On the contribution of carbon nanotube deformation to piezoresistivity of carbon nanotube/polymer composites

The change in electrical resistance due to mechanical deformation of carbon nanotube (CNT)/polymer composites can be rationalized in terms of two effects: (i) changes in the composite electrical resistivity due to changes in the CNT network configuration and (ii) deformation of the CNTs themselves. The contribution of CNT dimensional changes (ii) to the piezoresistivity of CNT/polymer composites is investigated here. An analytical model based exclusively on dimensional changes which describes the CNT change of electrical resistance in terms of its mechanical deformation is proposed. A micromechanics approach and finite element analysis are performed to correlate the macroscale composite strain to the individual CNT strain. The CNT change of electrical resistance is quantified for different matrix elastic moduli and CNT weight fractions. The CNT/polymer composite is also modeled as an effective continuum material in terms of both its electrical and mechanical responses so that the effect of dimensional changes on the global piezoresistivity can be investigated. Based on the modeling predictions and previous experimental results, it is estimated that the CNT change of resistance due to the macroscale composite strain is marginal (∼5%) compared to the total composite change of resistance commonly measured in the laboratory, suggesting that the dominant effect in the piezoresistivity of CNT/polymer composites is the change in the CNT network configuration.     

Morphological characterization and modelling of electrical conductivity of multi-walled carbon nanotube/poly(p-phenylene sulfide) nanocomposites obtained by twin screw extrusion

In this study, poly(p-phenylene sulfide) based nanocomposites containing multi-walled carbon nanotubes (MWNTs) were produced by dilution of a 15 wt.% MWNT/PPS masterbatch via twin screw extrusion process. The electrical conductivities of the nanocomposites were measured and percolation threshold was observed below 0.77 vol.% MWNTs. The state of dispersion and distribution quality of MWNTs was analyzed on macro- and nanoscale through transmission light and scanning electron microscopy (SEM). A good deagglomeration of primary macroagglomerates and a homogenous MWNT distribution on nanoscale was found. The dependence of conductivity on MWNT concentration was estimated using statistical percolation theory which matches the experimental data quite well. A new empirical equation was set up to fit the electrical conductivity using quantitative values of visible percolating MWNTs which were detected by charge contrast imaging in SEM.     

Experiments and micromechanical modeling of electrical conductivity of carbon nanotube/cement composites with moisture

Carbon nanotube (CNT)/cement composites have been proposed as a multifunctional material for self-sensing and traffic monitoring due to their unique electric conductivity which changes with the application of mechanical load. However, material constituent and environmental factors may significantly affect the potential application of these materials. Therefore, it is necessary to understand an influence of material constituent such as porosity and dispersion of CNT and environmental factor such as moisture on the electrical conductivity of CNT/cement composite. This paper investigates the effect of moisture on the effective electrical conductivity of CNT/cement composites. To prepare the specimens, multi-walled carbon nanotubes (MWCNTs) are well dispersed in cement paste, which is then molded and cured into cubic test specimens. By drying the specimens from the fully saturated state to the fully dry state, the effective electrical conductivity is measured at different moisture contents. As the water in the specimen is replaced by air voids, the electrical conductivity significantly decreases. Different ratios of MWCNTs to cement have been used in this study. Micromechanical models have been used to predict the effective electrical conductivities. A comprehensive model is proposed to take into account the effects of individual material phases on the effective electrical conductivity of CNT/cement composites with moisture effect.     

Investigation of electrical conductivity of carbon black-copper phthalocyanine matrix composites

Electrical conductivity results obtained for two component composites were measured and discussed. The composites consisted of copper phthalocyanine (semiconductor) and 7 different kinds of carbon black. The dependence of the electrical conductivity on the composite composition was examined. The percolation theory as well as the Yoshida's and McLachlan's models were utilised to describe the experimental data. The relationships between the carbon black physico-chemical properties and some parameters of the theories were found.     

Structure and tensile properties of polypropylene/carbon nanotubes composites prepared by melt extrusion

Polypropylene/carbon nanotubes (PP/CNTs) nancomposites were prepared with a single screw extruder by adding maleic anhydride-grafted poplypropylene (PP-g-MAH) as compatibilizer to polypropylene (PP) with different amounts of carbon nanotubes (CNTs) in the range of 0.1–0.7 wt.%. Structure and morphology of the prepared samples were examined by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), polarizing light microscopy (PLM) and X-ray diffraction (XRD). The results showed that PP spherulites decreased in size when CNTs were introduced into the polymer. Mechanical properties of the samples were also studied. Tensile tests showed that with increasing amount of CNTs the strain at break decreased whereas the Young’s modulus was improved of 16.41 % to 36.05 % and tensile strength of 36.67 % to 64.70 % compared to pristine PP. The SEM microphotographs showed that majority of the CNTs were dispersed individually and oriented along the shear flow direction.     

