Effects of carbon fiber modification with multiwall CNT on the electrical conductivity and EMI shielding effectiveness of polycarbonate/carbon fiber/CNT composites

The effect of carbon fiber (CF) modification with multiwall carbon nanotube (CNT) on the electrical, mechanical, and rheological properties of the polycarbonate (PC)/CF/CNT composite was investigated. The CF and multiwall CNT (MWCNT) were treated with sulfuric acid and nitric acid (3:1 wt %) mixture, to modify the CF with the CNT. For the PC with acid-treated CNT (a-CNT) modified acid-treated CF (a-CF) (PC/a-CF/a-CNT) composite, the electrical conductivity, and the electromagnetic interference shielding effectiveness (EMI SE) showed the highest values, compared with those of the PC/a-CF and PC/a-CF/CNT composites. The EMI SE of the PC/a-CF (10 wt %)/a-CNT (0.5 wt %) composite was found to be 26 (dB at the frequency of 10.0 GHz, and the EMI SE was increased by 91.2%, compared to that of the PC/a-CF composite at the same amount of total filler content. Among the composites studied in this work, the PC/a-CF/a-CNT composite also showed the highest values of relative permittivity (ε_r) and dielectric loss factor. The above results suggest that the CF modification with the a-CNT significantly affected the electrical conductivity and EMI SE of the composite, and the hybrid fillers of the a-CNT and a-CF resulted in good electrical pathways in the PC/a-CF/a-CNT composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47302.     

Morphology and electrical properties of short carbon fiber-filled polymer blends: High-density polyethylene/poly(methyl methacrylate)

Morphology and electrical properties of short carbon fiber-filled high-density polyethylene (HDPE)/poly(methyl methacrylate)(PMMA) polymer blends have been studied. The percolation threshold of HDPE50/PMMA50 blends filled with vapor-grown carbon fiber (VGCF), 1.25 phr VGCF content, is much lower than those of the individual polymers. The SEM micrographs verified that the enhancement of conductivity could be attributed to the selective location of VGCF in the HDPE phase. A double percolation is the basic requirement for the conductivity of the composites, i.e., the percolation of carbon fibers in the HDPE phase and the continuity of this phase in the blends, which hereby are defined as the first percolation and the second percolation, respectively. The SEM micrographs also showed that the short carbon fibers could affect the morphology of the blends. With the increase of VGCF content, the HDPE domains are elongated from spherical into strip shape, finally develop to a continuous structure. As a result, the second percolation threshold of the blends filled with 2.5 phr VGCF, 20 wt % HDPE, is lower than that of the blends filled with 1.5 phr VGCF, 30 wt % HDPE. The influence of molding temperature and time on the second percolation threshold has also been investigated. For the composites molded at a lower temperature, the second percolation threshold is shifted to a higher VGCF content, but there is little influence of molding time on the second percolation threshold. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1813–1819, 1998     

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     

Mechanical,electrical, and dielectric properties of polyvinylidene fluoride/short carbon fiber composites with low‐electrical percolation threshold

In this investigation, polyvinylidene fluoride (PVDF)/short carbon fiber (SCF) composites have been prepared by solution casting technique to enhance electrical and dielectric properties with very low‐electrical percolation threshold (0.5 phr SCF). The effect of SCF content on mechanical, thermal and morphological properties of the composites have also been investigated. The mechanical properties of the composites are found to reduce compared to neat PVDF due to poor polymer–filler interaction which can be concluded from FESEM micrographs showing poor bonding between PVDF and SCF. The PVDF/SCF composites exhibit either positive temperature coefficient effect of resistivity or negative temperature coefficient effect of resistivity depending on the loading of SCF in the polymer matrix. The change in conductivity during heating–cooling cycle for these composites shows electrical hysteresis along with electrical set. The melting point of the composites marginally increases with the increase in fiber loading in PVDF matrix as evidenced from DSC thermograms. X‐ray diffraction analysis reveals the crystallinity of PVDF decreases with the increase in SCF loading in matrix polymer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39866.     

