The electrical properties of polymer nanocomposites with carbon nanotube fillers

The electrical properties of polymer nanocomposites containing a small amount of carbon nanotube (CNT) are remarkably superior to those of conventional electronic composites. Based on three-dimensional (3D) statistical percolation and 3D resistor network modeling, the electrical properties of CNT nanocomposites, at and after percolation, were successfully predicted in this work. The numerical analysis was also extended to investigate the effects of the aspect ratio, the electrical conductivity, the aggregation and the shape of CNTs on the electrical properties of the nanocomposites. A simple empirical model was also established based on present numerical simulations to predict the electrical conductivity in several electronic composites with various fillers. This investigation further highlighted the importance of theoretical and numerical analyses in the exploration of basic physical phenomena, such as percolation and conductivity in novel nanocomposites.     

Crystalline morphology and properties of multi-walled carbon nanotube filled isotactic polypropylene nanocomposites: Influence of filler size and loading

Isotactic polypropylene (PP) nanocomposites with multi-walled carbon nanotubes (MWCNTs) of various diameters (10–50 nm) were fabricated by extrusion and compression-molding techniques and characterized by X-ray diffraction measurements, differential scanning calorimetry, scanning electron microscopy, mechanical test and differential thermal analyses. The pure PP exhibits both the a- and b-axes oriented α-crystal, whereas the MWCNTs induce the b-axis orientation of the α-crystal along with the formation of minor γ-phase crystal in nanocomposites. Crystallinity, long period of lamellae, tensile strength, tensile modulus (TM) and microhardness (H) of PP considerably change by different loading and sizes of MWCNTs. The estimated values H/TM = 0.09–0.10 for all samples approach the predicted value of 0.10 for polymers. The increase in crystallinity has been demonstrated by both XRD and DSC studies. Mathematical models have been invoked to explain the changes in mechanical properties. An increase in thermal stability of polymer matrix occurs with increasing MWCNTs size and loading.     

Masterbatch-based multi-walled carbon nanotube filled polypropylene nanocomposites: Assessment of rheological and mechanical properties

Polypropylene (PP)/multi-wall carbon nanotubes (MWNTs) nanocomposites were prepared by diluting a PP/MWNT masterbatch by melt compounding with a twin screw extruder and prepared nanocomposites were characterized for their rheological, mechanical and morphological properties in terms of MWNT loading. The rheological results showed that the materials experience a fluid–solid transition at the composition of 2 wt.%, beyond which a continuous MWNT network forms throughout the matrix and in turn promotes the reinforcement. The tensile modulus and yield stress of the nanocomposites are substantially increased relative to the neat polypropylene. Nanotube reinforcement thus enhanced the yield stress, while reducing the ductility. The same behavior is observed in flexural tests. Charpy impact resistance of the notched samples increases slightly by the addition of MWNT, while impact resistance for the un-notched samples decreases with the addition of MWNTs. Finally, optimum in mechanical properties was observed at 2 wt.% MWNTs, which is near the rheological percolation threshold. From transmission electron microscopic (TEM) and scanning electron microscopy (SEM) images, it was observed that nanotubes are distributed reasonably uniformly indicating a good dispersion of nanotubes in the PP matrix. These results reveal that, preparation of nanocomposites from masterbatch dilution is an excellent method to obtain well-dispersed CNTs, while limiting the handling difficulties in plastics processing industrial workshops.     

Effects of carbon nanotube alignment on electrical and mechanical properties of epoxy nanocomposites

This paper reports the alignment of multi-walled carbon nanotubes (MWCNTs) in an epoxy matrix as a result of DC electric fields applied during composite curing. Optical microscopy and polarized Raman spectroscopy are used to confirm the CNT alignment. The alignment of CNTs gives rise to much improved electrical conductivity, elastic modulus and quasi-static fracture toughness compared to those with CNTs of random orientation. An extraordinarily low electrical percolation threshold of about 0.0031 vol% is achieved when measured along the alignment, which is more than one order of magnitude lower than 0.034 vol% with random orientation or that measured perpendicular to the aligned CNTs. The examination of the fracture surfaces identifies pertinent toughening mechanisms in aligned CNT composites, namely crack tip deflection and CNT pullout. The significance of this paper is that the technique employed here can tailor the physical, mechanical and fracture properties of bulk nanocomposites even at a very low CNT concentration.     

