Analysis of clustering, interphase region, and orientation effects on the electrical conductivity of carbon nanotube-polymer nanocomposites via computational micromechanics

A multiscale model based on computational micromechanics techniques is developed for determining the effective electrical conductivity of carbon nanotube-polymer nanocomposites containing bundles of SWCNTs at a wide range of SWCNT volume fractions above and below the observed percolation concentrations. The model is applied for both randomly oriented and fully aligned nanotube bundle orientation distributions, with emphasis on the latter in elucidating the relative impact of clustering and nanoscale effects on the effective electrical conductivity of nanocomposites. Nanocomposites consisting of aligned, well-dispersed and clustered/bundled SWCNTs are studied to indicate the influence of clustering on the effective electrical conductivity. A parametric study in terms of interphase thickness and interphase conductivity for both the well-dispersed and clustered arrangements is conducted to allow for the assessment of both the independent influence of the interphase layer and of the combined effects of clustering and interphase regions on the effective electrical conductivity of nanocomposites with aligned SWCNTs. Effective nanotube bundle properties obtained from clustered nanotube arrangements both with and without interphase regions are subsequently applied in an orientation distribution homogenization technique in order to obtain the effective electrical conductivity of nanocomposites consisting of randomly oriented SWCNT bundles. The resulting nanocomposite electrical conductivities are compared with characterization data available in the literature, and are discussed in terms of two mechanisms proposed in the literature for the low volume fraction electrical percolation observed in nanocomposites.     

Imaging conduction pathways in carbon nanotube network transistors by voltage-contrast scanning electron microscopy

The performance of field-effect transistors based on single-walled carbon nanotube (SWCNT) networks depends on the electrical percolation of semiconducting and metallic nanotube pathways within the network. We present voltage-contrast scanning electron microscopy (VC-SEM) as a new tool for imaging percolation in a SWCNT network with nano-scale resolution. Under external bias, the secondary-electron contrast of SWCNTs depends on their conductivity, and therefore it is possible to image the preferred conduction pathways within a network by following the contrast evolution under bias in a scanning electron microscope. The experimental VC-SEM results are correlated to percolation models of SWCNT-bundle networks.     

The incorporation of single-walled carbon nanotubes into polymerized high internal phase emulsions to create conductive foams with a low percolation threshold

New methods for the incorporation of single-walled carbon nanotubes (SWCNTs) into styrene-divinylbenzene-based high internal phase emulsions (HIPEs) are addressed with specific attention to minimizing the SWCNT loading while maintaining a high level of conductivity of the final polyHIPE–SWCNT composites. Stable HIPEs were achieved using sodium dodecyl sulfate-stabilized SWCNTs, thus eliminating the necessity of SWCNT functionalization. PolyHIPE–SWCNT composites were made with water: oil ratios (vol/vol) of 75:25 and of 84:16. The percolation threshold was determined to be 0.2 and 0.1 wt%, respectively. These threshold values are lower than that obtained for non-porous, polystyrene–SWCNT composites made by means of a latex-based route followed by melt-processing.     

The effect of geometric factor of carbon nanofillers on the electrical conductivity and electromagnetic interference shielding properties of poly(trimethylene terephthalate) composites: a comparative study

In this study, the effects of filler geometry on the electrical conductivity and electromagnetic interference (EMI) shielding properties of poly(trimethylene terephthalate) (PTT) composites filled with graphene nanosheets (GNSs), carbon nanotubes (CNTs), and GNS–CNT hybrid nanofillers have been investigated. The GNSs, CNTs, and hybrid GNS–CNT were well dispersed in the PTT matrix using a simple coagulation process. GNSs were prepared from graphene oxide (GO) through hydrazine reduction, and thermal reduction of GO at two different temperatures of 1050 and 1500 °C. PTT filled with different aspect ratios and oxygen functional groups of GNS were also prepared in order to compare the electrical conductivity and EMI shielding properties. The aspect ratios of GNSs and CNTs were estimated by using an ellipsoid model. Percolation scaling laws were applied to the magnitudes of conductivity to reveal the percolation network and filler dispersion. The percolation exponent of the PTT/GNS composites was larger than that of the PTT/CNT composites. The percolated filler–filler network at which the percolation exponent changed was correlated with the filler geometric structure. GNS–CNT hybrid nanofillers formed a complex double brush structure in the PTT/GNS–CNT composites. The geometric structure, aspect ratio, and intrinsic conductivity of carbon nanofillers affected the electrical percolation threshold and EMI shielding efficiency of the composites.     

