Multifunctional properties of high volume fraction aligned carbon nanotube polymer composites with controlled morphology

Advanced composites, such as those used in aerospace applications, employ a high volume fraction of aligned stiff fibers embedded in high-performance polymers. Unlike advanced composites, polymer nanocomposites (PNCs) employ low volume fraction filler-like concepts with randomly-oriented and poorly controlled morphologies due to difficult issues such as dispersion and alignment of the nanostructures. Here, novel fabrication techniques yield controlled-morphology aligned carbon nanotube (CNT) composites with measured non-isotropic properties and trends consistent with standard composites theories. Modulus and electrical conductivity are maximal along the CNT axis, and are the highest reported in the literature due to the continuous aligned-CNTs and use of an unmodified aerospace-grade structural epoxy. Rule-of-mixtures predictions are brought into agreement with the measured moduli when CNT waviness is incorporated. Waviness yields a large (10×) reduction in modulus, and therefore control of CNT collimation is seen as the primary limiting factor in CNT reinforcement of composites for stiffness. Anisotropic electron transport (conductivity and current-carrying capacity) follows expected trends, with enhanced conductivity and Joule heating observed at high current densities.     

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.     

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.     

Properties of composites of carbon nanotube fibres

Composites have set the standard for high strength materials for several decades. With the discovery of nanotubes, new possibilities for reinforced composites have arisen, with potential mechanical properties superior to those of currently available materials. This paper reports the properties of epoxy matrix reinforced with fibres of carbon nanotubes (CNTs) which, in many ways, are similar to standard composites reinforced with commercial fibres. The composites were formed by the back diffusion of the uncured epoxy into an array of aligned fibres of CNTs. The fibre density and volume fraction were measured from thermogravimetric analysis (TGA). Properties in tension and compression were measured, and the level of fibre–matrix interaction analysed fractographically. The results show the significant potential for this route to CNT reinforcement.     

Novel method for functionalising and patterning textile composites: Liquid resin print

The paper reports a novel method of integrating resin into continuous textile reinforcement. The method presents a print of liquid reactive resin into textile preforms. A series of targeted injections forms a patch which upon consolidation and curing transforms into a stiff region continuously spanning through preform thickness. Enhancing the injected resin with conductive phase allows creating a pattern of patches with controlled dimensions and added functionalities. Patterned composites reveal features which are not typical for conventional composites such as fibre bridged interfaces, regular thickness variation, and gradient matrix properties. The presented study explores the role of these features in (a) the mechanical behaviour of these materials, focusing on their deformation and failure mechanisms in tension, and (b) the feasibility of adding functionality by printing electrically conductive resins containing carbon nano-tubes (CNT). It was shown that resin print is a promising method for local functionalization of structural composites.     

Effects of CNT diameter on mechanical properties of aligned CNT sheets and composites

Drawing, winding, and pressing techniques were used to produce horizontally aligned carbon nanotube (CNT) sheets from free-standing vertically aligned CNT arrays. The aligned CNT sheets were used to develop aligned CNT/epoxy composites through hot-melt prepreg processing with a vacuum-assisted system. Effects of CNT diameter change on the mechanical properties of aligned CNT sheets and their composites were examined. The reduction of the CNT diameter considerably increased the mechanical properties of the aligned CNT sheets and their composites. The decrease of the CNT diameter along with pressing CNT sheets drastically enhanced the mechanical properties of the CNT sheets and CNT/epoxy composites. Raman spectra measurements showed improvement of the CNT alignment in the pressed CNT/epoxy composites. Research results suggest that aligned CNT/epoxy composites with high strength and stiffness are producible using aligned CNT sheets with smaller-diameter CNTs.     

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.     

Strain sensing in composites using aligned carbon nanotube sheets embedded in the interlaminar region

This paper introduces a novel technique for embedding aligned sheets of two millimeters long, interconnected CNTs into the interlaminar region of composite structures. The potential of these embedded CNT sheets to function as damage detecting and strain sensing elements was demonstrated via various mechanical tests that were accompanied by real time electrical resistance change data acquisition. The experimental results suggested that the CNT sheet sensitivity could be further enhanced by an oxygen plasma treatment and also by pre-straining the CNT sheets before embedding them. The samples containing two CNT sheets layers exhibited long term stability, sensitivity and repeatability which are vital features for health monitoring.     

