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.     

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.     

Influence of carbon nanotube-polymeric compatibilizer masterbatches on morphological, thermal, mechanical, and tribological properties of polyethylene

Study was made of the effect of multiwall carbon nanotubes (MWCNTs) and polymeric compatibilizer on thermal, mechanical, and tribological properties of high density polyethylene (HDPE). The composites were prepared by melt mixing in two steps. Carbon nanotubes (CNTs) were melt mixed with maleic anhydride grafted polyethylene (PEgMA) as polymeric compatibilizer to produce a PEgMA-CNT masterbatch containing 20 wt% of CNTs. The masterbatch was then added to HDPE to prepare HDPE nanocomposites with CNT content of 2 or 6 wt%. The unmodified and modified (hydroxyl or amine groups) CNTs had similar effects on the properties of HDPE-PEgMA indicating that only non-covalent interactions were achieved between CNTs and matrix. According to SEM studies, single nanotubes and CNT agglomerates (size up to 1 μm) were present in all nanocomposites regardless of content or modification of CNTs. Addition of CNTs to HDPE-PEgMA increased decomposition temperature, but only slight changes were observed in crystallization temperature, crystallinity, melting temperature, and coefficient of linear thermal expansion (CLTE). Young’s modulus and tensile strength of matrix clearly increased, while elongation at break decreased. Measured values of Young’s moduli of HDPE-PEgMA-CNT composites were between the values of Young’s moduli for longitudinal (E₁₁) and transverse (E₂₂) direction predicted by Mori-Tanaka and Halpin-Tsai composite theories. Addition of CNTs to HDPE-PEgMA did not change the tribological properties of the matrix. Because of its higher crystallinity, PEgMA possessed significantly different properties from HDPE matrix: better mechanical properties, lower friction and wear, and lower CLTE in normal direction. Interestingly, the mechanical and tribological properties and CLTEs of HDPE-PEgMA-CNT composites lie between those of PEgMA and HDPE.     

Effect of surfactant treatment on thermal stability and mechanical properties of CNT/polybenzoxazine nanocomposites

The mechanical and thermo-mechanical properties of polybenzoxazine nanocomposites containing multi-walled carbon nanotubes (MWCNTs) functionalized with surfactant are studied. The results are specifically compared with the corresponding properties of epoxy-based nanocomposites. The CNTs bring about significant improvements in flexural strength, flexural modulus, storage modulus and glass transition temperature, T_g, of CNT/polybenzoxazine nanocomposites at the expense of impact fracture toughness. The surfactant treatment has a beneficial effect on the improvement of these properties, except the impact toughness, through enhanced CNT dispersion and interfacial interaction. The former four properties are in general higher for the CNT/polybenzoxazine nanocomposites than the epoxy counterparts, and vice versa for the impact toughness. The addition of CNTs has an ameliorating effect of lowering the coefficient of thermal expansion (CTE) of polybenzoxazine nanocomposites in both the regions below and above T_g, whereas the reverse is true for the epoxy nanocomposites. This observation has a particular implication of exploiting the CNT/polybenzoxazine nanocomposites in applications requiring low shrinkage and accurate dimensional control.     

Effect of carbon nanotube (CNT) content on the mechanical properties of CNT-reinforced aluminium composites

The interest in carbon nanotubes (CNTs) as reinforcements for aluminium (Al) has been growing considerably. Efforts have been largely focused on investigating their contribution to the enhancement of the mechanical performance of the composites. The uniform dispersion of CNTs in the Al matrix has been identified as being critical to the pursuit of enhanced properties. Ball milling as a mechanical dispersion technique has proved its potential. In this work, we use ball milling to disperse up to 5 wt.% CNT in an Al matrix. The effect of CNT content on the mechanical properties of the composites was investigated. Cold compaction and hot extrusion were used to consolidate the ball-milled Al–CNT mixtures. Enhancements of up to 50% in tensile strength and 23% in stiffness compared to pure aluminium were observed. Some carbide formation was observed in the composite containing 5 wt.% CNT. In spite of the observed overall reinforcing effect, the large aspect ratio CNTs used in the present study were difficult to disperse at CNT wt.% greater than 2, and thus the expected improvements in mechanical properties with increase in CNT weight content were not fully realized.     

Elevated temperature tensile properties and thermal expansion of CNT/2009Al composites

1.5 vol.% and 4.5 vol.% carbon nanotubes reinforced 2009Al (CNT/2009Al) composites with homogeneously dispersed CNTs and refined matrix grains, were fabricated using powder metallurgy (PM) followed by 4-pass friction stir processing (FSP). Tensile properties of the composites between 293 and 573 K and the coefficient of thermal expansion (CTE) from 293 to 473 K were tested. It was indicated that load transfer mechanism still takes effect at temperatures elevated up to 573 K, thus the yield strength of the 1.5 vol.% CNT/2009Al composite at 423–573 K, was enhanced compared with the 2009Al matrix. However, for the 4.5 vol.% CNT/2009Al composite, the yield strength at 573 K was even lower than that for the matrix, due to the quicker softening of ultrafine-grained matrix. Compared with the 2009Al matrix, the CTEs of the composites were greatly reduced for the zero thermal expansion and high modulus of the CNTs and could be well predicted by the Schapery’s model.     