The effect of pH on the functionalization of nylon fabric with carbon nanotubes

Single walled carbon nanotubes (SWCNTs) were dispersed in water and attached to nylon fabrics by a dip-drying procedure; scanning electron microscopy and Raman spectroscopy suggest the attachment of the SWCNTs. The electrical resistance of the functionalized fabrics is found to be pH-dependent, which is correlated with the quantity of SWCNTs dispersed in water at different values of pH. This can be further ascribed to the influence of the pK(a) of the acid (e.g., acetic acid in this study) used to tune pH. The acid may affect the dispersion of SWCNTs through two different mechanisms: (1) the free protons may protonate the amine and/or sulfonate group in the dye molecules, resulting in a variety of interactions among the dye molecules, SWCNTs and water molecules and (2) the resulting ions may increase the ionic strength of the solution, compressing the electric double layers of SWCNT colloids and thus impairing their stability. The former possibility is ruled out by data obtained using X-ray photoelectron spectroscopy, Raman spectroscopy, and ultraviolet-visible-near infrared spectroscopy; thus the latter is proposed to account for the experimental results. The colour strength of the functionalized fabrics increases with increasing pH, which is in agreement with their measured electrical properties.     

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.     

A surfactant dispersed SWCNT-polystyrene composite characterized for electrical and mechanical properties

Single wall carbon nanotubes (SWCNTs) were dispersed in polystyrene (PS) at 0.1, 0.2, 0.3 and 1.0 wt.% (weight percent) concentrations using a surfactant assisted method. The resulting nanocomposites were characterized for their electrical conductivity, mechanical strength and fracture toughness properties. Results show a significant improvement in electrical conductivity with electrical percolation occurring by 0.2 wt.% SWCNT loading and the SWCNT-PS nanocomposite fully conductive at 1.0 wt.%. Three-point bend tests showed a decline in flexural strength and break strain with the addition of 0.1 wt.% SWCNTs. Improvements in the flexural modulus, strength and break strain with increasing SWCNT wt.% content followed The fracture toughness of the SWCNT-PS nanocomposites, in terms of the critical stress-intensity factor K_IC, was reduced relative to the neat material. From optical and high resolution scanning electron microscopy the presence of the carbon nanotubes is shown to have an adverse effect on the crazing mechanism in this PS material, resulting in a deterioration of the mechanical properties that depend on this mechanism.     

Mechanical and electrical properties of carbon nanotube/poly(phenylene sulphide) composites incorporating polyetherimide and inorganic fullerene-like nanoparticles

The mechanical and electrical properties of single-walled carbon nanotube (SWCNT) reinforced poly(phenylene sulphide) (PPS) composites prepared by melt-extrusion have been evaluated. The wrapping of SWCNTs in polyetherimide (PEI) and the addition of inorganic fullerene-like tungsten disulfide (IF-WS₂) nanoparticles provided an effective method for dispersing the SWCNTs, leading to enhanced properties of the resulting hybrid composites. Mechanical tests demonstrated significant enhancements in stiffness, strength and toughness by the addition of both nanofillers, and the Young’s modulus of the hybrid composites was fairly well predicted by two-phase modelling. The electrical conductivity of PPS improved dramatically at low SWCNT content (0.1-0.5 wt%). At higher concentrations, the replacement of part of the SWCNTs with IF-WS₂ maintained the level of conductivity of the composites. Overall, the hybrids possess superior performance than composites reinforced solely with wrapped or non-wrapped SWCNTs, and their properties can be tailored by modifying the SWCNT/IF-WS₂ ratio.     

