High electrical performance of carbon nanotubes/rubber composites with low percolation threshold prepared with a rotation-revolution mixing technique

The present study demonstrates a novel mixing approach for achieving a good dispersion of carbon nanotubes (CNTs) in a styrene-butadiene rubber (SBR), which leads to a significant improvement in electrical properties. Our mixing technique consists of (1) pretreatment by ultrasonication to disentangle the bundles of CNTs in organic solvent and (2) “rotation-revolution” mixing of the CNTs with SBR without mechanical shear, which prevents CNTs from collapsing during the mixing process. The present mixing method does not require the addition of any dispersing agents (amphiphilic molecules) or chemical modification of the CNTs to obtain a good dispersion. Compared with a conventional Banbury mixing technique, our method leads to a significant decrease in the percolation threshold (less than 1 phr), where the electrical conductivity suddenly increases due to the formation of percolation networks of CNTs in SBR. This is because the aspect ratio of the CNTs was maintained even after the mixing process, whereas CNTs were broken during the conventional Banbury mixing. The effect of using different types of CNTs on electrical conductivity was also investigated. The results show that the percolation threshold is largely related to the structural quality (graphitization) of the CNTs as well as their aspect ratio.     

Effect of moisture on elastic and viscoelastic properties of epoxy and epoxy-based carbon fibre reinforced plastic filled with multiwall carbon nanotubes

In this study, we investigated the peculiarities of moisture absorption and moisture-induced effects on the elastic and viscoelastic flexural properties of epoxy resin and carbon fibre reinforced plastic (CFRP) filled with multiwall carbon nanotubes (MWCNTs). Short-term cyclic creep-recovery tests of moistened epoxy and CFRP filled with MWCNTs revealed improvements in creep resistance for both materials. The addition of MWCNTs to the epoxy resin suppressed the moisture absorption by the material, causing a reduction in the diffusion coefficient by 31% and equilibrium moisture content by 15%. The addition of MWCNTs reduced the flexural strength of moistened epoxy and CFRP samples by approximately half, and also lowered the flexural modulus by ∼1.4 and ∼3 times, elastic strain by 1.25 and 1.04 times, viscoelastic strain by 1.39 and 1.03 times, and plastic strain by 2.68 and 1.60 times, respectively.     

Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

Comparison of nanotubes produced by fixed bed and aerosol-CVD methods and their electrical percolation behaviour in melt mixed polyamide 6.6 composites

The electrical percolation behaviour of five different kinds of carbon nanotubes (CNTs) synthesised by two CVD techniques was investigated on melt mixed composites based on an insulating polyamide 6.6 matrix. The electrical percolation behaviour was found to be strongly dependent on the properties of CNTs which varied with the synthesis conditions. The lowest electrical percolation threshold (0.04 wt.%) was determined for as grown multi-walled carbon nanotubes without any purification or chemical treatment. Such carbon nanotubes were synthesised by the aerosol method using acetonitrile as ferrocene containing solvent and show relatively low oxygen content near the surface, high aspect ratio, and good dispersability. Similar properties could be found for nanotubes produced by the aerosol method using cyclohexane, whereas CNTs produced by the fixed bed method using different iron contents in the catalyst material showed much higher electrical percolation thresholds between 0.35 and 1.02 wt.%.     

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.     

High performance PA6/CNTs nanohybrid fibers prepared in the melt

Commercial and home-made carbon nanotubes (CNTs) were plasma treated under oxygen atmosphere and then added to polyamide 6 (PA6) in order to prepare fibres by melt spinning. For comparison, pristine nanofillers were used too. The effect of functionalization and of filler characteristics on the morphological, rheological, mechanical and electrical properties of the fibres was studied by TEM and SEM, rheological measurements, tensile and electrical conductivity tests. The results demonstrated that the functionalization led to a better mechanical performance and the morphological analysis confirmed that the adhesion, the dispersion and the alignment of the nanotubes within the polymer matrix were improved when using functionalized CNTs. Electrical tests marked that functionalization slightly reduced the conductivity of the materials.     