Effect of multi-walled carbon nanotubes on mechanical,thermal and electrical properties of phenolic foam via in-situ polymerization

In this study, phenolic foam (PF)/multi-walled carbon nanotubes (MWCNTs) composites were fabricated by in-situ polymerization, and carbonized foams based on these PF foams were prepared and the electrical property was investigated. TEM results indicated excellent dispersion of MWCNTs in the phenolic resin matrix. Scanning electron microscope results indicated that PF composites exhibited smaller cell size, thicker cell wall thickness, and higher cell density, compared with pure PF. The incorporating of MWCNTs significantly improved the mechanical properties of PF. All PF composites showed a lower thermal conductivity versus pure PF. Moreover, the carbonized pure and composites PF exhibited open-cell three-dimensional skeleton carbon structure and the MWCNTs were well-dispersed on the surface of the skeletons. It is noteworthy that the introduction of MWCNTs significantly improved the electrical performances of foams and carbonized foams by construction of conductive MWCNTs network.     

Reinforcing brittle and ductile epoxy matrices using carbon nanotubes masterbatch

In this study, the mechanical and thermal properties of epoxy composites using two different forms of carbon nanotubes (powder and masterbatch) were investigated. Composites were prepared by loading the surface-modified CNT powder and/or CNT masterbatch into either ductile or brittle epoxy matrices. The results show that 3 wt.% CNT masterbatch enhances Young’s modulus by 20%, tensile strength by 30%, flexural strength by 15%, and 21.1 °C increment in the glass transition temperature (by 34%) of ductile epoxy matrix. From scanning electron microscopy images, it was observed that the CNT masterbatch was uniformly distributed indicating the pre-dispersed CNTs in the masterbatch allow an easier path for preparation of CNT-epoxy composites with reduced agglomeration of CNTs. These results demonstrate a good CNT dispersion and ductility of epoxy matrix play a key role to achieve high performance CNT-epoxy composites.     

Preparation,processing and analysis of physical properties of calcium ferrite-CNTs/PET nano-composite

The present work is focused on the preparation of composites based on Poly(ethylene terephthalate) (PET) and novel nano-hybrid filler composed of Calcium Ferrite (CF)-Carbon Nanotubes (CNTs), obtained by direct growth of CNTs on CF based iron catalysts. The carbon content in the hybrid filler was 76 wt%. Composites loaded with 1.0, 1.5, 2.0, 3.0 wt% of filler were obtained by melt compounding and processed by thin-wall injection molding. Unfilled Poly(ethylene terephthalate) was processed using the same techniques. Structural characterization and physical properties (thermal, mechanical and electrical) were analyzed and correlated to the hybrid filler loading, and to the percentage of carbon nanotubes.     

The effective properties and local aggregation effect of CNT/SMP composites

A micromechanics model of the thermomechanical constitutive behavior and micro-structural inhomogeneity of carbon nanotubes (CNTs)/shape memory polymer (SMP) composites is presented. It is assumed that the CNTs are elastic and the SMP obeys a thermomechanical constitutive law. The effective properties of CNT/SMP composites are examined using a micro-mechanics method. The effect of CNT aggregation in the composite, frequently encountered in real engineering situations, is studied. The degree of aggregation is described by an aggregation coefficient, and the effective properties of SMP composites with aggregated CNTs are calculated using a stepping scheme. It is shown that the degree of CNT aggregation dramatically influences the effective properties of the CNT/SMP composites. A homogeneous microstructure leads to maximum levels of effective composite properties.     

纳米碳管增强炭/炭复合材料的研究进展

纳米碳管(CNTs)具有独特的结构、优异的力学性能、热稳定性与传导性能,是炭/炭(C/C)复合材料理想的增强体.综述了纳米碳管增强炭/炭(CNTs/C/C)复合材料的制备方法,讨论了该复合材料的微观结构、摩擦学性能和传导性能,并展望了CNTs/C/C复合材料的潜在应用和发展趋势.     

