Impact behavior and fractographic study of carbon nanotubes grafted carbon fiber-reinforced epoxy matrix multi-scale hybrid composites

Carbon nanotubes are the most promising reinforcement for high performance composites. Multiwall carbon nanotubes were directly grown onto the carbon fiber surface by catalytic thermal chemical vapor deposition technique. Multi-scale hybrid composites were fabricated using the carbon nanotubes grown fibers with epoxy matrix. Morphology of the grown carbon nanotubes was investigated using field emission scanning electron microscopy and transmission electron microscopy. The fabricated composites were subjected to impact tests which showed 48.7% and 42.2% higher energy absorption in Charpy and Izod impact tests respectively. Fractographic analysis of the impact tested specimens revealed the presence of carbon nanotubes both at the fiber surface and within the matrix which explained the reason for improved energy absorption capability of these composites. Carbon nanotubes presence at various cracks formed during loading provided a direct evidence of micro crack bridging. Thus the enhanced fracture strength of these composites is attributed to stronger fiber–matrix interfacial bonding and simultaneous matrix strengthening due to the grown carbon nanotubes.     

Hybrid carbon nanotube–carbon fiber composites with improved in-plane mechanical properties

In this study carbon nanotubes (CNTs) were grown on carbon fibers to enhance the in-plane and out-of-plane properties of fiber reinforced polymer composites (FRPs). A relatively low temperature synthesis technique was utilized to directly grow CNTs over the carbon fibers. Several composites based on carbon fibers with different surface treatments (e.g. growing CNTs with different lengths and distribution patterns and coating the fibers with a thermal barrier coating (TBC) layer) were fabricated and characterized via on- and off-axis tensile tests. The on-axis tensile strength and ductility of the hybrid FRPs were improved by 11% and 35%, respectively, due to the presence of the TBC and the surface grown CNTs. This configuration also exhibited 16% improvement on the off-axis stiffness. Results suggest that certain CNT growth patterns and lengths are more pertinent than the other surface treatments to achieve superior mechanical properties.     

A systematic investigation into a novel method for preparing carbon fibre–carbon nanotube hybrid structures

By electrospraying solvent dispersed carbon nanotubes (CNTs) with a binder onto carbon fibre (CF), hybrid structures, with an end aim to improve interfacial bonding in composites, were formed. The electrospray parameters controlling the modification of the CNT morphologies were studied. High-speed camera observations found applied voltage was critical for determining spray mode development. Electric field simulations revealed a concentrated electric field region around each fibre. Both voltage and distance played an important role in determining the CNT morphology by mediating anchoring strength and electric field force. The forming mechanism investigation of different surface morphologies suggested that binder with appropriate wetness gives freedom to the CNTs, allowing them to orientate radially from the CF surface. Linear density (LD) measurements and thermogravimetric analysis revealed that a 10 min coating increased the LD of a single CF filament by up to 31.7% while a 1 h treatment increased fibre bundle mass by 1%.     

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.     

Hierarchical composites of carbon nanotubes on carbon fiber: Influence of growth condition on fiber tensile properties

Growing carbon nanotubes (CNT) on the surface of high performance carbon fibers (CF) provides a means to tailor the thermal, electrical and mechanical properties of the fiber–resin interface of a composite. However, many CNT growth processes require pretreatment of the fiber, deposition of an intermediate layer, or harsh growth conditions which can degrade tensile properties and limit the conduction between the fiber and the nanotubes. In this study, high density multi-wall carbon nanotubes were grown directly on two different polyacrylonitrile (PAN)-based carbon fibers (T650 and IM-7) using thermal Chemical Vapor Deposition (CVD). The influence of CVD growth conditions on the single-fiber tensile properties and CNT morphology was investigated. The mechanical properties of the resultant hybrid fibers were shown to depend on the carbon fiber used, the presence of a sizing (coating), the CNT growth temperature, growth time, and atmospheric conditions within the CVD chamber. The CNT density and alignment morphology was varied with growth temperature and precursor flow rate. Overall, it was concluded that a hybrid fiber with a well-adhered array of dense MWCNTs could be grown on the unsized T650 fiber with no significant degradation in tensile properties.     

Compressibility of carbon woven fabrics with carbon nanotubes/nanofibres grown on the fibres

Growth of carbon nanotubes (CNT) or carbon nano-fibres (CNF) on carbon fibrous substrates is a way to increase the fracture toughness of fibre reinforced composites (FRC), with encouraging results reported in the recent years. If these nano-engineered FRC (nFRC) are destined to leave laboratories and enter industrial-scale production, a question of adapting the existing composite manufacturing methods will arise. The paper studies compressibility of woven carbon fibre performs (two types of fabrics) with CNT/CNF grown on the fibres using the CVD method. The results include pressure vs thickness and pressure vs fibre volume fraction diagrams for one and four layers of the fabric. Morphology of the nFRC is studied with SEM. It is shown that the pressure needed to achieve the target fibre volume fraction of the preform increases drastically (for example, from 0.05 MPa to more than 0.5 MPa for a fibre volume fraction of 52%) when CNT/CNF are grown on it. No change in nesting of the fabric plies is noticed. The poor compressibility can lower the achievable fibre volume fraction in composite for economical vacuum assisted light-RTM techniques and increase the pressure requirements in autoclave processing.     