Multi-scale investigation of electronic transport and electromechanical behavior in carbon nanotube materials

Using home-built experimental setups, electrical properties and electromechanical characterization of two systems based on multiwalled carbon nanotubes (MWNTs) were investigated at room temperature. The first system is formed by carbon nanotubes (CNTs) either isolated or in small groups on a gold substrate, while the second one concerns a macroscale three-dimensional entanglement of CNTs in powder form. The local electrical resistance on systems of the first type was measured using an atomic force microscopy with a conductive tip and showed a narrow distribution of resistance values as well for isolated CNTs as for small groups of them. However, in this latter case the average resistance value has been found to be one order of magnitude higher than that of individual CNTs, which was attributed to the contact resistance between CNTs. This parameter was then studied from a statistical viewpoint through electromechanical tests performed at a macroscopic scale. They consisted in applying an external compression to CNTs powder samples and measuring the evolution of the electrical resistance across the pressed material. These tests demonstrated an outstanding decrease of the electrical resistance resulting from the increasing number of random connections between CNTs under compression, and the experimental curves were fitted with an analytical model. Furthermore, it was deduced from this model that the elementary contact resistance between CNTs decreases under compression. The stability of this electrical contact was verified over several durations and under different constant applied loads.     

In situ polymerized nanocomposites: Polystyrene/CNT and Poly(methyl methacrylate)/CNT composites

Carbon nanotubes (CNTs) were incorporated into polystyrene (PS) and poly(methyl methacrylate) (PMMA) matrices via in situ emulsion and emulsion/suspension polymerization methods. The polymerizations were carried out using various initiators, surfactants, and carbon nanotubes to determine their influence on polymerization and on the properties of the composites. The loading of CNTs in the composites varied from 0 to 15 wt.%, depending on the CNTs used. Morphology and dispersion of the CNTs were analyzed by transmission and scanning electron microscopy techniques. The dispersion of multi-walled carbon nanotubes (MWCNT) in the composites was excellent, even at high CNT loading. The mechanical properties, and electrical and thermal conductivities, of the composites were also analyzed. Both electrical and thermal conductivities were improved.     

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.     

Advanced elastomer nano-composites based on CNT-hybrid filler systems

Different techniques to disperse multiwalled carbon nanotubes (CNT) in elastomers using an internal mixer are applied and physical properties of the composites are evaluated: stress–strain behavior, dynamic-mechanical, thermal diffusivity, dielectric and fracture mechanical properties. The electrical percolation threshold is found to decrease by using ethanol as dispersion agent, compared to “dry” mixing, correlating with improved optical dispersion. The effect of nanoscopic gaps between adjacent CNTs on the electrical and thermal conductivity of the composites and the missing percolation behavior of the thermal conductivity are discussed. We have found some technically promising synergetic effects of the hybrid filler systems. For all systems one observes significantly steeper stress–strain curves by addition of 1.6 vol.% CNT to the systems with conventional fillers. In natural rubber the fatigue crack propagation resistance, tensile strength and electrical conductivity is found to be improved also for dry mixed CNT-silica hybrid systems.     

Structure–property relationships in isotactic polypropylene/multi-walled carbon nanotubes nanocomposites

In this work, the influence of multi-walled carbon nanotubes (MWCNT) on electrical, thermal and mechanical properties of CNT reinforced isotactic polypropylene (iPP) nanocomposites is studied. The composites were obtained by diluting a masterbatch of 20 wt.% MWCNT with a low viscous iPP, using melt mixing. The morphology of the prepared samples was examined through SEM, Raman and XRD measurements. The effect of MWCNT addition on the thermal transitions of the iPP was investigated by differential scanning calorimetry (DSC) measurements. Significant changes are reported in the crystallization behavior of the matrix on addition of carbon nanotubes: increase of the degree of crystallinity, as well as appearance of a new crystallization peak (owing to trans-crystallinity). Dynamic mechanical analysis (DMA) studies revealed an enhancement of the storage modulus, in the glassy state, up to 86%. Furthermore, broadband dielectric relaxation spectroscopy (DRS) was employed to study the electrical and dielectric properties of the nanocomposites. The electrical percolation threshold was calculated 0.6–0.7 vol.% MWCNT from both dc conductivity and dielectric constant values. This value is lower than previous mentioned ones in literature in similar systems. In conclusion, this works provides a simple and quick way for the preparation of PP/MWCNT nanocomposites with low electrical percolation threshold and significantly enhanced mechanical properties.     