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.     

Complementary percolation characteristics of carbon fillers based electrically percolative thermoplastic elastomer composites

Electrically percolative composites of thermoplastic elastomers (TPE) filled with different concentrations of carbon nanotubes (CNT), carbon black (CB) and (CNT–CB) hybrid fillers were fabricated by melt blending. The effects of filler type and composition on the electrical properties of the percolative TPE composites were studied. Percolation threshold for CB-, CNT- and (CNT–CB)-based composites was found to be 0.06, 0.07 and 0.07 volume fraction respectively. Compared to CB-based composites and earlier reported results, CNT- and (CNT–CB)-based ones revealed an unexpectedly high percolation threshold, which otherwise considered an unwelcome phenomenon, lead to distinct and rare percolation characteristics of CNT filled percolative composites like per-percolation conductivity and a relatively steep percolation curves. CB-based composites showed a comparatively sharp insulator–conductor transition curve complementing the percolation characteristics CNT- and (CNT–CB)-based composites. Percolation threshold conductivity of the fillers was in the order of CB > CNT > (CNT–CB), while maximum attained conductivities followed the order of CNT > (CNT–CB) > CB. Conductivity order of fillers not only denied much reported synergic effect in (CNT–CB) filler but also highlighted the effect of percolation characteristics on the outcome of conductivity values. Results obtained were of theoretical as well as practical importance and were explained in the context of filler morphology and different dispersion characteristics of the carbon based fillers.     

Mechanical properties of carbon nanotube reinforced polymer nanocomposites: A coarse-grained model

In this work, a coarse-grained (CG) model of carbon nanotube (CNT) reinforced polymer matrix composites is developed. A distinguishing feature of the CG model is the ability to capture interactions between polymer chains and nanotubes. The CG potentials for nanotubes and polymer chains are calibrated using the strain energy conservation between CG models and full atomistic systems. The applicability and efficiency of the CG model in predicting the elastic properties of CNT/polymer composites are evaluated through verification processes with molecular simulations. The simulation results reveal that the CG model is able to estimate the mechanical properties of the nanocomposites with high accuracy and low computational cost. The effect of the volume fraction of CNT reinforcements on the Young's modulus of the nanocomposites is investigated. The application of the method in the modeling of large unit cells with randomly distributed CNT reinforcements is examined. The established CG model will enable the simulation of reinforced polymer matrix composites across a wide range of length scales from nano to mesoscale.     

Percolation model of reinforcement efficiency for carbon nanotubes dispersed in thermoplastics

Considerable experimental work on carbon nanotube-reinforced composites has shown that the reinforcement efficiency of carbon nanotubes (CNTs) becomes lower than the theoretical expectation when CNT content reaches a critical value. This critical volume fraction (percolation threshold) is considered related to the formation of percolating network. In this work, a percolation model is proposed to describe the observed sharp decrease in the reinforcement efficiency of multiwalled CNTs (MWCNTs) dispersed in thermoplastics when the CNT content exceeds the percolation threshold. The percolation threshold is estimated via a numerical simulation of randomly curved CNTs according to the statistics on geometrical features of real CNTs. The percolation model, integrated into the Halpin–Tsai equations, is verified using the experimental data of various thermoplastic composites reinforced with MWCNTs. The developed mechanical model achieves a good agreement with the measured moduli of nanocomposites, and demonstrates an excellent prediction capability over a wide range of CNT content.     

Highly aligned flax/polypropylene nonwoven preforms for thermoplastic composites

A major challenge for natural fibre composites is to achieve high mechanical performance at a competitive price. Composites constructed from unidirectional yarns and woven fabrics are known to perform significantly better than composites made from random nonwoven mats, but unidirectional yarns and fabrics are much more expensive to manufacture than random nonwoven mats. Here, we report on highly aligned natural fibre nonwoven mats that can be used as a replacement for unidirectional woven fabrics. A drawing operation is added to the conventional nonwoven process to improve fibre alignment in the nonwoven preforms and the final composites. The modified nonwoven manufacturing process is much simpler and cheaper than the unidirectional woven fabric process because of the elimination of expensive spinning and weaving operations. The composites fabricated from the highly aligned nonwoven mats showed similar mechanical strength as the composites made from unidirectional woven fabrics.     