Functionalized graphene sheets filled isotactic polypropylene nanocomposites

The graphene oxide sheets (GOs) reacted with 4,4′-diphenylmethane diisocyanate (MDI) and then stearic acid to form the functionalized graphene sheets (FGs), in order to improve their compatibility with isotactic polypropylene (iPP). The iPP incorporated with FGs were adequately mixed in a Haaker mixer and then compression molded to obtain the iPP/FGs nanocomposites. The crystallization, thermal stability and mechanical properties of the nanocomposites together with iPP/graphite sheets (Gs) and iPP/GOs composites were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and tensile test. The FGs achieved good dispersion with exfoliated and intercalated nanostructure and strong interfacial adhesion with iPP, which made the nanocomposites have a significant enhancement of thermal stability and mechanical properties at low FGs loadings.     

Effect of carbon nanotube orientation on the mechanical properties of nanocomposites

Carbon nanotubes (CNTs) have been regarded as ideal reinforcements of high-performance composites with enormous applications. In this paper, nano-structure is modeled as a linearly elastic composite medium, which consists of a homogeneous matrix having hexagonal representative volume elements (RVEs) and homogeneous cylindrical nanotubes with various inclination angles. Effects of inclined carbon nanotubes on mechanical properties are investigated for nano-composites using 3-D hexagonal representative volume element (RVE) with short and straight CNTs. The CNT is modeled as a continuum hollow cylindrical shape elastic material with different angles. The effect of the inclination of the CNT and its parameters is studied. Numerical equations are used to extract the effective material properties for the hexagonal RVE under axial as well as lateral loading conditions. The computational results indicated that elastic modulus of nano-composite is remarkably dependent on the orientation of the dispersed SWNTs. It is observed that the inclination significantly reduces the effective Young’s modulus of elasticity under an axial stretch. When compared with lateral loading case, effective reinforcement is found better in axial loading case. The effective moduli are very sensitive to the inclination and this sensitivity decreases with the increase of the waviness. In the case of short CNTs, increasing trend is observed up to a specific value of waviness index. It is also found from the simulation results that geometry of RVE does not have much significance on stiffness of nano-structures. The results obtained for straight CNTs are consistent with ERM results for hexagonal RVEs, which validate the proposed model results.     

Electric heating films based on m-aramid nanocomposites containing hybrid fillers of graphene and carbon nanotube

m-Aramid nanocomposite films containing 1.0 wt% hybrid fillers of different compositions of graphene and multi-walled carbon nanotube (MWCNT) are prepared by an efficient solution-casting method, and their electric heating behavior is investigated as a function of the composition of hybrid fillers. Electron microscope images and X-ray diffraction patterns reveal that the hybrid fillers are well dispersed in the m-aramid matrix by forming interconnected networks among graphene sheets and MWCNTs. The electrical resistivity of the nanocomposite films is decreased gradually from ~10⁵ to 10¹ Ω cm with increasing the MWCNT content in the hybrid fillers. Accordingly, maximum temperature attained at a given applied voltage for the nanocomposite films can be finely controlled by the graphene/MWCNT composition of 1.0 wt% hybrid fillers. The m-aramid/hybrid filler nanocomposite films also exhibit excellent electric heating performance in aspects of rapid temperature response and high electric power efficiency at applied voltages of 1–100 V.     

Effects of recycling on the microstructure and the mechanical properties of isotactic polypropylene

Polypropylene (PP) was injection moulded several times to mimic the effect of recycling procedures. The influence of the recycling was studied by following changes in chemical structure, melt viscosity, crystallisation behaviour, and tensile and fracture properties. The main effect of recycling is the lowering of the melt viscosity, which is attributed to molecular weight decrease. Recycled PP exhibits greater crystallisation rate, higher crystallinity and equilibrium melting temperature than those measured for virgin PP. Elastic modulus and yield stress increase with the number of recycling steps. However, elongation at break and fracture toughness decrease.     

Microwave-absorbing properties of silver nanoparticle/carbon nanotube hybrid nanocomposites

Silver (Ag) nanoparticles fabricated by chemical reduction process were grafted onto the surface of carbon nanotubes (CNTs) to prepare hybrid nanocomposites. The Ag/CNT hybrid nanomaterials were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The Ag/CNT hybrid nanomaterials were then loaded in paraffin wax, and pressed into toroidal shape with thickness of 1 mm to evaluate their complex permittivity and complex permeability by scattering parameters measurement method in reflection mode using vector network analyzer. The reflection loss of the samples was calculated according to the transmission line theory using their measured complex permittivity and permeability. The minimum reflection loss of the Ag/CNT hybrid nanocomposite sample with a thickness of 1 mm reached 21.9 dB (over 99 % absorption) at 12.9 GHz, and also exhibited a wide response bandwidth where the frequency bandwidth of the reflection loss of less than ?10 dB (over 90 % absorption) was from 11.7 to 14.0 GHz. The Ag/CNT hybrid nanocomposite with thickness of 6 mm showed a minimum reflection loss of ~?32.1 dB (over 99.9 % absorption) at 3.0 GHz and was the best absorber when compared with the other samples of different thickness. The reflection loss shifted to lower frequency as the thickness of the samples increased. The capability to modulate the absorption band of these samples to suit various applications in different frequency bands simply by manipulating their thickness indicates that these hybrid nanocomposites could be a promising microwave absorber.     