Enhancement of fracture toughness of hierarchical carbon fiber composites via improved adhesion between carbon nanotubes and carbon fibers

Hierarchical +1 composites consisting of carbon fibers with carbon nanotubes (CNTs) grown onto them and an epoxy matrix were processed, and the mode I fracture toughness of these composites was evaluated. The mode I fracture toughness of the initial batches of the hierarchical composites was lower than that of the baseline samples without CNTs. Hence, efforts to enhance the adhesion between carbon fibers and CNTs were made, resulting in enhanced adhesion. The enhanced adhesion was confirmed by Scotch tape tests and mode I fracture toughness tests followed by fractographic studies. The mode I fracture toughness of the hierarchical composites with enhanced adhesion was 51% and 89% higher than those of the baseline samples and hierarchical composites with poor adhesion, respectively. Moreover, fractographic studies of the fracture surfaces of the hierarchical composites with enhanced adhesion showed that CNTs were still attached to carbon fibers even after the mechanical tests.     

Mechanical and electrical property improvement in CNT/Nylon composites through drawing and stretching

The excellent mechanical properties of carbon nanotubes (CNTs) make them the ideal reinforcements for high performance composites. The misalignment and waviness of CNTs within composites are two major issues that limit the reinforcing efficiency. We report an effective method to increase the strength and stiffness of high volume fraction, aligned CNT composites by reducing CNT waviness using a drawing and stretching approach. Stretching the composites after fabrication improved the ultimate strength by 50%, 150%, and 190% corresponding to stretch ratios of 2%, 4% and 7%, respectively. Improvement of the electrical conductivities exhibited a similar trend. These results demonstrate the importance of straightening and aligning CNTs in improving the composite strength and electrical conductivity.     

Poly(vinyl alcohol) reinforced with large-diameter carbon nanotubes via spray winding

For practical application of carbon nanotube (CNT)/polymer composites, it is critical to produce the composites at high speed and large scale. In this study, multi-walled carbon nanotubes (MWNTs) with large diameter (∼45 nm) and polyvinyl alcohol (PVA) were used to increase the processing speed of a recently developed spraying winding technique. The effect of the different winding speed and sprayed solution concentration to the performance of the composite films were investigated. The CNT/PVA composites exhibit tensile strength of up to 1 GPa, and modulus of up to 70 GPa, with a CNT weight fraction of 53%. In addition, an electrical conductivity of 747 S/cm was obtained for the CNT/PVA composites. The good mechanical and electrical properties are attributed to the uniform CNTs and PVA matrix integration and the high degree of tube alignment.     

Long-term moisture effects on the interfacial shear strength between surface treated carbon fiber and epoxy matrix

In recent years, carbon fiber reinforced polymer (CFRP) composites have found increasing applications in marine and offshore area, where the CFRP components are subjected to a persistent attack of moisture. The performance degradation of composites under those critical service conditions becomes a key issue. In this work, silane coating and multiwalled carbon nanotubes were applied on carbon fibers to enhance the fiber/matrix interfacial bonding strength. The long-term effects of moisture on the interfacial shear strength (IFSS) of the composites in underwater environments, such as de-ionized water and simulated seawater, have been studied using single fiber microbond method. The silane coating and carbon nanotube-modified silane coating are found to contribute 14.5% and 26.3% increase in IFSS of the CFRP in dry air, and well maintain this improvement during a 120-day immersion test in de-ionized water and simulated seawater.     

Vibration damping characteristics of carbon fiber-reinforced composites containing multi-walled carbon nanotubes

Vibration damping characteristic of nanocomposites and carbon fiber reinforced polymer composites (CFRPs) containing multiwall carbon nanotubes (CNTs) have been studied using the free and forced vibration tests. Several vibration parameters are varied to characterize the damping behavior in different amplitudes, natural frequencies and vibration modes. The damping ratio of the hybrid composites is enhanced with the addition of CNTs, which is attributed to sliding at the CNT-matrix interfaces. The damping ratio is dependent on the amplitude as a result of the random orientation of CNTs in the epoxy matrix. The natural frequency shows negligible influence on the damping properties. The forced vibration test indicates that the damping ratios of the CFRP composites increase with increasing CNT content in both the 1st and 2nd vibration modes. The CNT-epoxy nanocomposites also show similar increasing trends of damping ratio with CNT content, indicating the enhanced damping property of CFRPs arising mainly from the improved damping property of the modified matrix. The dynamic mechanical analysis further confirms that the CNTs have a strong influence on the composites damping properties. Both the dynamic loss modulus and loss factor of the nanocomposites and the corresponding CFRPs show consistent increases with the addition of CNTs, an indication of enhanced damping performance.     

