Investigation of electrical,mechanical, and thermal properties of functionalized multiwalled carbon nanotubes‐reduced graphene Oxide/PMMA hybrid nanocomposites

Electrical, mechanical, and thermal properties of the poly(methyl methacrylate) (PMMA) composites containing functionalized multiwalled carbon nanotubes (f‐MWCNTs) and reduced graphene oxide (rGO) hybrid nanofillers have been investigated. The observed electrical percolation threshold of FHC is 0.8 wt% with maximum conductivity of 1.21 × 10^?3 S/cm at 4 wt% of f‐MWCNTs. The electrical transport mechanism and magneto resistance studied of hybrid composites have also been investigated. Progressive addition of f‐MWCNTs in rGO/PMMA composite results increase in mechanical (tensile strength and Young's modulus) and thermal (thermal stability) properties of f‐MWCNTs‐rGO/PMMA hybrid nanocomposites (FHC). The increased mechanical properties are due to the efficient load transfer from PMMA matrix to f‐MWCNTs and rGO through better chemical interaction. The strong interaction between PMMA and f‐MWCNTs‐rGO in FHC is the main cause for improved thermal stability. POLYM. ENG. SCI., 59:1075–1083, 2019. © 2019 Society of Plastics Engineers     

Nanoscale reinforcement of polypropylene composites with carbon nanotubes and clay: Dispersion state,electromagnetic and nanomechanical properties

In the present study, the bifiller system incorporating various amount of multiwalled carbon nanotubes (MWCNTs) and 3 wt% clay in polypropylene is investigated to obtain composites with multifunctional performance. The dispersion state of two nanofillers in the polypropylene matrix was characterized by applying TEM and Raman spectroscopy. Both composites demonstrate similar rheological behavior with a rheological percolation threshold of ?_p1 = 1.5 wt% for the monofiller (MWCNTs) and ?_p2 = 2 wt% for the bifiller systems (MWCNTs and 3% clay). The effect of two nanofillers on electromagnetic and nanomechanical properties was evaluated. Above rheological percolation both type composites show considerable electromagnetic shielding efficiency at small layer thickness due mostly to the addition of MWCNTs. The nanomechanical properties improvement is strongly dependent on the structure formed by MWCNTs in the polymer. The hardness and Young's modulus, measured by nanoindentation, is higher for the bifiller systems in comparison with the monofiller one above the rheological percolation threshold. This was attributed to the continuous network structure formed by interacted MWCNTs and infiltrated fine clay stacks. POLYM. ENG. SCI., 56:269–277, 2016. © 2015 Society of Plastics Engineers     

Dispersion and aspect ratio of carbon nanotubes in aqueous suspension and their relationship with electrical resistivity of carbon nanotube filled polymer composites

Multiwalled carbon nanotube (MWCNT)/acrylonitrile butadiene styrene (ABS) composites were prepared by a processing method using solvent–nonsolvent precipitation. Size distributions of MWCNT agglomerates in aqueous suspension were investigated in order to predict aspect ratio of nanotubes by evaluating the effects of sonication time, MWCNT content, and surfactant. Aspect ratios of MWCNTs were predicted on the basis of the size distribution measurements for MWCNT agglomerates. Sonication time or applied sonic energy has a strong effect on the size distribution of MWCNT agglomerates. Compared with simple shear mixing method, it was shown that this processing method is more suitable for the MWCNT/ABS composites. An electrical percolation threshold was observed for the weight fraction of MWCNTs in the range of about 0.5–1.0 wt.%. Shorter MWCNTs are more suitable to induce fine dispersion, but lead to higher percolation threshold weight fraction. It was illustrated that fine dispersion can overcome the handicap of short length or low aspect ratio of MWCNTs.     

Electrical and dielectric properties of multiwall carbon nanotube/polyaniline composites

In this paper, electrical and dielectric properties of multiwall carbon nanotubes (MWCNTs)/insulating polyaniline (PANI) composites were studied. A mixture of MWCNTs and insulating polyaniline was dispersed in an ethanol solution by ultrasonic process, subsequently dried, and was hot-pressed at 200 °C under 30 MPa. Electrical and dielectric properties of the composites were measured. The experimental results show that the dc conductivities of the composites exhibit a typical percolation behavior with a low percolation threshold of 5.85 wt.% MWCNTs content. The dielectric constant of the composites increases remarkably with the increasing MWCNTs concentration, when the MWCNTs concentration was close to percolation threshold. This may be attributed to the critical behavior of the dielectric constant near the percolation threshold as well as to the polarization effects between the clusters inside the composites.     