Strain sensing in polymer/carbon nanotube composites by electrical resistance measurement

In this work multiwall carbon nanotubes (MWCNTs) dispersed in a polymer matrix have been used for strain sensing of the resulting nanocomposite under tensile loading. This was achieved by measuring the relative electrical resistance change (ΔR/R₀) in conductive polyvinylidenefluoride (PVDF)/MWCNTs nanocomposites prepared by melt-mixing with varying filler content from 0.5 wt.% to 8 wt.%. Two main parameters were systematically studied. The PVDF/MWCNTs mixing procedure that results in a successful MWCNTs dispersion, and the effect of MWCNTs content on material’s sensing behaviour. The samples were subjected to tensile loading and the longitudinal strain was monitored together with the longitudinal electrical resistance. The results showed that MWCNTs dispersed in insulating PVDF matrix have the potential to be used as a sensitive network to monitor the strain levels in polymer/carbon nanotube nanocomposites as the deformation level of each sample was being reflected by the resistance changes.     

Synergistic effect on electrical conductivity of few-layer graphene/multi-walled carbon nanotube paper

A unique concept of making a paper from few-layer graphene (FLG) and multi-walled carbon nanotube (MWCNT) was explored. In the FLG/MWCNT paper, an entangled network of MWCNTs was formed to bridge the gap between FLG. The ratio of FLG and MWCNT in the paper was varied from FLG-dominated to MWCNT-dominated in order to study the efficiency in improving electrical conductivity. At a high weight fraction of MWCNTs in the paper, MWCNTs were oriented between FLG. A synergistic effect on electrical conductivity between two-dimensional FLG and one-dimensional MWCNT was demonstrated in the hybrid paper.     

Isotactic and syndiotactic polypropylene/multi-wall carbon nanotube composites: synthesis and properties

Isotactic polypropylene (iPP) and syndiotactic polypropylene (sPP) nanocomposites containing 0.1–3.5 wt.% multi-wall carbon nanotubes (MWCNTs) have been synthesized via in situ polymerization method with the use of C₂- and C_s- symmetry zirconocenes activated by methylaluminoxane (MAO) in liquid propylene medium. Fracture morphology studies by SEM reveal different MWCNT dispersion efficiency in various polymer matrices, which arises from the catalytic peculiarities of the composite synthesis. Considerable Young’s modulus enhancement of iPP and sPP (25–66%) takes place even at low MWCNT loadings (below 0.5 wt.%). The obtained nanocomposites can find use as efficient electromagnetic shielding materials and microwave absorbing filters due to relatively low permittivity values and considerable dielectric losses in microwave range. Calorimetry data demonstrate that MWCNTs exert evident influence as nucleating agents causing the rise of iPP and sPP crystallization temperature. Considerable retardation effect on iPP thermal oxidative degradation has been observed: the temperature of maximal weight loss rate rises by ~52 °C upon incorporating only 1.4 wt.% MWCNTs.     

Sugarcane bagasse cellulose/HDPE composites obtained by extrusion

Natural fibers used in this study were both pre-treated and modified residues from sugarcane bagasse. Polymer of high density polyethylene (HDPE) was employed as matrix in to composites, which were produced by mixing high density polyethylene with cellulose (10%) and Cell/ZrO₂·nH₂O (10%), using an extruder and hydraulic press. Tensile tests showed that the Cell/ZrO₂·nH₂O (10%)/HDPE composites present better tensile strength than cellulose (10%)/HDPE composites. Cellulose agglomerations were responsible for poor adhesion between fiber and matrix in cellulose (10%)/HDPE composites. HDPE/natural fibers composites showed also lower tensile strength in comparison to the polymer. The increase in Young’s modulus is associated to fibers reinforcement. SEM analysis showed that the cellulose fibers insertion in the matrix caused an increase of defects, which were reduced when modified cellulose fibers were used.     