Carbon nanotube grafted silica fibres: Characterising the interface at the single fibre level

Model polymer composites containing carbon nanotube (CNT) grafted fibres provide a means to investigate the influence of nanostructures on interfacial properties. Well-aligned nanotubes, with controllable length, were grown on silica fibres by using the injection chemical vapour deposition method, leading to a significant increase of the fibre surface area. In single fibre tensile tests, this CNT growth reaction reduced the fibre strength, apparently due to catalyst etching; however, the fibre modulus increased significantly. Contact angle measurements, using the drop-on-fibre method, indicated an excellent wettability of the CNT-grafted fibres by poly(methyl methacrylate) (PMMA). PMMA model composites were fabricated and studied using the single fibre fragmentation tests. A dramatic improvement (up to 150%) of the apparent interfacial shear strength (IFSS) was obtained for the composites containing CNT-grafted fibres. The improvement of IFSS was also influenced by the length and morphology of the grafted CNTs.     

Mechanical characterization of epoxy composite with multiscale reinforcements: Carbon nanotubes and short carbon fibers

Carbon nanotubes (CNT) and short carbon fibers were incorporated into an epoxy matrix to fabricate a high performance multiscale composite. To improve the stress transfer between epoxy and carbon fibers, CNT were also grown on fibers through chemical vapor deposition (CVD) method to produce CNT grown short carbon fibers (CSCF). Mechanical characterization of composites was performed to investigate the synergy effects of CNT and CSCF in the epoxy matrix. The multiscale composites revealed significant improvement in elastic and storage modulus, strength as well as impact resistance in comparison to CNT–epoxy or CSCF–epoxy composites. An optimum content of CNT was found which provided the maximum stiffness and strength. The synergic reinforcing effects of combined fillers were analyzed on the fracture surface of composites through optical and scanning electron microscopy (SEM).     

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.     

Unidirectional carbon fibre reinforced polyamide-12 composites with enhanced strain to tensile failure by introducing fibre waviness

Unidirectional (UD) carbon fibre reinforced polymers offer high specific strength and stiffness but they fail in a catastrophic manner with little warning. Gas-texturing and non-constrained annealing were used to introduce fibre waviness into UD polyamide 12 composites produced by wet-impregnation hoping to produce composites with a more gradual failure mode and increased failure strain. Both methods increased the variation of fibre alignment angle compared to the control samples. The composites containing wavy fibres exhibited a stepwise, gradual failure mode under strain controlled uniaxial tension rather than a catastrophic failure, observed in control samples. Gas-texturing damaged the fibres resulting in a decrease of the tensile strength and strain to failure, which resulted in composites with lower tensile strength and ultimate failure strain than the control composites. Non-constrained annealing of carbon fibre/PA-12 produced wavy fibre composites with ultimate failure strain of 2%, significantly higher than 1.6% of the control composite.     

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.     

Growth of long and aligned multi-walled carbon nanotubes on carbon and metal substrates

Well aligned, long and dense multi-walled carbon nanotubes (CNT) can be grown on both carbon fibres and any metal substrates compatible with the CNT synthesis temperature. The injection-CVD process developed involves two stages, including fibre pretreatment by depositing a SiO(2)-based sub-layer from an organometallic precursor followed by CNT growth from toluene/ferrocene precursor mixture. Carbon substrates, as well as metals, can easily be treated with this process, which takes place in the same reactor and does not need any handling in between the two stages. The aligned CNT carpets obtained are similar to the ones grown on reference quartz substrates. The CNT growth rate is fairly high (ca. 30?μm?min(-1)) and it is possible to control CNT length by varying the CNT synthesis duration. The thickness of the SiO(2)-based sub-layer can be varied and is shown to have an influence on the CNT growth. This layer is assumed to play a diffusion barrier layer role between the substrate and the iron based catalyst nanoparticles producing CNT. The CNT anchorage to the carbon fibres has been checked and good overall adhesion proved, which is in favour of a good transfer of electrical charge and heat between the nanotubes and fibre.     

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.     

