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.     

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.     

Strain-sensitive Raman spectroscopy and electrical resistance of carbon nanotube-coated glass fibre sensors

This paper presents the development of glass fibres coated with nanocomposites consisting of carbon nanotubes (CNTs) and epoxy. Single glass fibres with different CNT content coating are embedded in a polymer matrix as a strain sensor for composite structures. Raman spectroscopy and electrical response of glass fibres under mechanical load are coupled for in situ sensing of deformation in composites. The results show that the fibres with nanocomposite coating exhibit efficient stress transfer across the fibre/matrix interface, and these with a higher CNT content are more prone to fibre fragmentation at the same matrix strain. A relationship between the fibre stress and the change in electrical resistance against the fibre strain is established. The major finding of this study has a practical implication in that the fibres with nanocomposite coating can serve as a sensor to monitor the deformation and damage process in composites.     

Carbon nanotube grafted carbon fibres: A study of wetting and fibre fragmentation

Carbon nanotubes (CNTs) were grafted on IM7 carbon fibres using a chemical vapour deposition method. The overall grafting process resulted in a threefold increase of the BET surface area compared to the original primary carbon fibres (0.57 m²/g). At the same time, there was a degradation of fibre tensile strength by around 15% (depending on gauge length), due to the dissolution of iron catalyst into the carbon; the modulus was not significantly affected. The wetting behaviour between fibres and poly(methyl methacrylate) (PMMA) was directly quantified using contact angle measurements for drop-on-fibre systems and indicated good wettability. Single fibre fragmentation tests were conducted on hierarchical fibre/PMMA model composites, demonstrating a significant (26%) improvement of the apparent interfacial shear strength (IFSS) over the baseline composites. The result is associated with improved stress transfer between the carbon fibres and surrounding matrix, through the grafted CNT layer. The improved IFSS was found to correlate directly with a reduced contact angle between fibre and matrix.     

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.     

A chemical method to graft carbon nanotubes onto a carbon fiber

A simple method is developed for grafting carbon nanotubes (CNTs) onto a carbon fiber surface. CNT and carbon fiber undergo an oxidation treatment. Oxidation generates oxygen, like carboxyl, carbonyl or hydroxyl groups, or amine groups on nanotubes and carbon fiber surface. Functionalized CNTs are dispersed in a solvent and deposited on carbon fibers. The bonds between CNT and carbon fiber are operated by esterification, anhydridation or amidization of the chemical surface groups. The resulting materials are characterized by scanning electron microscopy (SEM). CNTs form a 3D network around the carbon fibers. Likewise, CNT bonding between two fibers is observed.     

RTM processing and electrical performance of carbon nanotube modified epoxy/fibre composites

This investigation focuses on nanoparticle filtration in the processing of multiscale carbon and glass fibre composites via resin transfer moulding. Surface modified and unmodified carbon nanotubes (CNTs) were incorporated into a commercial epoxy resin. The dispersion quality was evaluated using electrical measurements of the liquid suspensions. The manufacturing process was adapted to the challenges posed by the modified rheological behaviour of the CNT loaded resin. Nanoparticle filtration was observed; with some of the unmodified systems following so called ‘cake filtration’ behaviour. This resulted in nonlinear flow behaviour that deviated from the ideal response observed in RTM filling in conventional composites. The electrical conductivity of relatively high fibre volume fraction multiscale carbon and glass laminates increased by less than an order of magnitude with the addition of the nanotubes.     

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.     

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.     

Improved fracture toughness and integrated damage sensing capability by spray coated CNTs on carbon fibre prepreg

The development of a hierarchically engineered micro-nano hybrid composite system is described. A spray coating technique has been utilized as an effective way to deposit carbon nanotubes (CNTs) onto carbon fibre prepregs with good control of network formation and the potential for localization. Compared to more traditional approaches of introducing CNTs into epoxy matrices for enhancing composite properties, this technique has benefits in terms of its simplicity and versatility, as well as the potential for industrial scale-up. The effectiveness of the technique is demonstrated by the extremely low CNT loading (0.047 wt.%) needed to significantly increase the Mode-I fracture toughness of the carbon fibre laminates by about 50%, which is so far the largest reported improvement for such extremely low concentrations of non-functionalized CNTs. In-situ damage sensing has also been presented for the monitoring of structural health of these nano-engineered composite laminates upon loading, and a systematic analysis of sensing signals is performed.     

Progress on mechanics of carbon nanotubes and derived materials

This review focuses on the most recent progress in understanding mechanical properties of individual carbon nanotubes (CNT), carbon nanotube arrays, random networks, and polymer matrix composites. The key factors that influence the mechanical properties of these new (nano)materials are identified and discussed. The critical issue appears to be the load transfer efficiency; between nanotubes when organized in bundles, ropes, and networks; between matrix and nanotubes in composites. Among the different paths used to increase load transfer, cross-linking by irradiation is emphasized. A particular attention is paid on the role of nanotubes as nucleating agents in polymer composites, initiating the formation of a crystalline polymer sheath that has important consequence on the mechanical properties. The reinforcing element to be considered in that case is not CNT alone but CNT covered with a cylinder of crystalline polymer. Whereas a lot of effort has been focused on the problem of dispersion, it appears that the problem of nanotube-matrix interphase is almost as important. Recent works show that appropriate surface functionalization can be used both to improve dispersion and tailor the interphase. Nanotube surface engineering combined with methods producing oriented nanocomposites should bring exceptional materials in the near future.     