Modeling electrical conductivities of nanocomposites with aligned carbon nanotubes

We have developed an improved three-dimensional (3D) percolation model to investigate the effect of the alignment of carbon nanotubes (CNTs) on the electrical conductivity of nanocomposites. In this model, both intrinsic and contact resistances are considered, and a new method of resistor network recognition that employs periodically connective paths is developed. This method leads to a reduction in the size effect of the representative cuboid in our Monte Carlo simulations. With this new technique, we were able to effectively analyze the effects of the CNT alignment upon the electrical conductivity of nanocomposites. Our model predicted that the peak value of the conductivity occurs for partially aligned rather than perfectly aligned CNTs. It has also identified the value of the peak and the corresponding alignment for different volume fractions of CNTs. Our model works well for both multi-wall CNTs (MWCNTs) and single-wall CNTs (SWCNTs), and the numerical results show a quantitative agreement with existing experimental observations.     

Selective Growth of Metal‐Free Metallic and Semiconducting Single‐Wall Carbon Nanotubes

A major obstacle for the use of single‐wall carbon nanotubes (SWCNTs) in electronic devices is their mixture of different types of electrical conductivity that strongly depends on their helical structure. The existence of metal impurities as a residue of a metallic growth catalyst may also lower the performance of SWCNT‐based devices. Here, it is shown that by using silicon oxide (SiO_x) nanoparticles as a catalyst, metal‐free semiconducting and metallic SWCNTs can be selectively synthesized by the chemical vapor deposition of ethanol. It is found that control over the nanoparticle size and the content of oxygen in the SiO_x catalyst plays a key role in the selective growth of SWCNTs. Furthermore, by using the as‐grown semiconducting and metallic SWCNTs as the channel material and source/drain electrodes, respectively, all‐SWCNT thin‐film transistors are fabricated to demonstrate the remarkable potential of these SWCNTs for electronic devices.     

Nonlocal continuum model and molecular dynamics for free vibration of single-walled carbon nanotubes

Free transverse, longitudinal and torsional vibrations of single-walled carbon nanotubes (SWCNTs) are investigated through nonlocal beam model, nonlocal rod model and verified by molecular dynamics (MD) simulations. The nonlocal Timoshenko beam model offers a better prediction of the fundamental frequencies of shorter SWCNTs, such as a (5, 5) SWCNT shorter than 3.5 nm, than local beam models. The nonlocal rod model is employed to study the longitudinal and torsional vibrations of SWCNT and found to enable a good prediction of the MD results for shorter SWCNTs. Nonlocal and local continuum models provide a good agreement with MD results for relatively longer SWCNTs, such as (5, 5) SWCNTs longer than 3.5 nm. The scale parameter in nonlocal beam and rod models is estimated by calibrations from MD results.     

Length Distribution of Single‐Walled Carbon Nanotubes in Aqueous Suspension Measured by Electrospray Differential Mobility Analysis

The first characterization of the length distribution of single‐walled carbon nanotubes (SWCNT) dispersed in a liquid by electrospray differential mobility analysis (ES‐DMA) is presented. Although an understanding of geometric properties of SWCNTs, including length, diameter, aspect ratio, and chirality, is essential for commercial applications, rapid characterization of nanotube length distributions remains challenging. Here the use of ES‐DMA to obtain length distributions of DNA‐wrapped SWCNTs dispersed in aqueous solutions is demonstrated. Lengths measured by ES‐DMA compare favorably with those obtained from multiangle light scattering, dynamic light scattering, field flow fractionation with UV/vis detection, and atomic force microscopy, validating ES‐DMA as a technique to measure SWCNTs of <250 nm in length. The nanotubes are previously purified and dispersed by wrapping with oligomeric DNA in aqueous solution and centrifuging to remove bundles and amorphous carbon. These dispersions are particularly attractive due to their amenability to bulk processing, ease of storage, high concentration, compatibility with biological and high‐throughput manufacturing environments, and for their potential applications ranging from electronics and hydrogen‐storage vessels to anticancer agents.     