Effect of different carbon fillers and dopant acids on electrical properties of polyaniline nanocomposites

Electrically conducting nanocomposites of polyaniline (PANI) with carbon-based fillers have evinced considerable interest for various applications such as rechargeable batteries, microelectronics, sensors, electrochromic displays and light-emitting and photovoltaic devices. The nature of both the carbon filler and the dopant acid can significantly influence the conductivity of these nanocomposites. This paper describes the effects of carbon fillers like carbon black (CB), graphite (GR) and muti-walled carbon nanotubes (MWCNT) and of dopant acids like methane sulfonic acid (MSA), camphor sulfonic acid (CSA), hydrochloric acid (HCl) and sulfuric acid (H₂SO₄) on the electrical conductivity of PANI. The morphological, structural and electrical properties of neat PANI and carbon–PANI nanocomposites were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT–IR), UV–Vis spectroscopy and the four-point probe technique, respectively. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) studies were also conducted for different PANI composites. The results show that PANI and carbon–PANI composites with organic acid dopants show good thermal stability and higher electrical conductivity than those with inorganic acid dopants. Also, carbon–PANI composites generally show higher electrical conductivity than neat PANI, with highest conductivities for PANI–CNT composites. Thus, in essence, PANI–CNT composites prepared using organic acid dopants are most suitable for conducting applications.     

Processing and electrical properties of carbon nanotube/vinyl ester nanocomposites

Vinyl ester resins are often utilized in advanced naval composite structures due to the relatively low viscosity of the resin and the capability to cure at ambient temperatures. These qualities facilitate the production of large naval composite structures using resin infusion techniques. Vinyl ester monomer was synthesized from the epoxy resin to overcome processing challenges associated with volatility of the styrene monomer in vinyl ester resin. In this research we have investigated the use of a calendering approach for dispersion of multi-walled carbon nanotubes in vinyl ester monomer, and the subsequent processing of nanotube/vinyl ester composites. The high aspect ratios of the carbon nanotubes were preserved during processing and enabled the formation of a conductive percolating network at low nanotube concentrations. An electrical percolation threshold below 0.1 wt.% carbon nanotubes in vinyl ester was observed. Formation of percolating carbon nanotube networks at low concentration holds promise for the utilization of carbon nanotubes as in situ sensors for detecting deformation and damage in advanced naval composites.     

Static and dynamic mechanical properties of polydimethylsiloxane/carbon nanotube nanocomposites

The purpose of this study is to investigate the static and dynamic mechanical properties of polydimethylsiloxane (PDMS) and the mixture of PDMS and carbon nanotubes. The PDMS/CNT nanocomposites were stirred by an ultrasonic instrument to prevent agglomerations. The tested specimens of nanocomposites were manufactured by using the thermoforming method at 150 °C for 15 min. A micro tensile tester was adopted in this testing system with a maximum load of 500 mN and a crosshead extension of 150 mm. The static elastic modulus can be calculated by means of a tensile test and the average elastic modulus of pure PDMS is 1.65 MPa. In addition, the Nano Bionix tensile tester was also used to perform the dynamic mechanical analysis. Its dynamic frequency range is from 0.1 Hz to 2.5 KHz. The dynamic properties of PDMS/CNT nanocomposites such as storage and loss modulus can be obtained by this system. The storage modulus increased with the CNT content and also with the higher frequencies. Finally, the nanoindentation measurement system was employed to characterize the mechanical properties of PDMS and PDMS/CNTs. The measurement results of elastic modulus by a nanoindentation test have the similar trend with the results obtained by the tensile test method.     