Surface oxidation of carbon fibre on tribological properties of PEEK composites

Abstract

In this work, ozone modification method and air oxidation were used for the surface treatment of polyacrylonitrile (PAN) based carbon fibre. The surface characteristics of carbon fibres were characterised by X-ray photoelectron spectroscopy. The interfacial properties of carbon fibre reinforced PEEK (CF/PEEK) composites were investigated by means of the single fibre pull-out tests. As a result, it was found that IFSS values of the composites with ozone treated carbon fibre are increased by 60% compared with that without treatment. X-ray photoelectron spectroscopy results show that ozone treatment increases the amount of carboxyl groups on carbon fibre surface, thus the interfacial adhesion between carbon fibre and PEEK matrix is effectively promoted. The effect of surface treatment of carbon fibres on the tribological properties of CF/PEEK composites was comparatively investigated. Experimental results revealed that surface treatment can effectively improve the interfacial adhesion between carbon fibre and PEEK matrix. Thus the wear resistance was significantly improved.     

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).     

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.     

Comparison of chemical vapor deposition and chemical grafting for improving the mechanical properties of carbon fiber/epoxy composites with multi-wall carbon nanotubes

By engineering the fiber/matrix interface, the properties of the composite can be changed significantly. In this work, we increased the effective surface area of the fiber/matrix interface, to facilitate additional stress transfer between fibers and matrix, by grafting carbon nanotubes on to carbon fibers (in the form of carbon fabric) by two different methods: (1) chemical vapor deposition (CVD) method and (2) a purely chemical method. With the CVD process, carbon nanotubes (CNT) were directly grown on carbon fiber substrate using chemical vapors. For the chemical method, CNT with carboxyl groups were grafted on functionalized carbon fiber via a chemical reaction. The morphology of CNT/carbon fibers was examined by scanning electron microscope (SEM) which revealed uniform coverage of carbon fibers with CNT in both of CVD method and chemical grafting method. CNT-grafted woven carbon fibers were used to make carbon/epoxy composites, and their mechanical properties were measured using three-point bending and tension tests which showed that those with CNT-grafted carbon fiber reinforcements using the CVD process has 11 % higher tensile strength compared to those containing carbon fibers modified with the chemical method. Also, composites with CNT-grafted carbon fibers with chemical method showed 20 % higher tensile strength compared to composites with unmodified carbon fibers. The results of tensile test revealed that both CVD and chemical grafting could significantly improve the mechanical properties of the carbon fiber composites.     

Effect of carbon nanotubes on the interfacial shear strength of T650 carbon fiber in an epoxy matrix

The interfacial shear strength of carbon nanotube coated carbon fibers in epoxy was studied using the single-fiber composite fragmentation test. The carbon fibers were coated with carbon nanotubes (CNT) on the fiber surface using thermal chemical vapor deposition (CVD). The CVD process was adjusted to produce two CNT morphologies for the study: radially aligned and randomly oriented. The purpose of the CNT coating was to potentially produce a multifunctional structural composite. Results of the single-fiber fragmentation tests indicate an improvement in interfacial shear strength with the addition of a nanotube coating. This improvement can most likely be attributed to an increase in the interphase yield strength as well as an improvement in interfacial adhesion due to the presence of the nanotubes.     

Impact and after-impact properties of carbon fibre reinforced composites enhanced with multi-wall carbon nanotubes

The goal of the present study was to investigate the influence of multi-wall carbon nanotubes (MWCNTs) on the impact and after impact behaviour of carbon fiber reinforced polymer (CFRP) laminates. About 0.5% per weight MWCNTs were dispersed via a high shear device in the epoxy matrix (Bisphenol A) of carbon reinforced quasi-isotropic laminates. Subsequently, the modified CFRPs were subjected to low-energy impact and directly compared with unmodified laminates. In previous studies, the beneficial effect of the MWCNT inclusion to the fracture properties of CFRPs has been demonstrated. In terms of the CFRP impact performance, enhanced performance for the CNT doped specimens was observed for higher energy levels. However, the after-impact properties and more specifically compression after impact were improved for both the effective compression modulus and the compression strength. In addition, compression–compression fatigue after impact performance of the CNT modified laminates was also improved, by extending the fatigue life.     

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.     

Reinforcing effect of carbon nanotubes on PEEK composite filled with carbon fibre

Abstract

The main objective of the present paper is to develop high wear resistance carbon fibre reinforced polyether ether ketone composite with addition of multiwall carbon nanotubes. These compounds were well mixed in a batch mixer, and compounded polymers were fabricated into sheets of known thickness by compression moulding. Samples were tested for wear resistance with respect to different concentration of fillers. The wear resistance properties of these samples depend on filler aspect ratio. Wear resistance of composite with 20 wt-% of carbon fibre increases when multiwall carbon nanotubewas introduced. The worn surface features have been examined using scanning electron microscope. Photomicrographs of the worn surfaces revealed higher wear resistance with the addition of carbon nanotube. Also better interfacial adhesion between carbon and vinyl ester in carbon reinforced vinyl ester composite was observed.