Compression resistance and hysteresis of carbon fibre tows with grown carbon nanotubes/nanofibres

Growth of carbon nanotubes (CNT) or carbon nano-fibres (CNF) on fibrous substrates is a way to increase the fracture toughness of fibre reinforced composites (FRC), with encouraging results reported in the recent years. The issues for these materials related to manufacturing of these composites are, however, less investigated. Following the study of compressibility of woven carbon fibre preforms with CNT/CNFs grown on the fibres using the CVD method [Compos Sci Technol 2011; 71(3): 315-325], this paper describes compression tests on the carbon tows used in these fabrics. The results of the measurements include pressure vs. thickness diagrams in consecutive compression cycles and hysteresis of the compression. The results confirm a drastic change of compressibility of fibrous assemblies in the presence of CNT/CNF grafting.     

Recycled carbon fibre-reinforced polypropylene thermoplastic composites

Comingled carbon fibre (CF)/polypropylene (PP) yarns were produced from chopped recycled carbon fibres (reCF) (20 mm in length, 7-8 μm diameter) blended with matrix polypropylene staple fibres (60 mm in length, 28 μm diameter) using a modified carding and wrap spinning process. Microscopic analysis showed that more than 90% of the reCF were aligned along the yarn axis. Thermoplastic composite test specimens fabricated from the wrap-spun yarns had 15-27.7% reCF volume content. Similar to the yarn, greater than 90% of the reCF comprising each composite sample made, showed a parallel alignment with the axis of the test specimens. The average values obtained for tensile, and flexural strengths were 160 MPa and 154 MPa, respectively for composite specimens containing 27.7% reCF by volume. It was concluded that with such mechanical properties, thermoplastic composites made from recycled CF could be used as low cost materials for many non-structural applications.     

Study on the semi-empirical model for the complex permittivity of carbon nanocomposite laminates in microwave frequency band

A semi-empirical model is proposed for the complex permittivity of composites containing electrical conductive carbon nanomaterials such as carbon black (CB), carbon nanofiber (CNF) and multi-walled carbon nanotube (CNT). The composites were fabricated with E-glass fabric/epoxy prepregs. The model is based on the percolation theory. The model is available for the composite of filler content over the percolation threshold and applicable within the high frequency band in which AC electrical conductivity of the composite is continuously proportional to the frequency. The proposed model is composed of the numerical equations of the scaling law in percolation theory and constants obtained from experiments to quantify the model. The model describes the complex permittivity as a function of frequency and filler content. The model was verified when compared with the measurements. The measurements for the complex permittivities of the composites were performed at the frequency band between 0.5 and 18.0 GHz using a vector network analyzer with a 7 mm coaxial air line.     

A novel approach to fabricate high volume fraction nanocomposites with long aligned carbon nanotubes

Conventional micro-fiber-reinforced composites provide insight into critical structural features needed for obtaining maximum composite strength and stiffness: the reinforcements should be long, well aligned in a unidirectional orientation, and should have a high reinforcement volume fraction. It has long been a challenge for researchers to process CNT composites with such structural features. Here we report a method to quickly produce macroscopic CNT composites with a high volume fraction of millimeter long, well aligned CNTs. Specifically, we use the novel method, shear pressing, to process tall, vertically aligned CNT arrays into dense aligned CNT preforms, which are subsequently processed into composites. Alignment was confirmed through SEM analysis while a CNT volume fraction in the composites was calculated to be 27%, based on thermogravimetric analysis data. Tensile testing of the preforms and composites showed promising mechanical properties with tensile strengths reaching 400 MPa.     

Enhancement of carbon nanotube fibres using different solvents and polymers

Liquid infiltration is an efficient way to densify carbon nanotubes (CNTs) and was used to strengthen CNT fibres in the method of array spinning. Rather than the volatility, the dipole moment of solvent plays a more important role in determining the densification level. The fibres densified by highly polar but non-volatile solvents such as N,N-dimethylformamide, dimethyl sulphoxide, and N-methyl-2-pyrrolidone were 100–200 MPa stronger than those by ethanol and acetone. Ethylene glycol is the most efficient solvent due to its two polar OH groups and improved the fibre strength to 1.45 GPa. Long chain or cross-linked polymers like polyvinyl alcohol, polyimide, and bismaleimide (BMI) were introduced into CNT fibres by infiltration with aid of polar solvents. These polymers reinforced the fibres significantly, as they can connect non-neighboring CNTs and benefit the load transfer. The strongest CNT/BMI fibre was 2.38 GPa in strength and 110 GPa in modulus.     