Mechanical,dielectric, and magnetic properties of the silicone elastomer with multi‐walled carbon nanotubes as a nanofiller

Silicone elastomer and multi‐walled carbon nanotubes (MWCNTs) composites, applicable as actuators and controllable dampers, were studied. Dynamic mechanical analysis (DMA) and vibrating sample magnetometry (VSM) were used to investigate the mechanical and magnetic properties of silicone elastomers and MWCNTs composites. Also, measurement of their dielectric property was conducted. The addition of MWCNT was able to tailor the damping and dielectric properties of the silicone elastomer. In this study, a 0.7 wt% of MWCNT composite demonstrated an attractive condition for the damping and the dielectric property. Exceedingly, the modulus increased with the application of a magnetic field. The good filler effect with the small addition of the MWCNTs content is caused by their unique structure, catalytic effect, and magnetic property. POLYM. ENG. SCI., 47:1396–1405, 2007. © 2007 Society of Plastics Engineers     

The electrical properties and crystallization of stereocomplex poly(lactic acid) filled with carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) filled poly(l-lactic acid) (PLLA) and PLLA/poly(d-lactic acid) (PDLA) composites were prepared through a directly melt mixing process. A special crystalline structure of stereocomplex was formed by PLLA and PDLA, which was easily found when mixing two polymers with identical chemical composition but different steric structures. The electrical conductivities were greatly improved by the formation of stereocomplex compared to that of PLLA/MWCNT composites at same MWCNT content. The percolation threshold of the PLLA/PDLA/MWCNT composite at a PLLA/PDLA weight ratio of 50/50 was 0.35 wt%, while being 1.43 wt% of PLLA/MWCNT composites. The X-ray diffraction, non-isothermal and isothermal crystallization results showed that the formation of stereocomplex greatly increased the crystallinity of the composites, meanwhile MWCNTs acted as heterogeneous nucleating agent, which significantly accelerated the nucleation and spherulite growth. Therefore, the PLLA/PDLA/MWCNT composites have a very low percolation threshold due to the volume exclusion effect.     

Injection‐molded parts of polypropylene/multi‐wall carbon nanotubes composites with an electrically conductive tridimensional network

Polypropylene‐based composites filled with multi‐wall carbon nanotubes (MWCNTs), ranging from 1 to 6 wt%, were obtained by injection molding from a previous masterbatch compounded by twin‐screw extrusion (TSE). Resultant electrical percolation phenomenon was related to the ultrathin structure of the carbon‐based fillers and the high dispersion achieved in the thermoplastic matrix. In particular, conductivity experiments showed a threshold value of 3 wt% (1.3 vol%) of MWCNTs for percolation to occur. Electrical percolation was achieved as a result of the formation of an interconnected three‐dimensional structure compromising a top average inter‐nanotube distance of about 493 nm among isolated nanotubes in polypropylene. The current work is hoped to bear significance toward understanding of the electrical performance for industrial ultrathin carbon black‐based polyolefin composites. POLYM. COMPOS., 37:488–496, 2016. © 2014 Society of Plastics Engineers     

Synthesis and characterization of multiwalled carbon nanotube/polyurethane composites via surface modification multiwalled carbon nanotubes using silane coupling agent

