Improved dispersion of carbon nanotubes in poly(vinylidene fluoride) composites by hybrids with core–shell structure

Core–shell structure hybrids of carbon nanotubes (CNTs)/BaTiO₃ (H‐CNT‐BT) and commercial multi‐wall CNTs are respectively incorporated into poly(vinylidene fluoride) (PVDF) for preparing the composites near the percolation thresholds. A comprehensive investigation for CNT's dispersion and composite's conductivity is conducted between H‐CNT‐BT/PVDF and CNT/PVDF at different depths vertical to the injection's direction. Gradual increases of the conductivity in two composites are observed from the out‐layer to the core part which infers an inhomogeneous CNT's dispersion in the interior of composites due to their migration under flow during the injection. However, the use of H‐CNT‐BT fillers with core–shell structure enables to reduce this inhomogeneous dispersion in the composite. Furthermore, the conductive network of CNTs in H‐CNT‐BT/PVDF is less sensitive to the thermal treatment than the one in CNT/PVDF composite, which infers the core–shell structure of hybrids can ameliorate the sensitivity of the conductive network. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45693.     

Polyaniline/silver/cerium nitrate ternary composite: Synthesis,characterization and enhanced electrochemical properties

Polyaniline/Ag/Ce (NO₃)₃ ternary composites were prepared by in situ polymerization in a poly (2‐arcylamido‐2‐methylpropane sulfonic acid) aqueous solution. Fourier transform infrared spectroscopy and Ultraviolet‐visible spectroscopy analyses indicated that Ce ions had a conjugated interaction with N, O of polyaniline (PANI), and poly (2‐arcylamido‐2‐methylpropane sulfonic acid). By comparison with PANI and PANI binary composite, this ternary composite had a better thermal stability, a high conductivity (3.49 S/cm), a large capacitance, and a high electrochemical activity. Especially, the corrosion potential of this ternary composite can reach ?418 mV and the inhibition efficiency can be increased by 68.08%. This ternary porous composite has promising applications in capacitor, conductive materials, anticorrosion coating, and other related fields. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42785.     

Conductive and flexible multi-walled carbon nanotube/polydimethylsiloxane composites made with naphthalene/toluene mixture

Conventional conductive materials face challenges when utilizing them for flexible and wearable electronics and soft robotics. Carbon nanotube/polydimethylsiloxane (CNT/PDMS) composites are a promising alternative to the conventional hard conductors because they are light and can realize large deformation. To date, well dispersion of CNTs into PDMS to increase conductivity while maintaining flexibility remains challenging. We aimed at developing highly electrically conductive and flexible multi-walled carbon nanotube/PDMS (MWCNT/PDMS) composites. To this end, we proposed a method to enhance the dispersion of MWCNTs into PDMS using naphthalene and toluene. Our results showed that the addition of naphthalene and toluene into the composites improved dispersion of the MWCNTs and increased the direct current (DC) electrical conductivity. We also found that the morphology of primary aggregates of the MWCNTs influenced the DC electrical conductivity of the composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48167.     

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.     

Enhancement of electrical conductivity and other related properties of epoxidized natural rubber/carbon nanotube composites by optimizing concentration of 3‐aminopropyltriethoxy silane

Carbon nanotube (CNT)‐filled epoxidized natural rubber (ENR) composites were prepared by mixing in an internal mixer and thereafter on a two‐roll mill. Silane coupling agent, namely 3‐aminopropyltriethoxy silane (APTES), was directly incorporated in the ENR‐CNT composites during mixing of rubber and CNTs in the mixer, to perform in situ functionalization. It was found that pre‐crosslinking of ENR and APTES occurred especially at high APTES concentrations, such as 0.06 mL/(g of CNTs) and caused strong CNT agglomeration in the ENR matrix. However, the pre‐crosslinking could be reduced or avoided by decreasing the APTES concentration. In the concentration range 0.01–0.015 mL/(g of CNTs) of APTES, the APTES molecules were grafted on the CNT surfaces and generated new chemical linkages with the ENR. This improved the CNT dispersion in the ENR matrix and enhanced the composite properties. A very low approximately 0.5 phr of CNT threshold concentration for electric percolation was achieved in this type of composites. Also, three‐dimensional connected CNT networks were found to form in the ENR matrix at very low APTES levels. Thus, the electrical conductivity achieved in these composites reached the level required of conductive materials. POLYM. ENG. SCI., 57:381–391, 2017. © 2016 Society of Plastics Engineers     