Electrical conductivity and mechanical properties of multiwalled carbon nanotube-reinforced polypropylene nanocomposites

In this paper, the electrical conductivity and mechanical properties such as elastic modulus of multiwalled carbon nanotubes (MWCNTs) reinforced polypropylene (PP) nanocomposites were investigated both experimentally and theoretically. MWCNT-PP nanocomposites samples were produced using injection mold at different injection velocities. The range of the CNT fillers is from 0 up to 12?wt%. The influence of the injection velocity and the volume fraction of CNTs on both electrical conductivity and mechanical properties of the nanocomposites were studied. The injection speed showed some effect on the electrical conductivity, but no significant influence on the mechanical properties such as elastic modulus and stress-strain relations of the composites under tensile loading. Parallel to the experimental investigation, for electrical conductivity, a percolation theory was applied to study the electrical conductivity of the nanocomposite system in terms of content of nanotubes. Both Kirkpatrick (Rev Mod Phys 45:574?C588, 1973) and McLachlan et?al. (J Polym Sci B 43:3273?C3287, 2005) models were used to determine the transition from low conductivity to high conductivity in which designates as percolation threshold. It was found that the percolation threshold of CNT/PP composites is close to 3.8?wt%. For mechanical properties of the system, several micromechanical models were applied to elucidate the elastic properties of the nanocomposites. The results indicate that the interphase between the CNT and the polymers plays an important role in determining the elastic modulus of the system.     

Electrically conductive carbon nanotube/polypropylene nanocomposite with improved mechanical properties

Conductive polymer nanocomposites based on carbon nanotubes (CNTs) have wide range of applications in the electronics and energy sectors. For many of these applications, such as the electromagnetic interference (EMI) shielding, high nanofiller loading is typically needed to achieve the desired properties. The high nanofiller concentration deteriorates the composite's tensile strength due to the increase in nanofiller aggregation. In this work, highly conductive CNT/polypropylene (PP) nanocomposite with improved tensile strength was prepared by melt mixing. The effects of CNT content on the processing behavior, microstructure, mechanical and electrical properties of the nanocomposite were investigated. Scanning electron microscopy was used to investigate the composite microstructure. Good level of CNT dispersion with remarkable adhesion at the CNT/PP interface was observed. Based on a theoretical model, the interfacial strength was estimated to be in the range of 36–58 MPa. As a result of this microstructure, significant enhancement in ultimate tensile strength was reported with the increase of CNT content. The tensile strength of the 20 wt.% CNT/PP nanocomposite was 80% higher than that of the unfilled PP. Moreover, and due to the good dispersion of CNT particles, an electrical percolation threshold concentration of 0.93 wt.% (0.5 vol.%) was obtained.     

An investigation on the dispersibility of carbon nanotube in the latex nanocomposites using rheological properties

This study focuses on the preparation and rheological investigations of carboxylated styrene butadiene rubber latex (XSBR) – multiwall carbon nanotube (CNT) nanocomposites. Two types of non-functionalized CNT and hydroxyl functionalized multiwall carbon nanotube (CNTOH) were used. A new approach based on concurrent ball milling of CNT and XSBR latex was applied to embed the nano material into the carboxylated latex. To do so, first of all, the effect of ball milling on the colloidal stability of the carboxylated latex was examined by the use of Dynamic Light Scattering (DLS) method. The results of DLS revealed that the particle size of the carboxylated latex did not seriously alter during ball milling, implying that the milling process had no significant impact on the aggregation of particles. The study of rheological properties of nanocomposites showed that the simultaneous milling of the latex and CNT can lead to a relatively better dispersion of CNT in the latex compared to the dispersion obtained by ultrasonication which provides a new opportunity to produce latex nanocomposites in large scales using industrial ball mills. The hydroxyl functionality of CNT led to an enhanced dispersion of CNTOH into the polymer matrix through reaction with carboxyl group of the latex. These findings were also confirmed by infrared spectroscopy. Finally, ZnO was proposed as a Lewis catalyst for the improvement of CNT dispersion in the carboxylated latex and an improved dispersion was gained.     

Analysis of elastic properties of carbon nanotube reinforced nanocomposites with pinhole defects

Due to their unique molecular structure, carbon nanotubes exhibit outstanding properties. They are regarded as ideal reinforcements of composites. In this paper, the effects of pinhole defects on mechanical properties are investigated for wavy carbon nanotubes based nanocomposites using 3-D Representative Volume Element with long carbon nanotubes. The carbon nanotubes are modeled as continuum hollow cylindrical shape elastic material with pinholes, having some curvature in its shape. These defects are considered on the single walled carbon nanotubes. The mechanical properties like Young’s modulus of elasticity are evaluated for various values of waviness index, as well as type and number of pinhole defects. The effects of interactions between both defects as well as their influence on the nanocomposites are studied under an axial loading condition. Numerical equations are used to extract the effective material properties for the different geometries of Representative Volume Elements with non-defective carbon nanotubes. The finite element method results obtained for non-defective carbon nanotubes are consistent with analytical results for cylindrical Representative Volume Elements, which validate the proposed model. It is observed that the presence of pinhole defects as well as waviness, can significantly reduces the effective reinforcement, when compared with nanotubes without pinhole defects and this reinforcement decreases with the increase of the number of pinhole defects.     

