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.     

Preparation of porous alumina-carbon nanotube composites via direct growth of carbon nanotubes

A simple approach is reported for the in situ growth of carbon nanotube-containing porous alumina structures by a thermal pyrolysis method. The composite was created by direct on-site growth of carbon nanotubes inside the porous alumina matrix, after introducing both a catalyst (Ni(NO₃)₂) and a carbon source (camphor) into the cavities of the large matrix brick. Pyrolysis was carried out when the pre-treated brick was heated in a furnace at 850 °C under a H₂-Ar atmosphere. The resulting multi-walled carbon nanotubes with average diameters of 30-70 nm and lengths up to several micrometers are dispersed uniformly at each section of the alumina matrix. An improvement in the compression strength of the composites has been obtained, due to the inclusion of carbon nanotubes.     

Optimization of processing parameters of the chemical vapor deposition process for synthesizing high-quality single-walled carbon nanotube fluff and roving

The use of the Taguchi method to optimize the processing parameters for the synthesis of high-quality single-walled carbon nanotubes (SWCNTs) in a vertical chemical vapor deposition reactor was demonstrated. An investigation containing 18 experiments featuring different parameters and levels was performed. SWCNTs with a low intensity D-band to G-band ratio of 0.027 of a Raman spectrum were obtained when the optimal processing conditions were adopted. The quantitative contribution of the processing parameters can be calculated using the analysis of variance. According to the analysis, the reactor temperature and the evaporation temperature of ferrocene significantly affect the graphitization of the synthesized SWCNTs, while the chamber pressure exerts an insignificant effect. The formation of carbon nanotube films with entangled networks during synthesis was recorded using a digital camera, and a synthesis mechanism was proposed. Using the optimal parameters, SWCNT fluff with a diameter of 7.0 cm and SWCNT roving with a diameter of approximately 1.0 cm and a length of over 30.0 cm can be attained. In this work, field-emission scanning electron microscopy and Raman spectroscopy and high-resolution transmission electron microscopy were adopted to examine the morphology and microstructure, respectively.     

Multi-barrier layer-mediated growth of carbon nanotubes

Variation in the height of carbon nanotubes (CNTs) grown has been co-related to the type of multi-barrier-layer used. Initially, various types of barrier-layers such as Al, Al₂O₃, Al/SiO₂, Al₂O₃/SiO₂ were prepared onto a n-type Si (100) substrate. The thickness of SiO₂ was ∼ 550 nm, where as, Al₂O₃ and Al were ∼ 15 nm thick. These samples were covered with ∼ 1 nm thick Fe catalyst layer. The coated samples were subjected to the thermal chemical vapor deposition (T-CVD) process. SEM analysis showed that, for Al₂O₃/SiO₂ barrier layers, the average height of the CNTs was ∼ 10 μm, where as, for other types of samples it was less than ∼ 1 μm. To investigate this, multi-barrier layers were characterized by dynamic secondary ion mass spectrometry (D-SIMS). The observed variation in height of CNTs is attributed to the variation in diffusivity of Fe atoms into multi-barriers-layers. The results showed that, diffusion of Fe catalyst atoms could severally affect height of CNTs.     

Carbon nanotubes as structural material and their application in composites

In the present paper, we will introduce the synthesis and application of carbon nanotubes as filler for nanocomposite materials. Physical and chemical properties such as mechanical strength, thermal and electrical conductivity, chemical stability, density and affinity with the matrix vary a lot among different types of carbon nanotubes. We first will overview the main component of nanocomposite, carbon nanotube and its synthesis and purification, and introduce some of the nanocomposites and its applications that we have taken part in the development.     