Poly(3-hexylthiophene) wrapped carbon nanotube/poly(dimethylsiloxane) composites for use in finger-sensing piezoresistive pressure sensors

We fabricated a piezoresistive composite using multi-walled carbon nanotubes (MWCNTs) as a conductive filler and polydimethylsiloxane (PDMS) as a polymer matrix, which operated in the extremely small pressure range required for finger-sensing. To achieve a homogeneous dispersion of MWCNTs in PDMS, the MWCNTs were modified by a polymer wrapping method using poly(3-hexylthiophene) (P3HT). The percolation threshold of the composites was significantly lowered by the presence of P3HT. The electrical conductivity and piezoresistive sensitivity of the composite were found to strongly depend on the P3HT concentration. The well-dispersed P3HT-MWCNT/PDMS composite showed good piezoresistive characteristics in the 0–0.12 MPa pressure range.     

Preparation and properties of carbon nanotube/binary‐polymer composites with a double‐segregated structure

A carbon nanotube (CNT)/poly(methyl methacrylate) (PMMA)/ultrahigh molecular weight polyethylene (UHMWPE) composite containing a double‐segregated structure was formalized by means of a facile mechanical mixing technology. In the composite, the CNTs were decorated on the surfaces of PMMA granules, and the CNTs decorated granules formed the continuous segregated conducting layers at the interfaces between UHMWPE particles. Morphology observations confirmed the formation of a specific double‐segregated CNT conductive network, resulting in an ultralow percolation threshold of ～0.2 wt %. The double‐segregated composite containing only 0.8 wt % CNT loading exhibited a high electrical conductivity of ～0.2 S m^?1 and efficient electromagnetic shielding effectiveness of ～19.6 dB, respectively. The thermal conductivity, temperature‐resistivity behaviors, and mechanical properties of the double‐segregated composites were also studied. This work provided a novel conductive network structure to attain a high‐performance conducting polymer composite at low filler loadings. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39789.     

Morphology and properties of electrically and rheologically percolated PLA/PCL/CNT nanocomposites

Poly(lactic acid)/poly(?‐caprolactone)/carbon nanotube (PLA/PCL/CNT) nanocomposites (NCs) were melt‐processed in a conventional industrial‐like twin‐screw extruder maintaining a constant PLA/PCL 80/20 wt. ratio. CNTs located in the thermodynamically favored PCL phase and, as a result, the “sea–island” morphology of the unfilled blend was replaced by a more continuous PCL dispersed phase in the ternary NCs. Rheological and electrical percolation took place at the same CNT contents (over 1.2 wt %) that TEM images suggest continuity of the PCL phase. The electrical and the low‐strain mechanical behaviors upon CNT addition were similar in the reference binary PLA/CNT and ternary PLA/PCL/CNT NCs. In the percolated NCs, the conductivity became 10⁶–10⁷ times higher than in the insulating compositions, while the Young modulus increased linearly upon the addition of CNT (12% increase at 4.9 wt % loading). Moreover, all the PLA/PCL/CNT NCs showed a ductile behavior (elongation at break >130%) similar to that of the unfilled PLA/PCL blend (140%), in contrast to the brittle behavior of binary PLA/CNT NCs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45265.     

Synergistic effect of graphene and carbon nanotube on lap shear strength and electrical conductivity of epoxy adhesives

In this study, synergy between graphene platelets (GnPs) and carbon nanotubes (CNTs) in improving lap shear strength and electrical conductivity of epoxy composite adhesives is demonstrated. Adding two-dimensional GnPs with one-dimensional CNTs into epoxy matrix helped to form global three-dimensional network of both GnPs and CNTs, which provide large contact surface area between the fillers and the matrix. This has been evidenced by comparing the mechanical properties and electrical conductivity of epoxy/GnP, epoxy/CNT, and epoxy/GnP-CNT composites. Scanning electron microscopic images of lap shear fracture surfaces of the composite adhesives showed that GnP-CNT hybrid nanofillers demonstrated better interaction to the epoxy matrix than individual GnP and CNT. The lap shear strength of epoxy/GnP-CNT composite adhesive was 89% higher than that of the neat epoxy adhesive, compared with only 44 and 30% increase in the case of epoxy/GnP and epoxy/CNT composite adhesives, respectively. Electrical percolation threshold of epoxy/GnP-CNT composite adhesive is recorded at 0.41 vol %, which is lower than epoxy/GnP composite adhesive (0.58 vol %) and epoxy/CNT composite adhesive (0.53 vol %), respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48056.     