Fabrication and characterization of recyclable carbon nanotube/polyvinyl butyral composite fiber

A surface-draw method to fabricate recyclable carbon nanotube/polyvinyl butyral (CNT/PVB) composite fibers is reported. This method is effective for both single-walled carbon nanotube (SWCNT) and multi-walled carbon nanotube. The CNT mass content of CNT/PVB composite fibers can vary from 0 to 80 wt.%, which is higher than most CNT/polymer composites reported to date. The diameter of the composite fibers can be controlled in the range of 10-100 μm, with essentially unlimited draw length. The composite fibers with 7.4 wt.% SWCNTs showed optimal tensile properties. Compared with pure PVB fibers, the tensile strength, failure strain, and elastic modulus of the composite fiber have improved about 127%, 27%, and 73%, respectively. In addition, SWCNT/PVB composites with 66.7 wt.% SWCNTs have the highest conductivity of 42.9 S m⁻¹. More importantly, the major benefit is the “greenness” of the method, which involves environment friendly ethanol-water solvent with no functionalization of the nanotube required, and only simple apparatus are needed. The CNT/PVB composite fibers obtained can be dissolved in ethanol solution and reformed with the surface draw method without any additional treatment; and the material properties after recycle is comparable to those fabricated in the first round.     

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.     

Highly strong and conductive carbon nanotube/cellulose composite paper

Carbon nanotube (CNT)/cellulose composite materials were fabricated in a paper making process optimized for a CNT network to form on the cellulose fibers. The measured electric conductivity was from 0.05 to 671 S/m for 0.5–16.7 wt.% CNT content, higher than that for other polymer composites. The real permittivities were the highest in the microwave region. The unique CNT network structure is thought to be the reason for these high conductivity and permittivity values. Compared to other carbon materials, our carbon CNT/cellulose composite material had improved parameters without decreased mechanical strength. The near-field electromagnetic shielding effectiveness (EMI SE) measured by a microstrip line method depended on the sheet conductivity and qualitatively matched the results of electromagnetic field simulations using a finite-difference time-domain simulator. A high near-field EMI SE of 50-dB was achieved in the 5–10 GHz frequency region with 4.8 wt.% composite paper. The far-field EMI SE was measured by a free space method. Fairly good agreement was obtained between the measured and calculated results. Approximately 10 wt.% CNT is required to achieve composite paper with 20-dB far-field EMI SE.     

Thermomechanical properties of copper–carbon nanofibre composites prepared by spark plasma sintering and hot pressing

Several types of carbon nanofibres (CNF) were coated with a uniform and dense copper layer by electroless copper deposition. The coated fibres were then sintered by two different methods, spark plasma sintering (SPS) and hot pressing (HP). The Cu coating thickness was varied so that different volume fraction of fibres was achieved in the produced composites. In some cases, the CNF were pre-coated with Cr for the improvement the Cu adhesion on CNF. The results show that the dispersion of the CNF into the Cu matrix is independent of the sintering method used. On the contrary, the dispersion is directly related to the efficiency of the Cu coating, which is tightly connected to the CNF type. Overall, strong variations of the thermal conductivity (TC) of the composites were observed (20–200 W/mK) as a function of CNF type, CNF volume fraction and Cr content, while the coefficient of thermal expansion (CTE) in all cases was found to be considerably lower than Cu (9.9–11.3 ppm/K). The results show a good potential for SPS to be used to process this type of materials, since the SPS samples show better properties than HP samples even though they have a higher porosity, in applications where moderate TC and low CTE are required.     

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.     

Effect of carbon nanofibers on the infiltration and thermal conductivity of carbon/carbon composites

Preforms containing 0, 5, 10, 15 and 20 wt.% carbon nanofibers (CNFs) were fabricated by spreading layers of carbon cloth, and infiltrated using the electrified preform heating chemical vapor infiltration method (ECVI) under atmospheric pressure. Initial thermal gradients were determined. Resistivity and density evolutions with infiltration time have been recorded. Scanning electron microscopy, polarized light micrograph and X-ray diffraction technique were used to analyze the experiment results. The results showed that the infiltration rate increased with the rising of CNF content, and after 120 h of infiltration, the density was the highest when the CNF content was 5 wt.%, but the composite could not be densified efficiently as the CNF content ranged from 10 wt.% to 20 wt.%. CNF-reinforced C/C composites have enhanced thermal conductivity, the values at 5 wt.% were increased by nearly 5.5-24.1% in the X-Y direction and 153.8-251.3% in the Z direction compared to those with no CNFs. When the additive content was increased to 20 wt.%, due to the holes and cavities in the CNF web and between carbon cloth and matrix, the thermal conductivities in the X-Y and Z directions decreased from their maximum values at 5 wt.%.     