Morphological changes of carbon nanotubes in polyethylene matrices under oscillatory tests as determined by dielectrical measurements

By combining a high sensitive dielectric sensor into a parallel plate rheometer, the time evolution of the dielectric properties of polyethylene/carbon nanotube composites was measured in the molten state under oscillatory shear. Composites with single- (SWCNT) or multiwall (MWCNT) carbon nanotubes initially decrease its conductivity proportional to the oscillatory shear-strain applied. After this initial drop, some composites increase the conductivity under these non-quiescent conditions reflecting a possible shear-induced agglomeration process. The latter based on the complex permittivity spectrum showing a shortening in the CNT-CNT distances in these composites after shear. At concentrations below the electrical percolation threshold, the presence of both SWCNTs and MWCNTs reduces the DC conductivity of the molten matrices. This result shows that carbon nanotubes can act as a scavenger for impurities or additives present in commercial polyethylenes.     

Three-dimensional electrical percolation behaviour in conductive short-fibre composites

The percolation behaviour and electrical conductivity in unidirectional composites made of short conductive fibres embedded in an insulating matrix were examined by Monte Carlo simulation as a function of aspect ratio, volume fraction and angle. The unidirectional composite exhibited a highly anisotropic percolation behaviour with respect to the fibre direction for both fibre normal and fixed-length distribution. For the direction parallel to the fibre, the electrical conductivity increased exponentially with the volume fraction and the exponent increased as the aspect ratio increased. The conductivity in the transverse direction exhibited a sharp transition, from zero to nearly the same level as parallel conductivity at the critical volume fraction. The percolation threshold for the transverse direction also increased with aspect ratio up to 20, above which it decreased in parabolic manner. Both the threshold volume fraction and transient increase in conductivity in the transverse direction varied parabolically with aspect ratio, the maximum being an aspect ratio of 20.     

Effect of oxygen doping on electrical properties of small radius (2,1) single-walled carbon nanotubes

We investigated the electrical conductivity of the small radius oxygen-doped (2,1) single-walled carbon nanotubes (SWCNTs) using first-principles density functional theory (DFT). We found that introduction of oxygen does not significantly change the global structure of the SWCNT, and thus the bonding mode of the structure is not remarkably altered. The results show that doping enhances the conductivity of the SWCNT. Oxygen doping increases density of states at the Fermi level, thus the conductivity of the doped SWCNT increases when oxygen is introduced, consistent with experimental observations. These observations were further clarified by comparing band structures of pristine and doped nanotubes.     

Numerical and analytical study of rotating flow in an enclosed cylinder under an axial magnetic field

Summary. A numerical and analytical study of the steady laminar flow driven by a rotating disk at the top of an enclosed cylinder, having an aspect ratio H/R equal to 1, filled with a liquid metal, and submitted to an axial magnetic field B, is presented. The governing equations in cylindrical coordinates are solved by a finite volume method. In the absence of a magnetic field, the numerical method is validated via a comparison with experimental data; the latter was found to be in good agreement with the predictions. In the presence of a magnetic field, the analytical velocity profiles under the rotating disk and on the bottom wall obtained for a high value of the magnetic interaction parameter N are in excellent agreement with those obtained by numerical simulations. The effect of the top, bottom and vertical walls' conductivity on the flow is studied and found to be an important parameter in the control of the flow.     

High-performance single-wall carbon nanotube transparent conductive films

A single-wall carbon nanotube(SWCNT) has superior optical,electrical,and mechanical properties due to its unique structure and is therefore expected to be able to form flexible high-performance transparent conductive films(TCFs).However,the optoelectronic performance of these films needs to be improved to meet the requirements of many devices.The electrical resistivity of SWCNTTCFs is mainly determined by the intrinsic resistivity of individual SWCNTs and their junction resistance in networks.We analyze these key factors and focus on the optimization of SWCNTs and their networks,which include the diameter,length,crystallinity and electrical type of the SWCNTs,and the bundle size and interconnects in networks,as well as chemical doping and microgrid design.We conclude that isolated/small-bundle,heavily doped metallic or semiconducting SWCNTs with a large diameter,long length and high crystallinity are necessary to fabricate high-performance SWCNTTCFs.A simple,controllable way to construct macroscopic SWCNT networks with Y-type connections,welded junctions or microgrid design is important in achieving a low resistivity.Finally,some insights into the key challenges in the manufacture and use of SWCNT TCFs and their prospects are presented,hoping to shed light on promoting the practical application of SWCNT TCFs in future flexible and stretchable optoelectronics.     