Elastomeric ethylene copolymers with carbon nanostructures having tailored strain sensor behavior and their interpretation based on the excluded volume theory

Two ethylene/1‐butene thermoplastic elastomer copolymers were melt mixed with either multiwalled carbon nanotubes (CNTs) or thermally reduced graphite oxide (TrGO) resulting in piezoresistive composite materials. The effect of the polymer matrix, carbon nanostructure and filler concentration on the electrical behavior of the sensors was analyzed. The percolation process confirmed the relevance of these parameters as different thresholds were found depending on both the matrix and the filler. For instance, composites based on TrGO presented higher percolation thresholds than those based on CNTs. Regarding the strain sensor behavior of the electrically conductive composites, by using a matrix with a low amount of 1‐butene comonomer, higher resistance sensitivities were observed compared with the other matrix. Noteworthy, composites based on TrGO filler presented strain sensitivities one order of magnitude higher than composites based on CNT filler. These results are explained by the excluded volume theory for percolated systems. Based on these findings, polyethylene piezoresistive sensors can be designed by a proper selection of polymer matrix, filler concentration and carbon nanoparticles. © 2016 Society of Chemical Industry     

Fabrication and electrochemical capacitance of hierarchical graphene/polyaniline/carbon nanotube ternary composite film

A film composed of graphene (GN) sheets, polyaniline (PANI) and carbon nanotubes (CNTs) has been fabricated by reducing a graphite oxide (GO)/PANI/CNT precursor prepared by flow-directed assembly from a complex dispersion of GO and PANI/CNT, followed by reoxidation and redoping of the reduced PANI in the composite to restore the conducting PANI structure. Scanning electron microscope images indicate that the ternary composite film is a layered structure with coaxial PANI/CNT nanocables uniformly sandwiched between the GN sheets. Such novel hierarchical structure with high electrical conductivity perfectly facilitates contact between electrolyte ions and PANI for faradaic energy storage and efficiently utilizes the double-layer capacitance at the electrode–electrolyte interfaces. The specific capacitance of the GN/PANI/CNT estimated by galvanostatic charge/discharge measurement is 569 F g⁻¹ (or 188 F cm⁻³ for volumetric capacitance) at a current density of 0.1 A g⁻¹. In addition, the GN/PANI/CNT exhibits good rate capability (60% capacity retention at 10 A g⁻¹) and superior cycling stability (4% fade after 5000 continuous charge/discharge cycles).     

Electrical and thermal conductivity and tensile and flexural properties of carbon nanotube/polycarbonate resins

Adding conductive carbon fillers to insulating thermoplastic polymers increases the resulting composite's electrical conductivity. Carbon nanotubes (CNTs) are very effective at increasing composite electrical conductivity at low loading levels without compromising composite tensile and flexural properties. In this study, varying amounts (2–8 wt %) of CNTs were added to polycarbonate (PC) by melt compounding, and the resulting composites were tested for electrical conductivity (1/electrical resistivity), thermal conductivity, and tensile and flexural properties. The percolation threshold was less than 1.4 vol % CNT, likely because of CNTs high aspect ratio (1000). The addition of CNT to PC increased the composite electrical and thermal conductivity and tensile and flexural modulus. The 6 wt % (4.2 vol %) CNT in PC resin had a good combination of properties for electrical conductivity applications. The electrical resistivity and thermal conductivity were 18 Ω‐cm and 0.28 W/m · K, respectively. The tensile modulus, ultimate tensile strength (UTS), and strain at UTS were 2.7 GPa, 56 MPa, and 2.8%, respectively. The flexural modulus, ultimate flexural strength, and strain at ultimate flexural strength were 3.6 GPa, 125 MPa, and 5.5%, respectively. Ductile tensile behavior is noted in pure PC and in samples containing up to 6 wt % CNT. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Control of Conductive and Mechanical Performances of Poly(Amide‐Imide) Composite Films Utilizing Synergistic Effect of Polyaniline and Multi‐Walled Carbon Nanotube