Effect of a multiscale reinforcement by carbon fiber surface treatment with graphene oxide/carbon nanotubes on the mechanical properties of reinforced carbon/carbon composites

An effective carbon fiber/graphene oxide/carbon nanotubes (CF-GO-CNTs) multiscale reinforcement was prepared by co-grafting carbon nanotubes (CNTs) and graphene oxide (GO) onto the carbon fiber surface. The effects of surface modification on the properties of carbon fiber (CF) and the resulting composites was investigated systematically. The GO and CNTs were chemically grafted on the carbon fiber surface as a uniform coating, which could significantly increase the polar functional groups and surface energy of carbon fiber. In addition, the GO and CNTs co-grafted on the carbon fiber surface could improve interlaminar shear strength of the resulting composites by 48.12% and the interfacial shear strength of the resulting composites by 83.39%. The presence of GO and CNTs could significantly enhance both the area and wettability of fiber surface, leading to great increase in the mechanical properties of GO/CNTs/carbon fiber reinforced composites.     

Fabrication and mechanical properties of well-dispersed multiwalled carbon nanotubes/epoxy composites

Multiwalled carbon nanotubes (MWCNTs)/epoxy nanocomposites were fabricated by using ultrasonication and the cast molding method. In this process, MWCNTs modified by mixed acids were well dispersed and highly loaded in an epoxy matrix. The effects of MWCNTs addition and surface modification on the mechanical performances and fracture morphologies of composites were investigated. It was found that the tensile strength improved with the increase of MWCNTs addition, and when the content of MWCNTs loading reached 8 wt.%, the tensile strength reached the highest value of 69.7 MPa. In addition, the fracture strain also enhanced distinctly, implying that MWCNTs loading not only elevated the tensile strength of the epoxy matrix, but also increased the fracture toughness. Nevertheless, the elastic modulus reduced with the increase of MWCNTs loading. The reasons for the mechanical property changes are discussed.     

Enhancement of tensile and thermal properties of epoxy nanocomposites through chemical hybridization of carbon nanotubes and alumina

This paper presents the properties of epoxy nanocomposites, prepared using a synthesized hybrid carbon nanotube–alumina (CNT–Al₂O₃) filler, via chemical vapour deposition and a physically mixed CNT–Al₂O₃ filler, at various filler loadings (i.e., 1–5%). The tensile and thermal properties of both nanocomposites were investigated at different weight percentages of filler loading. The CNT–Al₂O₃ hybrid epoxy composites showed higher tensile and thermal properties than the CNT–Al₂O₃ physically mixed epoxy composites. This increase was associated with the homogenous dispersion of CNT–Al₂O₃ particle filler; as observed under a field emission scanning electron microscope. It was demonstrated that the CNT–Al₂O₃ hybrid epoxy composites are capable of increasing tensile strength by up to 30%, giving a tensile modulus of 39%, thermal conductivity of 20%, and a glass transition temperature value of 25%, when compared to a neat epoxy composite.     

Interconnected multi-walled carbon nanotubes reinforced polymer-matrix composites

A modified method for interconnecting multi-walled carbon nanotubes (MWCNTs) was put forward. And interconnected MWCNTs by reaction of acyl chloride and amino groups were obtained. Scanning electron microscopy shows that hetero-junctions of MWCNTs with different morphologies were formed. Then specimens of pristine MWCNTs, chemically functionalized MWCNTs and interconnected MWCNTs reinforced epoxy resin composites were fabricated by cast moulding. Tensile properties and fracture surfaces of the specimens were investigated. The results show that, compared with pristine MWCNTs and chemically functionalized MWCNTs, the chemically interconnected MWCNTs improved the fracture strain and therefore the toughness of the composites significantly.     

Pristine and amino functionalized carbon nanotubes reinforced glass fiber epoxy composites

Multi-phase composites have been studied by incorporating carbon nanotubes (CNTs) as a secondary reinforcement in an epoxy matrix which was then reinforced with glass fiber mat. Different types of CNTs e.g. amino functionalized carbon nanotubes (ACNT) and pristine carbon nanotubes (PCNT) were homogeneously dispersed in the epoxy matrix and two-ply laminates were fabricated using vacuum-assisted resin infusion molding technique. The issues related to CNT dispersion and interfacial bonding and its affect on the mechanical properties have been studied. An important finding of this study is that PCNT scores over ACNT in composites prepared under certain conditions. This is a very significant finding since PCNT is available at a much lower cost than ACNT.     