Design of electrical conductive poly(lactic acid)/carbon black composites by induced particle aggregation

The electrical conductivity of ternary composites composed of a biopolymer blend with conductive particles (carbon black [CB]) is induced by the control of particle dispersion in the dispersed phase. If the CB particles have higher chemical affinity for the secondary phase (poly(caprolactone) [PCL]]) than the matrix (poly(lactic acid) [PLA]), especially as the concentration of the PCL phase decreases significantly to 4 wt%, the PCL phase induces the aggregation of CB particles beyond the selective localization, resulting in a shift of the particle percolation threshold to a lower concentration of particles (2.44 wt% CB). Moreover, the mixing ratio between the CB and the PCL phase significantly affects the formation of percolation of particles. When the mixing ratio of CB to PCL is equivalent (1:1), the ternary composite shows high electrical DC conductivity above 1 S/m with 10 wt% CB. The addition of a small amount of PCL induces the formation of particle aggregates with a high aspect ratio, providing more electron transfer pathways due to the multiple points of contact between the particle aggregates (power law scaling exponent of the composites ~2.14). Meanwhile, a binary composite (PLA/CB) never reaches high electrical conductivity of 1 S/m and even requires a greater concentration of CB (13 wt% CB for 10⁻³ S/m) to accomplish electron transfer because of the small aspect ratio of randomly dispersed particle aggregates (power law scaling exponent ~3.20).     

Evaluation of the rheological and electrical percolation of high-density polyethylene/carbon black composites using mathematical models

In this work, conductive polymer composites (CPCs) of bio-based polyethylene (BioPe) containing different concentrations of carbon black (CB) were developed. By using oscillatory rheology analysis, a Newtonian plateau was observed in BioPe, and all BioPe/CB composites had a behavior of a pseudo-solid and that composites with volume fractions ranging from 0.24 to 0.56 presented higher viscosity, storage, and loss modulus. This suggests the formation of a percolated network and by using the power-law models, it was observed that the electrical percolation threshold was higher than the rheological percolation threshold. The electrical conductivity was measured using the four-point probe method and a sigmoid model was used to predict the CPCs' electrical conductivity percolation threshold. The results indicated that the four-point probe method presented satisfactory results according to the calculated standard deviations and voltage–current characteristics for each round of measurements considering the same ranging as used in rheology analysis. The analytical model used showed a coefficient of determination (R²) higher than 95%, allowing the prediction of the electrical conductivity of the CPC and the percolation threshold as a function of the volumetric fraction of the CB.     

A modified model of electrical conduction for carbon black–polymer composites

A modified model of electrical conduction for carbon black‐polymer composites is proposed based on the general effective media theory and the number of carbon black particles per aggregate to describe their nonlinear conductive behavior. In order to consider the interactions between carbon black particles, a simple self‐consistent approach is used to improve the model. Expressions of electrical conductivity and percolation threshold are derived from the modified model. The predicted results of electrical conductivity and percolation threshold are in good agreement with experimental data reported in previous literature. Moreover, the dependences of electrical conductivity and percolation threshold on the number of carbon black particles per aggregate are discussed. Copyright © 2010 Society of Chemical Industry     

Conductive network formation and electrical properties of poly(vinylidene fluoride)/multiwalled carbon nanotube composites: Percolation and dynamic percolation

Conductive network formation and its dynamic process for multiwalled carbon nanotubes (MWNTs) and carboxyl‐tethered MWNT (MWNT‐COOH) filled poly(vinylidene fluoride)(PVDF) systems were investigated. Based on real‐time tracing the variation of electrical resistivity of systems with isothermal treatment time, the conductive network formation was evaluated. It was found that the conductive network formation was temperature and time dependent. The percolation time, characterized at a certain annealing time where the electrical resistivity started to decrease drastically, decreased with the increase of the filler concentration or the annealing temperature. However, the values of the percolation time and the activation energy of conductive network formation for the PVDF/MWNT‐COOH system were higher than those of the PVDF/MWNT system, indicating that the interaction between MWNTs and PVDF molecules played an important role in the conductive network formation of the composites. Furthermore, a modified thermodynamic percolation model was proposed to predict the percolation time of PVDF/MWNT composites. It was found that the calculated results fit the experimental data very well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