Well‐dispersed multiwalled carbon nanotubes/polyurethane (MWCNTs/PU) composites were synthesized in situ polymerization based on treating MWCNTs with nitric acid and silane coupling agent. The morphology and degree of dispersion of the MWCNTs were studied using a high resolution transmission electron microscopy (HR‐TEM) and X‐ray powder diffraction (XRD). The result showed that MWCNTs could be dispersed still in the PU matrix well with the addition of 2 wt% MWCNTs. The thermal and mechanical properties of the composites were characterized by dynamic mechanical thermal analysis, thermogravimetric analysis, tensile, and impact testing. The result suggested that the glass transition temperature (T_g) of composites increased greatly with increasing MWCNTs content slightly, and the MWCNTs is also helpful to improve mechanical properties of composites. Furthermore, the composites have an excellent mechanical property with the addition of 0.5 wt% MWCNTs. The electrical property testing indicates that the MWCNTs can improve evidently the electrical properties of composites when adding 1 wt% MWCNTs to the PU matrix. The volume resistivity of composites reaches to an equilibrium value. POLYM. COMPOS., 33:1866–1873, 2012. © 2012 Society of Plastics Engineers     

Effects of multi‐walled carbon nanotubes and conductive carbon black on electrical,dielectric, and mechanical properties of epoxidized natural rubber composites

The influence of multi‐walled carbon nanotubes (MWCNTs) and conductive carbon black (CCB) on cure, electrical, dielectric, and mechanical properties of epoxidized natural rubber (ENR) composites was investigated. It was found that short MWCNTs (S‐MWCNTs) with low loading significantly affected the cure characteristics in a way similar to high loading of CCB. Moreover, the ENR/S‐MWCNTs composites exhibited high AC conductivity, dielectric constant, and dielectric loss tangent (tan δ ) compared to the ENR/CCB and ENR/L‐MWCNTs (long MWCNTs) composites. In addition, the S‐MWCNTs composites showed the lowest percolation threshold concentration, defined as the lowest loading to form conductive paths in the insulating ENR matrix. This might be attributed to the comparatively high interfacial polarization, with good dispersion and distribution, of the S‐MWCNTs in ENR matrix. These characteristics were confirmed by TEM imaging and by a high bound rubber content, corroborating strong filler–rubber interactions in the ENR/S‐MWCNTs composites. However, the L‐MWCNTs composites showed the lowest electrical and other related properties, despite the highest aspect ratio and specific surface area of this filler. This might be because of the flocculation of nanotubes by mutual entanglement, leading to a poor uneven distribution in the ENR matrix. POLYM. COMPOS., 38:1031–1042, 2017. © 2015 Society of Plastics Engineers     

Control of carbon nanotubes at the interface of a co-continuous immiscible polymer blend to fabricate conductive composites with ultralow percolation thresholds

The concept of “double percolation”, i.e., conductive fillers are selectively located in one phase of a co-continuous polymer blend to form a percolated network in the selected phase, is widely used to reduce the percolation thresholds of conductive polymer composites to a fraction of their original values. However, it is expected that the percolation threshold can be significantly reduced further if the conductive fillers are only selectively distributed at the continuous interface of the co-continuous polymer blend, where only a very small amount of fillers are needed to build up the conductive percolated network. Multiwalled carbon nanotubes (MWCNTs) with very high aspect ratio (ca. 1000) are selectively distributed at a continuous interface of a co-continuous immiscible poly(lactic acid)/poly(ε-caprolactone) (PLA/PCL) blend at a weight ratio of 50/50 by controlling the migration process of MWCNTs from the unfavorable PLA to the favorable PCL phase. Compared to the PLA/PCL/MWCNTs composites by the traditional double percolation method (percolation threshold is ca. 0.97 wt%), the percolation threshold of PLA/MWCNTs/PCL composites (ca. 0.025 wt%) drops 2 orders of magnitude due to controlling the MWCNTs at the continuous interface between the PLA and PCL phases.     

Rheology,crystallization behavior,and dielectric study on molecular dynamics of polypropylene composites with multiwalled carbon nanotubes and clay