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.     

Nanoscale structure and local mechanical properties of fiber-reinforced composites containing MWCNT-grafted hybrid glass fibers

Carbon nanotubes (CNTs) were grown from the surface of glass fibers by chemical vapor deposition, and these hybrid fibers were individually dispersed in an epoxy matrix to investigate the local composite structure and properties near the fiber surface. High-resolution transmission electron microscopy revealed the influence of infiltration and curing of a liquid epoxy precursor on the morphology of the CNT “forest” region, or region of high CNT density near the fiber surface. Subsequent image analysis highlighted the importance of spatially dependent volume fractions of CNTs in the matrix as a function of distance from the fiber surface, and nanoindentation was used to probe local mechanical properties in the CNT forest region, showing strong correlations between local stiffness and volume fraction. This work represents the first in situ measurements of local mechanical properties of the nano-structured matrix region in hybrid fiber-reinforced composites, providing a means of quantifying the reinforcement provided by the grafted nanofillers.     

Mechanical properties of high density polyethylene/carbon nanotube composites

Carbon-nanotubes (CNTs) have been used with polymers from the date of their inception to make composites having remarkable properties. An attempt has been made in this direction, in order to enhance mechanical and tribological properties of the composite materials. The latter, were achieved through the injection molding of high density polyethylene (HDPE) reinforced with specific volume fraction of CNTs. A considerable improvement on mechanical properties of the material can be observed when the volume fraction of CNT is increased. The composite reinforcement shows a good load transfer effect and interface link between CNT and HDPE. The volumetric wear rate is calculated from the Wang’s model, Ratner’s correlation and reciprocal of toughness. The results obtained clearly show the linear relationship with CNT loading which supports the microscopic wear model. It is concluded that both Halpin–Tsai and modified series model can be used to predict Young’s modulus of CNT–HDPE composites. From thermal analysis study, it is found that melting point and oxidation temperature of the composites are not affected by the addition of CNTs, however its crystallinity seems to increase.     

Fabrication of nature-inspired bulk laminar composites by a powder processing

Among many kinds of “nano-laminar” composites inspired by the brick and mortar structure of nacre in mollusk shells, a bulky, dense and ceramics–base composite has been a missing piece despite its importance. Here we report that such a composite with a submicron-order layered structure can be fabricated by a simple method, sintering aligned flake-like inorganic powder coated with ductile matrix material. The composites fabricated by this method had crack extension resistance by interface delamination, crack deflection, and ligament bridging by the ductile matrix. They showed non-brittle fracture behavior in a bending test despite a quite high flake volume fraction of over 80%, and had a work of fracture (WOF) of more than 300 J/m², several hundreds times as large as that of monolithic glass.     

Modelling of the carbon nanotube bridging effect on the toughening of polymers and experimental verification

The effect of aligned and randomly oriented carbon nanotube (CNT), with respect to the crack growth plane, on the fracture toughness of polymers is modelled in this paper using the Elastic Plastic Fracture Mechanics. According to a critical length, two dominant toughening mechanisms for CNT-modified polymers are presented, i.e. CNT pull-out and CNT rupture. The model is then used to identify the effect of CNTs geometrical and mechanical properties on the enhancement of fracture toughness in CNT-modified polymers. The key CNT properties are the CNT radius, average length, ultimate strength, elongation before failure, interfacial shear strength between CNTs and the polymer and nanotube volume fraction. Finally, experimental results are compared with the model predictions. The correlation shows that processing of long, aligned CNTs remains the main barrier in achieving major fracture toughness enhancement.     

Effect of MWCNT alignment on mechanical and self-monitoring properties of extruded PET–MWCNT nanocomposites

Self-monitoring aligned MWCNT loaded PET composites, with different CNT content, were prepared via twin-screw extrusion starting from a PET/MWCNT masterbatch, and fully characterized. All electrically conductive samples showed self-monitoring ability, i.e. a variation in electrical resistance as a function of stress. Moreover, the insertion of MWCNTs resulted in mechanical reinforcement with respect to neat PET. It was found that both self-monitoring behavior and mechanical performance are directly related to MWCNT content and to the direction of applied stress with respect to CNT orientation. In particular, too high MWCNT content decreased sensitivity at low strain, whereas a minimum MWCNT content was required to insure ohmic conductivity.