Mechanical properties of aligned multi-walled carbon nanotube/epoxy composites processed using a hot-melt prepreg method

This study examined the mechanical properties of aligned multi-walled carbon nanotube (CNT)/epoxy composites processed using a hot-melt prepreg method. Vertically aligned ultra-long CNT arrays (forest) were synthesized using chemical vapor deposition, and were converted to horizontally aligned CNT sheets by pulling them out. An aligned CNT/epoxy prepreg was fabricated using hot-melting with B-stage cured epoxy resin film. The resin content in prepreg was well controlled. The prepreg sheets showed good drapability and tackiness. Composite film specimens of 24-33 μm thickness were produced, and tensile tests were conducted to evaluate the mechanical properties. The resultant composites exhibit higher Young’s modulus and tensile strength than those of composites produced using conventional CNT/epoxy mixing methods. For example, the maximum elastic modulus and ultimate tensile strength (UTS) of a CNT (21.4 vol.%)/epoxy composite were 50.6 GPa and 183 MPa. These values were, respectively, 19 and 2.9 times those of the epoxy resin.     

Growth of carbon nanotubes on carbon fibre substrates to produce hybrid/phenolic composites with improved mechanical properties

Carbon nanotubes were grown by chemical vapor deposition (CVD) on different carbon fibre substrates namely, unidirectional (UD) carbon fibre tows, bi-directional (2D) carbon fibre cloth and three dimensional (3D) carbon fibre felt. These substrates were used as the reinforcement in phenolic resin matrix to develop hybrid CF–CNT composites. The growth morphology and other characteristics of the as grown tubes were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermal gravimetry (TGA) which confirmed a copious growth of multiwalled carbon nanotubes (MWNTs) on these substrates. The mechanical properties of the hybrid composites was found to increase with the increasing amount of deposited carbon nanotubes. The flexural strength (FS) improved by 20% for UD, 75% for 2D and 66% for 3D hybrid composites as compared to that prepared by neat reinforcements (without CNT growth) under identical conditions. Flexural modulus (FM) of these composites also improved by 28%, 54% and 46%, respectively.     

A negative Poisson’s ratio carbon fibre composite using a negative Poisson’s ratio yarn reinforcement

The manufacture of negative Poisson’s ratio (auxetic) composites, containing inherently auxetic phases is rare and has been confined to relatively low modulus composite systems with stiffnesses several orders of magnitude below those of structural composites. This paper presents the use of an auxetic double helix yarn that is used to produce a unidirectional fibre composite with both relatively high stiffness (4 GPa) and negative Poisson’s ratio (−6.8), at 30% fibre volume fraction, compared to other auxetic composites. This is the first structural auxetic composite to be produced using carbon fibre and importantly it was produced using standard manufacturing techniques and therefore is potentially applicable in a variety of engineering applications.     

Increasing the through-thickness thermal conductivity of carbon fiber polymer-matrix composite by curing pressure increase and filler incorporation

The low through-thickness thermal conductivity limits heat dissipation from continuous carbon fiber polymer-matrix composites. This conductivity is increased by up to 60% by raising the curing pressure from 0.1 to 2.0 MPa and up to 33% by incorporation of a filler (?1.5 vol.%) at the interlaminar interface. The 7-μm-diameter 7-W/m K-thermal-conductivity continuous fiber volume fraction is increased by the curing pressure increase, but is essentially unaffected by filler incorporation. The thermal resistivity is dominated by the lamina resistivity (which is contributed substantially by the intralaminar fiber-fiber interfacial resistivity), with the interlaminar interface thermal resistivity being unexpectedly negligible. The lamina resistivity and intralaminar fiber-fiber interfacial resistivity are decreased by up to 56% by raising the curing pressure and up to 36% by filler incorporation. The curing pressure increase does not affect the effectiveness of 1-mm-long 10-μm-diameter 900-1000-W/m K-thermal-conductivity K-1100 carbon fiber or single-walled carbon nanotube (SWCNT) as fillers for enhancing the conductivity, but hinders the effectiveness of carbon black (CB, low-cost), which is less effective than K-1100 or SWCNT at the higher curing pressure, but is almost as effective as K-1100 and SWCNT at the lower curing pressure. The effectiveness for enhancing the flexural modulus/strength/ductility decreases in the order: SWCNT, CB, K-1100.     