The study is focused on joint effects of two nanofillers in polypropylene (PP) reinforced with 3 wt% organo‐clay (ОC) and 0.1–5 wt% multi‐wall carbon nanotubes (MWCNTs). The composites were produced by extrusion and characterized by rheology, differential scanning calorimeter (DSC), thermally stimulated depolarization currents (TSDC), and dielectric relaxation spectroscopy (DRS). Rheological data indicates а formation of a network structure related to percolation above 1 wt% nanotubes. The flow activation energy (Ea) decreases above the percolation threshold, thus, the presence of clay improves the debundling of MWCNTs and releases the segmental motion of polymer chains. The clay does not affect the crystallization behavior of PP, but the nucleation is enhanced strongly by the MWCNTs. Dielectric measurements reveal that the presence of clay affects the molecular mobility of PP at the amorphous phase. The DSC results imply that around 80°C a cold crystallization process occur in the PP phase which has a significant impact on the dielectric segmental relaxation process and gives rise to the appearance of an additional process, the so called “interfacial” relaxation process. This new relaxation process in the three‐phase composites was attributed to an interfacial polarization process due to blocking of charge carriers at polymer/clay interfaces. POLYM. COMPOS., 37:2756–2769, 2016. © 2015 Society of Plastics Engineers     

Electrical conductivity of poly(vinylidene fluoride)/carbon nanotube composites with a spherical substructure

Poly(vinylidene fluoride) (PVDF)/multiwalled carbon nanotube (MWCNT) conducting composites were prepared with a percolation threshold as low as 0.07 wt%. The MWCNTs in a PVDF solution can lead to the formation of spherical PVDF/MWCNT composite particles by sonication. The MWCNTs coated on the surfaces of the spherical particles form a conduction network when the spheres coalesce to form a solid composite. The existence of the spherical particles with a substructure results in the reduction in MWCNT content and improves the electrical conductivity of the composites.     

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     

Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm⁻¹ for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10⁻²⁰ to 10⁻⁴ S/cm. The storage modulus (G′) versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical properties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T_c) and fraction of PE that was crystalline (F_c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT.     

Fabrication and dielectric properties of poly(ether ether ketone)/polyimide blends with selectively distributed multi‐walled carbon nanotubes

The distribution and contents of conductive fillers have a decisive influence on the dielectric properties of polymer/conductive filler composites. Herein, we clarified how the phase morphology and filler contents affect the dielectric properties of poly(ether ether ketone) (PEEK)/polyimide (TPI)/multi‐walled carbon nanotubes (MWCNTs) composites, in which MWCNTs were selectively located in the TPI phase. Firstly, PEEK/TPI/MWCNTs composites with identical MWCNTs content but different PEEK/TPI ratios were prepared. The composites with co‐continuous phase structure exhibited much better dielectric properties than those with sea–island structure. Then, PEEK/TPI/MWCNTs composites with the same PEEK/TPI ratio but various MWCNTs contents were prepared. The dielectric constant of the composite with 2 wt% MWCNTs reached 11306, which is because the formation of a co‐continuous phase structure benefited the mini‐capacitor network. Our results provide an effective method to develop high‐dielectric‐constant composites using the concept of double percolation. © 2015 Society of Chemical Industry     

Electrical,mechanical, and crystallization properties of ethylene‐tetrafluoroethylene copolymer/multiwalled carbon nanotube composites

Multiwalled carbon nanotubes (MWCNTs) were melt‐mixed in a conical twin‐screw extruder with a random copolymer of ethylene and tetrafluoroethylene. Surprisingly, the electrical percolation threshold of the resultant composites was quite low; ～0.9 wt %. In fact, this value is as low or lower than the value for most MWCNT/semicrystalline polymer composites made with roughly equivalent aspect ratio tubes mixed in a similar manner, for example, melt mixing. This low percolation threshold, suggestive of good dispersion, occurred even though the polymer surface energy is quite low which should make tubes more difficult to disperse. Dynamic mechanical measurements confirmed the rather low percolation threshold. The effect of nanotubes on crystallization kinetics was quite small; suggesting perhaps that a lack of nucleation which in turn reduces/eliminates an insulating crystalline polymer layer around the nanotubes might explain the low percolation threshold. Finally, the modulus increased with the addition of nanotubes and the strain at break decreased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41052.     