Effect of fibre coating and geometry on the tensile properties of hybrid carbon nanotube coated carbon fibre reinforced composite

Hierarchically structured hybrid composites are ideal engineered materials to carry loads and stresses due to their high in-plane specific mechanical properties. Growing carbon nanotubes (CNTs) on the surface of high performance carbon fibres (CFs) provides a means to tailor the mechanical properties of the fibre–resin interface of a composite. The growth of CNT on CF was conducted via floating catalyst chemical vapor deposition (CVD). The mechanical properties of the resultant fibres, carbon nanotube (CNT) density and alignment morphology were shown to depend on the CNT growth temperature, growth time, carrier gas flow rate, catalyst amount, and atmospheric conditions within the CVD chamber. Carbon nanotube coated carbon fibre reinforced polypropylene (CNT-CF/PP) composites were fabricated and characterized. A combination of Halpin–Tsai equations, Voigt–Reuss model, rule of mixture and Krenchel approach were used in hierarchy to predict the mechanical properties of randomly oriented short fibre reinforced composite. A fractographic analysis was carried out in which the fibre orientation distribution has been analyzed on the composite fracture surfaces with Scanning Electron Microscope (SEM) and image processing software. Finally, the discrepancies between the predicted and experimental values are explained.     

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.     

Influence of different carbon nanotubes on the electrical and mechanical properties of melt mixed poly(ether sulfone)-multi walled carbon nanotube composites

Commercial Udel® poly(ether sulfone) (PSU) was filled with three different commercially available multiwalled carbon nanotubes (MWCNTs) by small scale melt mixing. The MWCNTs were as grown NC 7000 and two of its derivatives prepared by ball milling treatment. One of them was unmodified (NC 3150); the other was amino modified (NC 3152). The main difference beside the reactivity was the reduced aspect ratio of NC 3150 and NC 3152 caused by ball milling process. All PSU/MWCNT composites with similar filler content were prepared under fixed processing conditions and comparative analysis of their electrical and mechanical properties were performed and were correlated with their microstructure, characterized by optical microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A non-uniform MWCNT dispersion was observed in all composites. The MWCNTs were present in form of agglomerates in the size of 10–60 μm whereas the deagglomerated part was homogeneously distributed in the PSU matrix. The differences in the agglomeration states correlate with the variations of properties between different PSU/MWCNT composites. The lowest electrical percolation threshold of 0.25–0.5 wt.% was observed for the shortened non-functionalized MWCNT composites and the highest for amine-modified MWCNT composites (ca. 1.5 wt.%). The tensile behavior of the three composites was only slightly altered with CNT loading as compared to the pure PSU. However, the elongation at break showed a reduction with MWCNT loading and the reduction was least for composite with best MWCNT dispersion.     

Enhancement of mechanical performance of epoxy/carbon fiber laminate composites using single-walled carbon nanotubes

Carbon nanotubes (CNT) in their various forms have great potential for use in the development of multifunctional multiscale laminated composites due to their unique geometry and properties. Recent advancements in the development of CNT hierarchical composites have mostly focused on multi-walled carbon nanotubes (MWCNT). In this work, single-walled carbon nanotubes (SWCNT) were used to develop nano-modified carbon fiber/epoxy laminates. A functionalization technique based on reduced SWCNT was employed to improve dispersion and epoxy resin-nanotube interaction. A commercial prepregging unit was then used to impregnate unidirectional carbon fiber tape with a modified epoxy system containing 0.1 wt% functionalized SWCNT. Impact and compression-after-impact (CAI) tests, Mode I interlaminar fracture toughness and Mode II interlaminar fracture toughness tests were performed on laminates with and without SWCNT. It was found that incorporation of 0.1 wt% of SWCNT resulted in a 5% reduction of the area of impact damage, a 3.5% increase in CAI strength, a 13% increase in Mode I fracture toughness, and 28% increase in Mode II interlaminar fracture toughness. A comparison between the results of this work and literature results on MWCNT-modified laminated composites suggests that SWCNT, at similar loadings, are more effective in enhancing the mechanical performance of traditional laminated composites.     

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.     

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.     

Development of sizing-free multi-functional carbon fibre nanocomposites

High quality multi-walled carbon nanotubes (CNTs) grown at high density using a low temperature growth method are used as an alternative material to polymer sizing and is utilised in a series of epoxy composites reinforced with carbon fibres to provide improved physical and electrical properties. We report improvements for sizing-sensitive mechanical and physical properties, such as the interfacial adhesion, shear properties and handling of the fibres, whilst retaining resin-infusion capability. Following fibre volume fraction normalisation, the carbon nanotube-modified carbon fibre composite offers improvements of 146% increase in Young’s modulus; 20% increase in ultimate shear stress; 74% increase in shear chord modulus and an 83% improvement in the initial fracture toughness. The addition of CNTs imparts electrical functionalisation to the composite, enhancements in the surface direction are 400%, demonstrating a suitable route to sizing-free composites with enhanced mechanical and electrical functionality.