Functionalized multi‐walled carbon nanotubes (FMWCNTs) have been incorporated into binary composites of poly(amide‐imide) (PAI) and polyaniline (PANI) to improve their conductive and mechanical performances. The conductivity of PAI/PANI/FMWCNTs ternary composites significantly increased from 10^?3 to 8.3 S m^?1 with increasing the weight ratio of FMWCNTs from 0 to 10 wt%, which is much higher than that of the sum of PAI/PANI and PAI/FMWCNTs binary composites. The enhanced conductivity is mainly ascribed to be the more intensive conductive percolating network formed in the PAI/PANI/FMWCNTs ternary composites due to the hydrogen bond interaction among PAI, PANI and FMWCNTs. On the other hand, the tensile strength has been improved by 40% from 25 to 35 MPa. The self‐extinguishing property and phase transition of the ternary films have also been investigated by thermal gravimetric analysis and differential scanning calorimetry, respectively. It is found that the weight ratio of FMWCNTs and the special morphology are the two important factors that induce such unusual properties. POLYM. ENG. SCI., 59:E224–E230, 2019. © 2018 Society of Plastics Engineers     

Synthesis and characterization of polyaniline/carbon nanotube composites

The synthesis of polyaniline (PANI) containing different carbon nanotubes (CNTs) by in situ polymerization is reported in this study. The samples were characterized by X‐ray diffraction and scanning electron microscopy. Fourier transform infrared and ultraviolet–visible spectroscopy were used to determine the change in structure of the polymer/CNT composites. Thermogravimetric analysis showed that the composites had better thermal stability than the pure PANI. Photoluminescence spectra showed a blueshift in the PANI–single‐walled nanotube (SWNT) composite. Low‐temperature (77–300 K) electrical transport properties were measured in the absence and presence of a magnetic field up to 1 T. Direct‐current conductivity exhibited a nonohmic, three‐dimensional variable range hopping mechanism. The room‐temperature magnetoconductivity of all of the investigated samples except the PANI–SWNT composite were negative; however, it was positive for the PANI–SWNT composite, and its magnitude decreased with increasing temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enhanced electrical conductivity of nylon 6 composite using polyaniline-coated multi-walled carbon nanotubes as additives

Aggregation in polymer composites is one of the major obstacles in the carbon nanotubes (CNTs) applications. Authentic CNTs are known to have very good electrical conductivity and mechanical strengths. Surface functionalization can avoid aggregation and help dispersion of CNTs, but reduces CNT’s electrical conductivities and mechanical strengths dramatically. It needs a good way to resolve the above dilemma situation; i.e., poor dispersion-good conductivity vs. good dispersion-poor conductivity. Herein, we demonstrate that in-situ polymerized polyaniline (PANI)-coated CNTs have good polymer matrix compatibility, and are superior electrically conductive fillers to nylon 6 composites. In this report, multi-walled CNTs (MWCNTs) were surface-modified with poly(acrylic acids) (PAA), followed by further coating with PANI. The electrical conductivity of (PANI-MWCNTs)-nylon 6 composite thin film was increased from 10⁻¹² to 7.3 × 10⁻⁵ S/cm in the presence of 1 wt% PANI-coated MWCNTs prepared by physical mixing of PANI and PAA-grafted MWCNTs. When in-situ polymerized PANI-coated MWCNTs were added, the electrical conductivity of MWCNTs-nylon 6 composite was further enhanced by 3 orders to be 3.4 × 10⁻² S/cm at the same 1 wt% loading of MWCNTs. Both Fourier-transformed infrared and uv-visible absorption spectra indicate that there exist very strong site-specific charge transfer interactions between the quinoid rings of PANI and MWCNTs, which results in the superior electrical conductivity of MWCNT-nylon 6 composite.     