Electroactive shape memory polymer based on optimized multi-walled carbon nanotubes/polyvinyl alcohol nanocomposites

The development of shape memory polymers (SMPs) has gained remarkable attention due to their wide range of applications, from biomedical to electromechanical. In this work, we have developed and optimized an electroactive SMP based on polyvinyl alcohol/multi-walled carbon nanotubes (PVA/MWNTs) composites. When a constant voltage of 60 V was applied to the optimized sample, the polymer shape could be recovered to the original form within 35 s. Different weight fractions of MWNT/PVA composites were prepared by using a simple solution blending and transitional solution casting method, and their microstructures, electrical conductivities, thermal conductivities, and electroactive shape memory properties were investigated. According to our systematic analysis, the enhanced performance can be attributed to the reinforcement of MWNTs that led to the improved electrical and thermal conductivities of the PVA matrix.     

Mechanical reinforcement while remaining electrical insulation of glass fibre/polymer composites using core–shell CNT@SiO2 hybrids as fillers

Carbon nanotubes (CNTs) have been widely used as mechanical reinforcement agents of composites. However, their aggregations, weak interfacial interaction with polymer, as well as high electrical conductivity limit their use in some especial applications. In this paper, the silicon oxide (SiO₂)-coated (CNT@SiO₂) core–shell hybrids with different SiO₂ thickness were prepared and employed to reinforce glass fibre-reinforced bismaleimide–triazine (BT) resin (GFRBT) composites. The results indicated the mechanical properties, including tensile strength and Young’s modulus increased with the increase of SiO₂ thickness and CNT@SiO₂ loading. Such enhanced mechanical properties were mainly attributed to the intrinsically nature of CNTs, homogeneous dispersion of the hybrids, as well as improved interfacial interaction. Meanwhile, the composites remained high electrical insulation (9.63 × 10¹² Ω cm) due to the existence of SiO₂ layer on CNT surface. This study will guide the design of functionalized CNTs and the construction of high-performance composites.     

Preparation and properties of poly (p-phenylene sulfide)/multiwall carbon nanotube composites obtained by melt compounding

In this paper, electrical and mechanical properties of Poly (p-phenylene sulfide) (PPS)/multi-wall carbon nanotubes (MWNTs) nanocomposites were reported. The composites were obtained just by simply melt mixing PPS with raw MWNTs without any pre-treatment. The dispersion of MWNTs and interfacial interaction were investigated through SEM &TEM and Raman spectra. The rheological test and crystallization behavior were also investigated to study the effects of MWNTs concentration on the structure and chain mobility of the prepared composites. Though raw MWNTs without any pre-treatment were used, a good dispersion and interaction between PPS and MWNTs have been evidenced, resulting in a great improvement of electrical properties and mechanical properties of the composites. Raman spectra showed a remarkable decrease of G band intensity and a shift of D bond, demonstrating a strong filler–matrix interaction, which was considered as due to π–π stacking between PPS and MWNTs. The storage modulus (G′) versus frequency curve presented a plateau above the percolation threshold of about 2–3 wt% with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behavior. Meanwhile, a conductive percolation threshold of 5 wt% was achieved and the conductivity of nanocomposites increased sharply by several orders of magnitude. The difference between electrical and rheological percolation threshold, and the effect of critical percolation on the chain mobility, especially on crystallization behavior of PPS, were discussed. In summary, our work provides a simple and fast way to prepare PPS/MWNTs nanocomposites with good dispersion and improved properties.     

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.%.     

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.     

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.     

Experimental investigation on the compression behaviors of epoxy with carbon nanotube under high strain rates

The compressive properties of epoxy with different carbon nanotubes (CNTs) contents at quasi-static and high strain rates loading had been investigated via experiment to evaluate the compressive failure behaviors and modes at different CNTs contents and different strain rates. The results indicated that the stress train curves were strain rate sensitive, and the compressive stiffness, compressive failure stress of composites with various CNTs contents was increased with the strain rates and CNTs contents. The compressive failure stress and the compressive failure modes of the composites were apparently different as the change of CNTs contents.     

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.     

Preparation, morphology and properties of acylchloride-grafted multiwall carbon nanotubes/fluorinated polyimide composites

A fluorinated polyimide (PI) was synthesized by a two-step reaction from 4,4′-(hexafluoroisopropylidene) diphthalic anhydride and 2,2′-bis(trifluoromethyl)-4,4′diaminobiphenyl. A series of PI composites with various mass fractions of multi-walled carbon nanotubes (MWNTs) were prepared by either an in situ polymerization or blending process. To increase the chemical compatibility of carbon nanotubes with the PI matrix, MWNTs were treated with an acid mixture and sulfoxide chloride by turns. Results show that the dispersion of the MWNTs is highly improved in the PI by modification. The modified MWNTs are dispersed homogeneously in the matrix, while the structures of the PI and MWNTs are stable in the preparation process. The thermal stability of the nanocomposites is slightly lower than that of the pure PI. With incorporating MWNTs, the storage modulus and glass transition temperature of the composite films enhanced comparing to that of PI matrix. The dielectric constants of the composites increase sharply, which is favorable to their practical use in anti-static materials and embedded capacitors.