water-phase exfoliated few-defect graphene for high performance polymer nanocomposites

Application of graphene requires a high-yield, low-cost, scalable production method, but it remains highly challenging. We here report a water-phase technique to produce few-defect graphene nanosheets (FGS) with a high exfoliation yield (92%), based on the chemically expanded graphite with ultrahigh specific surface areas, and demonstrate the application in graphene-polymer nanocomposites. The exfoliated FGS has low degree of oxidation and preserves good mechanical and electrical properties, revealing promising potential for improving comprehensive properties of polymer composites. When 0.5 wt% FGS was incorporated to poly(methyl methacrylate) (PMMA), the 5% weight loss temperature and storage modulus increase by 87°C and 21%, respectively, relative to the neat polymer. With increasing the content of FGS to 4.6 wt%, the glass transition temperature of the composite increases by 25°C. In addition, the composites show a percolation threshold as low as 0.25 vol% and excellent electrical conductivity (50 S/m for 2.7 vol% FGS-PMMA composite).     

Study of carbon black‐filled poly(butylene succinate)/polylactide blend

In this study, carbon black (CB) was used to control the conductivity and the compatibility of immiscible poly(butylene succinate)/polylactide (PBS/PLA) blend. It is shown that most of the CB particles are selectively dispersed in the matrix PBS phase because of the viscosity ratio of the blend components. The increasing viscosity of PBS phase prevents the coalescence of the dispersed PLA domain during the melt mixing. The domain sizes of PLA are refined when compared with that of blank PBS/PLA blend. The ternary composite shows an onset of the electrical conductivity at low filler loadings (1.5 wt %), which is attributed to a percolation of CB in the insulating matrix polymer. Moreover, the composites exhibited remarkable improvement of rheological properties in the melt state when compared with that of blank PBS/PLA blend. According to the van Gurp‐Palmen plot, the rheological percolation threshold for ternary systems is lower than 1.5 wt %. Furthermore, the ternary composites present improved mechanical properties and thermal stability even at very low loading levels of the CB. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Lowering the percolation threshold of conductive composites using particulate polymer microstructure

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