The influence of carbon nanotube functionalization route on the efficiency of dispersion in polypropylene by twin-screw extrusion

The joint effect of chemical functionalization and polymer melt blending conditions on carbon nanotube dispersion in polypropylene, as well as its influence on the electrical and mechanical properties of the resulting composites were investigated. Melt blending was performed using a prototype twin screw extruder enabling sampling along the barrel. The carbon nanotube dispersion was assessed by optical and scanning electron microscopy. The functionalization reaction was tailored for compatibility with the polymer, and characterized by X-ray photoelectron spectroscopy. In particular, nanotubes covalently bonded to polypropylene showed distinctive dispersion ability, while the carbon nanotube dispersion remained stable even after re-melting. However, the polypropylene-functionalized nanotubes produced composites with higher electrical resistivity, possibly due to the insulating effect of the polymer bonded to the nanotubes surface.     

碳纳米管水泥基复合材料电学性能数值模拟

采用ANSYS12.0和蒙特卡洛随机方法构建了碳纳米管水泥基复合材料的有限元模型,并基于有限元法分析了碳纳米管长径比、直径和掺量对复合材料有效电阻率的影响,并在此基础上通过有效介质方程对有效电阻率数值解和电阻率实验值进行了拟合。数值计算结果表明,碳纳米管水泥基复合材料有效电阻率的有限元解与解析解较为一致,证明采用有限元法进行电学分析具有可行性;碳纳米管水泥基复合材料有效电阻率随碳纳米管掺量和碳纳米管长径比增加而减小,随着碳纳米管直径的减小而减小;有效介质方程对碳纳米管水泥基复合材料有效电阻率实验值和有限元数值解拟合曲线变化趋势是一致的。     

Low temperature electrical conductivity of low-density polyethylene/carbon black composites

The study deals with the electrical characteristics of carbon black/low-density polyethylene (CB/LDPE) composites of various CB filler concentrations (10, 15, and 20 wt.%). The DC electrical conductivity was studied as a function of filler concentration in low temperature range 25–285 K. It was found that the composites exhibit negative temperature coefficient of resistivity (TCR) at low temperatures and high enhancement in the electrical conductivity with both temperature and carbon black concentration. The observed increase of conductivity with the filler concentration was interpreted through the percolation theory. The dependence of the electrical conductivity of the given composites on temperature (25–285 K) was analyzed in terms of a formula in consistence with Mott hopping mechanism.Visiting scientist from the Jordan University of Science and Technology, Irbid-Jordan.     

Morphology and electrical properties of polyamide 6/polypropylene/multi-walled carbon nanotubes composites

Morphology, electrical properties and conductive mechanisms of polyamide 6/polypropylene/muti-walled carbon nanotubes (PA6/PP/MWNTs) composites with varied compositions and different blending sequences were investigated. The MWNTs were found to be located preferentially in the PA6 phase in the composites, whatever the PA6 was continuous or dispersed phase. While the incorporation of MWNTs changed the dispersed PA6 phase from spherical to elongated or irregular shape. The PA6/PP/MWNTs (20/80/4) composite with a dispersed PA6 phase exhibited a higher electrical conductivity in comparison with the PA6/PP/MWNTs (50/50/4) composite which has a co-continuous phase and exhibits double percolation. This was due to the formation of a conductive MWNTs networks in the PA6/PP/MWNTs (20/80/4) composite as proved by means of field emission scanning electron microscopy and rheological measurements. The morphology and electrical properties of the PA6/PP/MWNTs (20/80/4) composites were significantly influenced by blending sequences. When blending 3.9 phr MWNTs with a pre-mixed PA6/PP/MWNTs (20/80/0.1) composite, the dispersed PA6 phase formed an elongated structure, which was beneficial to the electrical properties.     

RTM processing and electrical performance of carbon nanotube modified epoxy/fibre composites

This investigation focuses on nanoparticle filtration in the processing of multiscale carbon and glass fibre composites via resin transfer moulding. Surface modified and unmodified carbon nanotubes (CNTs) were incorporated into a commercial epoxy resin. The dispersion quality was evaluated using electrical measurements of the liquid suspensions. The manufacturing process was adapted to the challenges posed by the modified rheological behaviour of the CNT loaded resin. Nanoparticle filtration was observed; with some of the unmodified systems following so called ‘cake filtration’ behaviour. This resulted in nonlinear flow behaviour that deviated from the ideal response observed in RTM filling in conventional composites. The electrical conductivity of relatively high fibre volume fraction multiscale carbon and glass laminates increased by less than an order of magnitude with the addition of the nanotubes.     