Numerical Investigation of Heat Transfer of Silver-Coated Glass Particles Dispersed in Ethylene Vinyl Acetate Matrix

The effective thermal conductivity of silver-coated glass spheres dispersed in an ethylene vinyl acetate matrix was investigated numerically as a function of filler concentration. The finite-element method was carried out for modeling the thermal heat transport and to calculate the effective thermal conductivity of the composite for three elementary cells; simple cubic (SC), body-centered cubic (BCC), and face-centered cubic (FCC). The effect of the inclusion/matrix thermal contact resistance and the ratio of thermal conductivities of the filler-to-matrix material are also taken into account. The numerical results are compared with previously published experimental data and some theoretical models. The calculated values of the thermal conductivity of the SC model are in good agreement with the measured results for all the filler volume fractions. Numerical results for FCC and BCC models were found to be in good agreement with analytical models. The results show that the filler/matrix contact resistance has an important effect on the effective thermal conductivity.     

p-n homo-junction arrays of aligned single walled carbon nanotubes fabricated by selective patterning of polyethyleneimine film

We describe the fabrication and electrical performance of p-n homo-junction diode arrays of horizontally aligned single walled carbon nanotubes (SWCNTs). Horizontally aligned SWCNTs grown on stable temperature-cut quartz with a density of ～ 6 SWCNTs μm(-1) were transferred onto a SiO(2)/Si substrate. After the electrical breakdown, aligned SWCNT field effect transistors (FETs) showed unipolar p-type characteristics with a large current on/off ratio of 10(6) at 1 V and a hole mobility per tube of 1500 cm(2) V(-1) s(-1). Spin-coating of polyethyleneimine (PEI) onto p-type SWCNT FETs showed the n-type transfer characteristics. Patterning of spin-coated PEI film enabled the fabrication of p-n homo-junction arrays of aligned SWCNTs in an easy way, where the rectifying behavior was observed with a rectification ratio of ～ 10(4) at ± 2 V. A comparative study with a p-n homo-junction of random networks of SWCNTs confirmed the advantage of aligned SWCNTs for applications in high performance electronic devices.     

Strain effects on percolation conduction in conductive particle filled composites

The effect of uniaxial and multiaxial mechanical strain on the electrical conductivity of particle filled polymer composites is investigated in the framework of concentration-driven percolation. For composites consisting of low aspect ratio, rigid conductive particles in a compliant polymer matrix, a simple argument leads to the conclusion that the effective volume fraction of conductive particles (the ratio of total particle volume to the total volume of the deformed composite) plays a dominant role, with conductivity remaining isotropic despite the directional bias of the strain state. As such, conductivity is expected to exhibit classical power, law-dependence on concentration, which in this case takes the form of a strain-dependent effective volume fraction. Consideration of deformation effects on particle agglomerates suggest, however, that particle-to-particle network connections are likely to be affected most significantly along directions experiencing the most severe strains, introducing a directional bias in network connectivity at a higher length scale. To assess the importance of this possible directional bias, random resistor network models are used to study the conductivity of uniaxially strained composites. For conservative assumptions on the severity of the bias in bond probabilities, network conductivities exhibit approximately isotropic, concentration-driven behavior for moderate strains, supporting the predictive utility of the simple percolation conduction-effective volume fraction approach. Further corroboration is provided by experiments in the literature on silicone-graphite composites subjected to uniaxial compressive strain, where good agreement is obtained through moderate strains for the theoretically correct value of the conduction exponent in concentration-driven percolation.