Effect of heat treatment of carbon nanofibres on electroless copper deposition

Cu is a well known heat sink material due to its high thermal conductivity. However, its coefficient of thermal expansion (CTE) is high. One of the most promising solutions for reducing it is to reinforce copper with carbon nanofibres (CNF) because of their low CTE. To exploit the properties of the CNFs a good dispersion of the reinforcement within the matrix must be achieved. One of the processing methods used to obtain a homogeneous CNF distribution is coating the CNF with Cu using electrochemical deposition. In this paper, the effect of the carbon structure on electroless deposition technique is studied. Different CNF have been compared: herringbone (HB), platelet (PL) and longitudinally aligned (previously heat treated) (LAHT). Herringbone and Platelet CNF were heat treated at 2750 °C for 30′ which resulted in a structure resembling graphite with loops at the fibre surface. These loops are responsible for an enhancement of the copper coating. It is shown that the Cu coverage in electroless deposition is high for the graphene plane and poor at the edges of the plane.     

Optimization of the chemical vapor deposition process for fabrication of carbon nanotube/Al composite powders

In order to optimize the chemical vapor deposition process for fabrication of carbon nanotube/Al composite powders, the effect of different reaction conditions (such as reaction temperature, reaction time, and reaction gas ratio) on the morphological and structural development of the powder and dispersion of CNTs in Al powder was investigated using transmission electron microscope. The results showed that low temperatures (500-550 °C) give rise to herringbone-type carbon nanofibers and high temperatures (600-630 °C) lead to multi-walled CNTs. Long reaction times broaden the CNT size distribution and increase the CNT yield. Appropriate nitrogen flow is preferred for CNT growth, but high and low nitrogen flow result in carbon nanospheres and CNTs with coarse surfaces, respectively. Above results show that appropriate parameters are effective in dispersing the nanotubes in the Al powder which simultaneously protects the nanotubes from damage.     

The effect of carbon nanotubes microstructures on reinforcing properties of SWNTs/alumina composite

Alumina reinforced with 1 wt% single-wall carbon nanotubes (SWNTs) was fabricated by hot-pressing. The fracture toughness of SWNTs/Al₂O₃ composite reaches 6.40 ± 0.3 MPa m^1/2, which is twice as high as that of unreinforced alumina. Nanoindentation introduced controlled cracks and the damage were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SWNTs reinforcing mechanisms including CNT pullout, CNT fracture, CNT bridging and crack deflection were directly observed, and the relationship between carbon nanotubes microstructures in the matrix and mechanical properties was also discussed in detailed.     

Conductive network formation in the melt of carbon nanotube/thermoplastic polyurethane composite

This research concerns the effect of conductive network formation in a polymer melt on the conductivity of multi-walled carbon nanotube/thermoplastic polyurethane composite systems. An extremely low percolation threshold of 0.13 wt.% was achieved in hot-pressed composite film samples, whereas a much higher CNT concentration (3–4 wt.%) is needed to form a conductive network in extruded composite strands. This is explained in terms of the dynamic percolation behaviour of the CNT network in the polymer melt. The temperature and CNT concentration needed for dynamic percolation to take effect were studied by the conductivity versus temperature behaviour of extruded strands, in an attempt to optimise the processing conditions.     

Formation and mechanical characterisation of SU8 composite films reinforced with horizontally aligned and high volume fraction CNTs

Carbon nanotube (CNT) reinforced composites have been identified as promising structural materials for the mechanical components of microelectromechanical systems (MEMS), potentially leading to advanced performance. High alignment and volume fraction of CNTs in the composites are the prerequisites to achieve such desirable mechanical characteristics. In particular, horizontal CNT alignment in composite films is necessary to enable high longitudinal moduli of the composites which is crucial for the performance of microactuators. A practical process has been developed to transfer CNT arrays from vertical to horizontal alignment which is followed by in situ wetting, realign and pressurized consolidation processes, which lead to a high CNT volume fraction in the range of 46-63%. As a result, SU8 epoxy composite films reinforced with horizontally aligned CNTs and a high volume faction of CNTs have been achieved with outstanding mechanical characteristics. The transverse modulus of the composite films has been characterised through nanoindentation and the longitudinal elastic modulus has been investigated. An experimental transverse modulus of 9.6 GPa and an inferred longitudinal modulus in the range of 460-630 GPa have been achieved, which demonstrate effective CNT reinforcement in the SU8 matrix.