短碳纤维增强碳化硅基复合材料的制备

短纤维的分散均匀性一直是短纤维复合材料应用受限的主要原因．采用固相球磨分散和熔融渗硅工艺,可得到均匀分散的短碳纤维增强碳化硅基复合材料．并利用金相显微镜见察复合材料微观形貌,测试复合材料的抗弯强度和断后韧性．     

Conductive sizing for improving electrical conductivity of carbon fiber/polyaryl ether ketone/AgNWs composites

The aim of this work is to enhance the electrical conductivity of PAEK/continuous carbon fiber (CF) composites while maintaining their mechanical properties. A conductive sizing was elaborated by mixing polyetherimide (PEI) with silver nanoplates (AgNpts) in suspension in dichloromethane. An aqueous PEI formulation was used as insulating sizing reference. The presence of AgNpts into the sizing enhances electrical conductivity up to 0.2 S.m⁻¹ for a silver content ∼ 0.2 vol % without any modification of mechanical properties. The influence of conductive sizing on PAEK–AgNWs/CF was observed. For low AgNWs content lower (<1 vol %); the conductive sizing increases the electrical conductivity of the composite by one decade. This result shows that both types of Ag particles participate to the conductive path. For higher AgNWs content, electrical conductivity (200 S.m⁻¹) is independent from the AgNpts content: the conductive path is only constituted by AgNWs. Mechanical properties of such composites show that the value of the conservative modulus is almost the same, while the dissipative modulus slightly increases. The global mechanical properties of the composite are preserved despite the addition of the CF, AgNWs, and AgNpts. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47872.     

Effects of the dispersion state and aspect ratio of carbon nanotubes on their electrical percolation threshold in a polymer

The electrical percolation threshold of carbon nanotubes (CNTs) is correlated with their dispersion state and aspect ratio through modeling. An analytical percolation model based on excluded volume theory and developed for systems containing two types of fillers is used. CNTs are modeled as two types of fillers: single CNT and m‐CNT bundle, and a variable P representing the dispersion state of CNTs is introduced. An equation showing the effects of the dispersion state and aspect ratio on the electrical percolation threshold of CNTs is established and verified with some of the published experimental data. It is useful for predicting the conductive behavior of polymer/CNT composites and for the design of their processing conditions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electromagnetic interference shielding effectiveness and skin depth of poly(vinylidene fluoride)/particulate nano‐carbon filler composites: prediction of electrical conductivity and percolation threshold

The addition of various particulate nano‐carbon (PNC) fillers to heat‐resistant poly(vinylidene fluoride) (PVDF) was carried out to prepare conductive composites for use in electromagnetic interference (EMI) shielding application. Three different PNC fillers, namely N472 (Vulcan XC‐72), N550 (Fast Extruding Furnace) and N774 (Semi‐Reinforcing Furnace), were used in various concentrations to prepare composite systems PVDF/N472, PVDF/N550 and PVDF/N774 by solution casting followed by a moulding technique. These PNC fillers have a particle size at the nanometre level, but they have an aggregating tendency; both these characteristics influence the properties of composites to which such fillers are added. The percolation threshold of the PVDF/PNC composites was theoretically determined using the sigmoidal Boltzmann model and classical theory and compared. Theoretical models were also used to predict composition‐dependent electrical conductivity. The electrical conductivity is correlated to that of EMI shielding effectiveness at ambient temperature. © 2019 Society of Chemical Industry     

Morphology of polystyrene/poly(methyl methacrylate) blends: Effects of carbon nanotubes aspect ratio and surface modification