Rheological and mechanical properties of polypropylene prepared with multi-walled carbon nanotube masterbatch

In this study, the effects of polypropylene-grafted maleic-anhydride-treated multi-walled carbon nanotubes (PP-MWNTs) on the viscoelastic behaviors and mechanical properties of a polypropylene-(PP)-based composite system were examined. The PP-MWNT/PP composites were prepared via melt mixing with a 3:1 ratio of PP-g-MA and acid-treated MWNTs at 220 degrees C. The surface characteristics of the PP-MWNTs were confirmed via Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). The viscoelastic behavior and mechanical properties of the PP-MWNT/PP composites were confirmed using a rheometer and an ultimate testing machine (UTM). The storage and loss moduli increased with increasing PP-MWNT content. The critical intensity stress factor (K(IC)) of the PP-MWNT/PP composites at high filler loading was also higher than that of the MWNT/PP composites. In conclusion, the viscoelastic behavior and mechanical properties of MWNT/PP can be improved by grafting MWNTs to PP-g-MA.     

Isothermal crystallization behavior and mechanical properties of polylactide/carbon nanotube nanocomposites

Carbon nanotube (CNT)–reinforced polylactide (PLA) nanocomposites were prepared using a melt compounding process employing a twin-screw extruder. The isothermal crystallization kinetics of PLA/CNT nanocomposites according to Avrami’s theory were analyzed using differential scanning calorimetry in the temperature range 90–120 °C. There was a significant dependence of CNT on the crystallization behavior of the PLA matrix. The incorporation of CNT improved effectively the crystallization rate of PLA/CNT nanocomposites through heterogeneous nucleation. The nucleating effect of CNTs which increased the number of nucleation sites and decreased the average spherulite size was confirmed using polarized optical microscopy. The rheological properties of the PLA/CNT nanocomposites were also investigated. Changes in the microstructure of the PLA/CNT nanocomposites occurred by incorporating CNT. Furthermore, the tensile strength/modulus and thermal stability of PLA/CNT nanocomposites were enhanced when a very small quantity of CNT was added. This research accounts for the effect of CNTs, which significantly influenced the isothermal behavior, thermal stability, mechanical, and rheological properties of the PLA/CNT nanocomposites, providing a design guide for PLA/CNT nanocomposites in industrial fields.     

Effect of fabrication process on electrical properties of polymer/multi-wall carbon nanotube nanocomposites

Polymer/carbon nanotubes nanocomposites were fabricated by an in situ polymerization process using multi-wall carbon nanotubes (MWNT) as filler in an epoxy polymer. Effects of curing process, mixing speed, mixing time, addition of ethanol, timing of hardener addition, etc., in the fabrication process on the electrical properties of nanocomposites have been investigated. In the fabrication process, the effective formation of macroscopic conducting network in matrix is most important to enhance the electrical properties of nanocomposites. It was found that the curing temperature and the mixing conditions are key factors in the fabrication process, which influence the formation of conducting network significantly. Therefore, careful design of these factors in the fabrication process is required to achieve high electrical performances of nanocomposites. The experimental percolation threshold of the resultant nanocomposites was around 0.1 wt%. Moreover, a statistical percolation model was built up to numerically investigate the percolation threshold. The experimental electrical conductivity increases from the percolation threshold following a percolation-like power law with the identified critical exponent t as 1.75.     

Mechanical properties of carbon nanotube reinforced polymer nanocomposites: A coarse-grained model

In this work, a coarse-grained (CG) model of carbon nanotube (CNT) reinforced polymer matrix composites is developed. A distinguishing feature of the CG model is the ability to capture interactions between polymer chains and nanotubes. The CG potentials for nanotubes and polymer chains are calibrated using the strain energy conservation between CG models and full atomistic systems. The applicability and efficiency of the CG model in predicting the elastic properties of CNT/polymer composites are evaluated through verification processes with molecular simulations. The simulation results reveal that the CG model is able to estimate the mechanical properties of the nanocomposites with high accuracy and low computational cost. The effect of the volume fraction of CNT reinforcements on the Young's modulus of the nanocomposites is investigated. The application of the method in the modeling of large unit cells with randomly distributed CNT reinforcements is examined. The established CG model will enable the simulation of reinforced polymer matrix composites across a wide range of length scales from nano to mesoscale.