Impedance characteristics and electrical modelling of multi-walled carbon nanotube/silicone rubber composites

Multi-walled carbon nanotube (MWCNT)-filled silicone rubber (SR) composites were prepared by solvent evaporation method, with different MWCNT concentrations from 0.5 wt% to 6.5 wt%. Alternating current (AC) electrical properties of samples with interdigital electrodes were measured in the frequency range from 20 Hz to 1 MHz. Impedance spectroscopy analysis reveals a frequency-independent percolation transition between 2.0 wt% and 2.9 wt%. Samples above the percolation threshold exhibit more regular variations: the magnitude of impedance decreases gradually with frequency in the low-frequency range, and then decreases as a power law beyond a critical frequency, with the exponent in a limited range indicating the AC universality of disordered solids; the plots of real and imaginary parts of impedance fit semicircles well in the complex plane, implying semiconductive behaviours. Over the concentration range tested, a multi-stage circuit model consisting of resistor–capacitor (RC) networks is proposed to simulate the electrical responses of samples. The validity of the modelling approach is verified by comparing simulation results to experimental results, and is further supported by the analysis of the characteristic frequency. The use of equivalent circuits in modelling provides a further insight into the conducting network inside nanocomposites and more valuable guidance for the design of correlative devices.     

Mechanical,electrical and thermal properties of aligned carbon nanotube/polyimide composites

Carbon nanotubes (CNTs) have high strength and modulus, large aspect ratio, and good electrical and thermal conductivities, which make them attractive for fabricating composite. The poly(biphenyl dianhydride-p-phenylenediamine) (BPDA/PDA) polyimide has good mechanical and thermal performances and is herein used as matrix in unidirectional carbon nanotube composites for the first time. The strength and modulus of the composite increase by 2.73 and 12 times over pure BPDA–PDA polyimide, while its electrical conductivity reaches to 183 S/cm, which is 10¹⁸ times over pure polyimide. The composite has excellent high temperature resistance, and its thermal conductivity is beyond what has been achieved in previous studies. The improved properties of the composites are due to the long CNT length, high level of CNT alignment, high CNT volume fraction and good CNT dispersion in polyimide matrix. The composite is promising for applications that require high strength, lightweight, or high electrical and thermal conductivities.     

On the effective thermal conductivity of carbon nanotube reinforced polymer composites

In this paper, a theoretical model has been developed for predicting the effective thermal conductivity of an aligned multi-walled nanotube polymer composite. This model is based on an effective medium theory that has been developed for composites containing aligned spheroidal inclusions with imperfect interfaces. To incorporate the nanotube structure into this theory, a continuum model of the nanotube geometry is developed by considering its structure and the mechanism of heat conduction through it. Results show that the overall conductivity will be much lower than expected due to the fact that in the composite, the outer nanotube layer carries the bulk of the heat flowing through the nanotube. It is also seen that the high nanotube–matrix boundary resistance does not significantly affect the overall conductivity. The effective conductivity was also found to be highly sensitive to the nanotube diameter.     

Temperature dependence of electrical conductivity in double-wall and multi-wall carbon nanotube/polyester nanocomposites

The aim of this study is to investigate temperature dependence of electrical conductivity of carbon nanotube (CNT)/polyester nanocomposites from room temperature to 77 K using four-point probe test method. To produce nanocomposites, various types and amounts of CNTs (0.1, 0.3 and 0.5 wt.%) were dispersed via 3-roll mill technique within a specially formulized resin blend of thermoset polyesters. CNTs used in the study include multi walled carbon nanotubes (MWCNT) and double-walled carbon nanotubes (DWCNT) with and without amine functional groups (–NH₂). It was observed that the incorporation of carbon nanotubes into resin blend yields electrically percolating networks and electrical conductivity of the resulting nanocomposites increases with increasing amount of nanotubes. However, nanocomposites containing amino functionalized carbon nanotubes exhibit relatively lower electrical conductivity compared to those with non-functionalized carbon nanotubes. To get better interpretation of the mechanism leading to conductive network via CNTs with and without amine functional groups, the experimental results were fitted to fluctuation-induced tunneling through the barriers between the metallic regions model. It was found that the results are in good agreement with prediction of proposed model.