Improving the flexural and thermomechanical properties of amino-functionalized carbon nanotube/epoxy composites by using a pre-curing treatment

A prior thermal (pre-curing) treatment of mixtures of epoxy monomer and amino-functionalized carbon nanotubes (CNTs) was used to promote a chemical reaction between the matrix and the reinforcement, favouring the formation of a strong interface. Samples of epoxy resin and different weight percentages of amino-functionalized multi-walled CNTs were prepared with and without the pre-curing treatment (150 °C, 1 h). The degree of dispersion of the nanofiller was better when this pre-curing treatment was used. This allowed a higher CNT content while keeping a high sample homogeneity. Without the pre-curing step, the addition of CNTs increases both the flexural strength and strain to failure by 45%. Moreover, with the pre-curing step, the nanocomposite with 0.25 wt.% CNTs presents an increase of flexural strength by 58% and strain to failure by 68% regard to neat epoxy resin.     

Hybrid network structure and thermal conductive properties in poly(vinylidene fluoride) composites based on carbon nanotubes and graphene nanoplatelets

A small quantity of carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) were introduced into the poly(vinylidene fluoride) (PVDF)/GNP and PVDF/CNT composites, respectively, to prepare the corresponding ternary PVDF/CNT/GNP and PVDF/GNP/CNT composites. The results demonstrated that adding CNTs into the PVDF/GNP composites greatly promoted the formation of the hybrid network structure of fillers. This was much different from the scenario that adding GNPs into the PVDF/CNT composites. GNPs and CNTs exhibited excellent nucleation effects for the crystallization of PVDF matrix; however, the variation of the PVDF crystallinity was small. Adding CNTs into the PVDF/GNP composites greatly enhanced the electrical conductivity of the PVDF/CNT/GNP composites. This was also different from the scenario of the PVDF/GNP/CNT composites. Furthermore, the PVDF/CNT/GNP composites exhibit higher thermal conductivity and higher synergistic efficiency compared with the PVDF/GNP/CNT composites. The conductive mechanisms and the synergistic effects of the ternary composites were then analyzed.     

Dispersion evaluation,processing and tensile properties of carbon nanotubes-modified epoxy composites prepared by high pressure homogenization

In this paper, high pressure homogenization (HPH) served as the main dispersion method for making carbon nanotubes (CNTs)-modified composite materials. A new quantitative approach was proposed to evaluate the dispersion of CNTs in epoxy resin by combining microscopic images with maximum likelihood estimation theory. The results were in good agreement with those obtained from optical observation and ultraviolet–visible (UV–vis) absorbance measurement. Moreover, the dispersion process specific to HPH processing was analyzed with the aid of the proposed approach. The changes of the morphologies and lengths of CNTs in HPH were illustrated. It was found that, in the first few cycles, the lengths of CNTs fell significantly and the entanglements remained severe. In the following cycles, individual CNTs were gradually separated from agglomerates and the lengths experienced a slow decline. After homogeneous dispersion, the transverse tensile properties of CNTs-modified carbon fiber reinforced epoxy composites (CFRP) got obviously ameliorated.     

Comparison of drying methods for the preparation of carbon fiber felt/carbon nanotubes modified epoxy composites

Carbon fiber felt with carbon nanotubes (CNTs) were prepared by immersing three-dimensional (3D) felt into CNT aqueous solution (with dispersant) followed by removing water with different drying methods. Epoxy resin was then introduced into the felt to obtain 3D fiber felt/CNTs modified epoxy composites. This paper highlights the effect of drying method on macro-morphologies of the felt, morphological dispersion of CNTs and some relevant properties of the composites, including electrical conductivity and flexural performance. The results demonstrate that compared to the commonly used heat drying method, freeze drying technique possesses obvious advantages for the fabrication of fiber felt/CNT modified epoxy composites.