Multiwalled carbon nanotubes (MWCNTs) with aspect ratios (ARs) ranging from 94 to 474 were incorporated into polystyrene (PS)/poly(methyl methacrylate) blends using solution mixing and melt mixing. Also, two functionalized MWCNTs were prepared from the nanotubes having AR 94: one was oxidized by nitric acid while the other was further modified with amine‐terminated PS attached to carboxyl groups to form amides. The two functionalized MWCNTs (1 wt %) were used to show that which phase the carbon nanotubes (CNTs) were located in could be controlled with nanotube surface chemistry. When nanotubes were confined to the minor phase, the size of the minor domain first decreased with adding low AR CNT as expected due to the increased viscosity of the minor phase. However, at higher ARs, the size increased beyond the size for the minor domain with no nanotubes, and at high enough AR, the shape of the minor domain changed from spherical to an elongated irregular shape. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3500–3510, 2015     

Electrical and rheological percolation in poly(vinylidene fluoride)/multi‐walled carbon nanotube nanocomposites

Nanocomposites of poly(vinylidene fluoride) (PVDF) and multi‐walled carbon nanotubes (MWCNTs) were prepared through melt blending in a batch mixer (torque rheometer equipped with a mixing chamber). The morphology, rheological behavior and electrical conductivity were investigated through transmission electron microscopy, dynamic oscillatory rheometry and the two‐probe method. The nanocomposite with 0.5 wt% MWCNT content presented a uniform dispersion through the PVDF matrix, whereas that with 1 wt% started to present a percolated network. For the nanocomposites with 2 and 5 wt% MWCNTs the formation of this nanotube network was clearly evident. The electrical percolation threshold at room temperature found for this system was about 1.2 wt% MWCNTs. The rheological percolation threshold fitted from viscosity was about 1 wt%, while the threshold fitted from storage modulus was 0.9 wt%. Thus fewer nanotubes are needed to approach the rheological percolation threshold than the electrical percolation threshold. Copyright © 2010 Society of Chemical Industry     

Electrical conductivity and mechanical strength of composites consisting of phenolic resin,carbon fibers,and metal particles

Composites of phenolic resin of novolac type as matrix, with metal particles of Zn as conducting filler, without or with 15% v/v carbon fibers were manufactured by hot pressing. The porosity ratio, the hardness, the flexural and shear strength, and the electrical conductivity of the composites were determined. The percolation threshold was determined based on two models of electrical conductivity versus the content of metal particles of Zn, namely, an analogous to polymer gelation model and the other based on the power law. The composites of carbon fibers combined with Zn particles have higher electrical conductivity than the corresponding without carbon fibers and high strength, lower than that of the composite reinforced with carbon fibers without Zn particles, but still acceptable. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

碳纤维和钢渣水泥基复合材料导电性及损伤识别研究

在水泥基复合材料中参入碳纤维和钢渣,以研究复合水泥基材的导电性能,结果表明,碳纤维能够显著改善水泥基材的导电性,碳纤维体积率为1.2%时,其导电性能最佳,且碳纤维对试件导电稳定性有显著影响;在碳纤维水泥基材中参入钢渣并不会显著影响试件导电性,会显著影响导电稳定性;抗压和抗折试验结果表明利用导电性判断构件是否损伤(开裂)及损伤程度在试验上是可行的。     

Preparation of conductive polylactic acid/high density polyethylene/carbon black composites with low percolation threshold by locating the carbon black at the Interface of co-continuous blends