Toward improved mechanical performance of multiscale carbon fiber and carbon nanotube epoxy composites

A novel class of multiscale epoxy composites was developed containing carbon fibers (CFs) and multiwalled carbon nanotubes (MWCNTs) to explore their mutual effect on the mechanical performance of composites. The loading of CFs in composites was kept constant at ∼60 wt%, while the contents of MWCNTs were increased from 0.5 to 2.0 wt%. MWCNTs were functionalized through acid treatment before incorporating into epoxy matrix to promote dispersion quality. The developed composites were characterized microstructurally by scanning electron microscopy and mechanically by tensile, flexural, edgewise compression, and hardness tests. Homogeneous dispersion of MWCNTs was observed until their loading of 1.5 wt%, which enhanced the mechanical performance of composites. Hardness increased up to 47% while tensile, flexural, and edgewise compressive moduli increased to 40%, 16.3%, and 164%, respectively. Moreover, tensile, flexural, and edgewise compressive strengths showed rises of 45%, 15.2%, and 43%, respectively. The fracture strain increased in both the tensile and flexural tests while it decreased in edgewise compressive tests. Increasing the MWCNTs in composites to 2.0 wt% produced their agglomerates and reversed the rising trend in mechanical properties. POLYM. COMPOS., 38:1519–1528, 2017. © 2015 Society of Plastics Engineers     

Enhancing electrical properties of MWCNTs in immiscible blends of poly(methyl methacrylate) and styrene‐acrylonitrile copolymer by selective localization

Multiwalled carbon nanotubes (MWCNTs) were introduced into poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile copolymer (SAN) blends by melt mixing in an asymmetric miniature mixer (APAM). A composition of 70 wt% of PMMA and 30 wt% of SAN was mixed to create a co‐continuous morphology. Transmission electron microscopy images of ultra‐microtomed samples (70 nm in thickness) showed selective localization of MWCNTs inside the percolated SAN phase. The occurrence of the double percolation phenomenon resulted in lower electrical percolation thresholds of PMMA/SAN/MWCNT blends molded at high temperatures. Dielectric spectroscopy indicated a higher electrical permittivity for samples that were compression molded at 260°C. Due to the higher affinity of MWCNTs to SAN, there was a migration of MWCNTs into the SAN phase during the melt processing. Conductivity measurements revealed a significant decrease in electrical percolation threshold (0.4 wt%) for PMMA70/SAN30 blends compared with MWCNT‐filled SAN and MWCNT‐filled PMMA (ca. 0.8 wt%). POLYM. COMPOS., 37:1523–1530, 2016. © 2014 Society of Plastics Engineers     

Characterization of conductive multiwall carbon nanotube/polystyrene composites prepared by latex technology

Conductive multiwall carbon nanotube/polystyrene (MWCNT/PS) composites are prepared based on latex technology. MWCNTs are first dispersed in aqueous solution of sodium dodecyl sulfate (SDS) driven by sonication and then mixed with different amounts of PS latex. From these mixtures MWCNT/PS composites were prepared by freeze-drying and compression molding. The dispersion of MWCNTs in aqueous SDS solution and in the PS matrix is monitored by UV–vis, transmission electron microscopy, electron tomography and scanning electron microscopy. When applying adequate preparation conditions, MWCNTs are well dispersed and homogeneously incorporated in the PS matrix. The percolation threshold for conduction is about 1.5 wt% of MWCNTs in the composites, and a maximum conductivity of about 1 S m⁻¹ can be achieved. The approach presented can be adapted to other MWCNT/polymer latex systems.     

Carbon nanotube/polymer nanocomposites: A study on mechanical integrity through nanoindentation

Carbon nanotubes (CNTs) are under intense investigation in materials science owing to their potential for modifying the mechanical proprieties of their composites. In this work, nanomechanical and nanotribological properties of polymer composites, reinforced with multiwall carbon nanotubes (MWCNTs) and single wall carbon nanotubes (SWCNTs), have been studied using the nanoindentation and nanoscratch technique. In particular, three different epoxy resins reinforced using several percentage of two different types of MWCNTs have been studied (range 0–7 wt%). Another resin was reinforced using MWCNTs (range 0–2.5 wt%) and SWCNTs (range 0–5 wt%) as fillers. Hardness and elastic modulus using nanoindenter instrument have been evaluated, while the coefficient of friction of the nanocomposites is obtained using nanoscratch. The results show an evident dependence with the percentage of CNTs. For all types of resins, an optimum in nanomechanical properties is found at intermediate levels of CNTs filling. POLYM. COMPOS., 36:1432–1446, 2015. © 2014 Society of Plastics Engineers