Constructing the core–shell structured island domain in polymer blends to achieve high dielectric constant and low loss

Carbon nanotubes (CNTs) and barium titanate (BaTiO₃) (BT) were simultaneously introduced into the immiscible blend poly(ethylene‐co‐vinyl acetate)/thermoplastic urethane (EVA/TPU), and the EVA/TPU/CNT/BT quaternary polymer composite blends with core–shell structured island TPU domain were successfully prepared, in which CNTs in the TPU domain act as the core and the BT spheres at the interface of the TPU and EVA act as the shell. A core–shell structured island can lead to the formation of micro‐capacitors and further accumulate electron storage owing to the incorporation of CNTs and BT; on the other hand, a BT shell can be assembled along the TPU spheres, reducing the possibility of formation of a conductive CNT network, resulting in suppressed dielectric loss. Therefore, CNTs and BT were tailor‐made into blend composites with a core–shell structured domain, which can achieve an increased dielectric constant by 176% and decreased low dielectric loss by 80% compared with the blend composites with only CNTs in the TPU domain. © 2019 Society of Chemical Industry     

Hybrid composites of ABS with carbonaceous fillers for electromagnetic shielding applications

This work evaluates the influence of two types of carbonaceous fillers, carbon black (CB) and carbon nanotubes (CNTs), on the electrical, electromagnetic, and rheological properties of composites based on poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) prepared by the melt mixing. Electrical conductivity, electromagnetic shielding efficiency (EMI SE) in the X‐band frequency range (8–12.4 GHz), and melt flow index (MFI) results showed that ABS/CNT composites exhibit higher electrical conductivity and EMI SE, but lower MFI when compared to ABS/CB composites. The electrical conductivity of the binary composites showed an increase of around 16 orders of magnitude, when compared to neat ABS, for both fillers. Binary composites with 5 and 15 wt % of filler showed an EMI SE of, respectively, ?44 and ?83 dB for ABS/CNT, and ?9 and ?34 dB for ABS/CB. MFI for binary composites with 5 wt % were 15.45 and 0.55 g/10 min for CB and CNT, respectively. Hybrid composites ABS/CNT.CB with 3 wt % total filler and fraction 50:50 and 75:25 showed good correlation between EMI SE and MFI. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46546.     

Thermal conductivity improvement in electrically insulating silicone rubber composites by the construction of hybrid three-dimensional filler networks with boron nitride and carbon nanotubes

In this study, we constructed hybrid three-dimensional (3D) filler networks by simply incorporating a relatively low content of one-dimensional carbon nanotubes (CNTs; 0.0005–0.25 vol %) and a certain content of two-dimensional boron nitride (BN; 30 phr) in a silicone rubber (SIR) matrix. As indicated by transmission electron microscopy observation, flexible CNTs can serve as bridges to connect BN platelets in different layers to form hybrid 3D thermally conductive networks; this results in an increase in thermally conductive pathways, and the isolation between CNTs can prevent the formation of electrically conductive networks. Compared to the SIR–BN composite with the same BN content, the SIR–BN–CNT composites exhibited improved thermal conductivity, slightly increased volume resistivity, and comparable breakdown strength without a largely decreased flexibility. When 0.25 vol % CNTs were incorporated, the SIR–BN–CNT composite exhibited 75 and 25% higher thermal conductivities relative to the neat SIR and SIR–BN composite with 30 phr BN, respectively, and a thermal conductivity that was even comparable to SIR–BN composite with 40 phr BN. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46929.     

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     

Flexible poly(styrene-b-(ethylene-co-butylene)-b-styrene) nanocomposites for electromagnetic interference shielding

In this report, multiwalled carbon nanotubes (CNT) embedded poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) microspheres (CNT/SEBS) were prepared by solvent evaporation method. Reduced graphene oxide (rGO) nanosheets were used to cover the surface of CNT/SEBS microspheres. The CNT/SEBS/rGO nanocomposites with special segregated conductive network were fabricated by hot pressing these as-prepared complex microspheres. The morphology, electrical percolation threshold, electrical conductivity, and electromagnetic interference (EMI) shielding effectiveness (SE) of CNT/SEBS/rGO composites were characterized. The shielding mechanisms were discussed in detail. Analysis of electrical conductive performance shows that the electrical percolation threshold of rGO is 0.22 vol %. Results of EMI shielding test confirmed the synergistic effect between CNT and rGO. The EMI SE of the composite filled by 2.1 vol % CNT and 3.35 vol % rGO can achieve 26 dB in 8.2− 12.4 GHz (X band), which exceeds the basic requirement for commercial application (20 dB). Its reflectance coefficient (19–41%) indicates that the most part of incident electromagnetic (EM) wave energy is attenuated through absorption mechanism. This kind of absorptive EMI shielding material can be applied without serious secondary EM radiation pollution problems. The effects of filler content, molding temperature on EMI SE, and shielding mechanism were also investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48542.