In the current study, polylactic acid/high density polyethylene/carbon black (PLA/HDPE/CB) composites are prepared via a two-step method. A double percolation network with co-continuous structure and filler distribution at the interface is constructed to design conductive polymer composites with low percolation threshold. The controllable distribution of CB at the interface is achieved by appropriate processing procedures involved mixing sequence and mixing time by taking advantage of the migration of CB from the unfavorable PLA phase to the favorable HDPE phase. Morphology characterization reveals that when the mixing time of the added HDPE is 3 min, the formation of co-continuous structure of PLA/HDPE (60/40, w/w) is observed, and CB particles migrate to the co-continuous interface. The electrical conductivity measurement shows that such double percolation conductive network reduces the percolation threshold of PLA/HDPE/CB to 2.42 wt%. The rheological property proves the establishment of particle percolation network, and the rheological percolation threshold is determined as 1.20 wt%. The prepared PLA/HDPE/CB composite by the two-step method displays a notably low percolation threshold than that prepared by one-step simultaneous mixing. Moreover, this strategy presents a high potential application in the fabrication of conductive polymer composites involving other miscible multiphase systems.     

Improving the interlaminar shear strength and thermal conductivity of carbon fiber/epoxy laminates by utilizing the graphene-coated carbon fiber

The poor interlaminar properties restrict the application of carbon fiber reinforced polymer (CFRP) composites. In this work, a novel method for fabricating a graded interface structure is developed to improve the through-thickness thermal conductivity of CFRP composites. High-strength graphene nano-plates (GnP) and phenolic resin (PF) were selected to deposit on the surface of carbon fiber to design a novel CF/Epoxy laminates, where a simultaneous improvement of interlaminar shear strength (ILSS) and through-thickness thermal conductivity was observed. With addition of 1 wt % of GnP-PF in CF, 37.04% increase of the ILSS, and 16.67% enhancement of thermal conductivity compared to the original CFRP. The mechanism for improvement of both ILSS and thermal conductivity was studied by scanning electron microscopy and nano-indentation, where a better interface formed by GnP-PF has been clearly observed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47061.     

Comparative study of EMI shielding effectiveness for carbon fiber pultruded polypropylene/poly(lactic acid)/multiwall CNT composites prepared by injection molding versus screw extrusion

The electrical conductivity and electromagnetic interference (EMI) shielding effectiveness of the composites of polypropylene/poly(lactic acid) (PP/PLA) (70/30, wt %) with single filler of multiwall carbon nanotube (CNT) or hybrid fillers of nickel‐coated carbon fiber (CF) and CNT were investigated. For the single filler composite, higher electrical conductivity was observed when the PP‐g‐maleic anhydride was added as a compatibilizer between the PP and PLA. For the composite of the PP/PLA (70/30)/CF (20 phr)/CNT (5 phr), the composite prepared by injection molding observed a higher EMI shielding effectiveness of 50.5 dB than the composite prepared by screw extrusion (32.3 dB), demonstrating an EMI shielding effectiveness increase of 49.8%. The higher values in EMI shielding effectiveness and electrical conductivity of the PP/PLA/CF (20 phr)/CNT (5 phr) composite seemed mainly because of the increased CF length when the composites were prepared using injection molding machine, compared with the composites prepared by screw extrusion. This result suggests that the fiber length of the conductive filler is an important factor in obtaining higher values of electrical conductivity and EMI shielding effectiveness of the PP/PLA/CF/CNT composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45222.     

Crystal morphology and nonisothermal crystallization kinetics of short carbon fiber/poly(trimethylene terephthalate) composites

The crystal morphology and nonisothermal crystallization kinetics of short carbon fiber/poly(trimethylene terephthalate) (SCF/PTT) composites were investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The optical micrographs suggest that the more content of SCF in composites, the smaller size of the spherulites is. Moreover, the addition of SCF can lead to forming banded spherulites in composites. The Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of nonisothermal crystallization of various composites. The results suggest that the SCF served as nucleation agent, accelerates the crystallization rate of the composites, and the more content of SCF, the faster crystallization rate is. Effective activation energy calculated by the differential iso‐conversional method developed by Friedman also concludes that the composite with more SCF component has higher crystallization ability than that with less SCF content. The kinetic parameters U* and K_g are determined, respectively, by the Hoffman–Lauritzen theory. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007