Mechanical properties of multi-walled carbon nanotube/epoxy composites

Untreated and acid-treated multi-walled carbon nanotubes (MWNT) were used to fabricate MWNT/epoxy composite samples by sonication technique. The effect of MWNT addition and their surface modification on the mechanical properties were investigated. Modified Halpin–Tasi equation was used to evaluate the Young’s modulus and tensile strength of the MWNT/epoxy composite samples by the incorporation of an orientation as well as an exponential shape factor in the equation. There was a good correlation between the experimentally obtained Young’s modulus and tensile strength values and the modified Halpin–Tsai theory. The fracture surfaces of MWNT/epoxy composite samples were analyzed by scanning electron microscope.     

Synthesis of uniformly dispersed carbon nanotube reinforcement in Al powder for preparing reinforced Al composites

In order to obtain homogeneously dispersed carbon nanotube (CNT) reinforcement with well structure in Al powder, a novel and simple approach was developed as a means of overcoming the limits of traditional mixing methods. This process involves the even deposition of Ni catalyst onto the surface of Al powder by impregnation route with a low Ni content (0.5 wt.%) and in situ synthesis of CNTs in Al powder by chemical vapor deposition. The in situ synthesized CNTs with well-crystallized bamboo-like structure in the composite powders can obviate the reaction with Al below 1000 °C. The feasibility of fabricating CNT/Al composites with high mechanical properties using the as-prepared composite powders was proved by our primary test, which indicated that the compressive yield stress and elastic modulus of 1.5 wt.%-CNT/Al composites synthesized by hot extrusion are 2.2 and 3.0 times as large as that of the pure Al matrix.     

Effect of epoxy coatings on carbon fibers during manufacture of carbon fiber reinforced resin matrix composites

The changes in oxygen and nitrogen during manufacture of the carbon fiber reinforced resin matrix composites were measured using the X-ray photoelectron spectroscopy method. The effects of the change in oxygen and nitrogen on the strength of the carbon fibers were investigated and the results revealed that the change of the tensile strength with increasing heat curing temperature was attributed to the change in the surface flaws of the carbon fibers because the carbon fibers are sensitive to the surface flaws. The effect of the surface energy that was calculated using Kaelble’s method on the strength of the carbon fibers was investigated. Furthermore, the surface roughness of the carbon fibers was measured using atom force microscopy. The change trend of roughness was reverse to that of the strength, which was because of the brittle fracture of the carbon fibers.     

Microstructure characterization of CVI-densified carbon/carbon composites with various fiber distributions

Mechanical behavior of multi-phase composites is crucially influenced by volume fractions, orientation distributions and geometries of microconstituents. In the case of carbon–carbon composites manufactured by chemical vapor infiltration, the microconstituents are carbon fibers, pyrolytic carbon matrix, and pores. The local variable thickness of the pyrolytic carbon coating, distribution of the fibers and porosity are the main factors influencing the properties of these materials. Two types of fiber arrangements are considered in this paper: 2D laminated preform and random felt. The materials are characterized by determining their densities and their fiber distribution functions, by establishing types of pyrolytic carbon matrix present in the composites, and by studying the porosity. A technique utilizing X-ray computed tomography for estimation of the orientation distribution of the fibers and pores with arbitrary shapes is developed. A methodology based on the processing of microstructure images with subsequent numerical simulation of the coating growth around the fibers is proposed for estimation of the local thickness of the coating. The obtained information is appropriate for micromechanical modeling and prediction of the overall thermo-mechanical properties of the studied composites.     

Functionalization of multi-wall carbon nanotubes with silane and its reinforcement on polypropylene composites

Multi-wall carbon nanotubes (MWCNTs) were functionalized with a silane coupling agent. The MWCNTs were first coated with inorganic silica by a sol–gel process and then grafted with 3-methacryloxypropyltrimethoxysilane (3-MPTS). The grafting of 3-MPTS onto the MWCNTs surface was confirmed by Fourier-transform infrared spectroscopy, transmission electron microscopy and X-ray photoelectron spectra. Polypropylene (PP) composites filled with raw MWCNTs and functionalized MWCNTs were prepared and characterized. The PP/3-MPTS functionalized MWCNTs composite has higher tensile strength than the PP/raw MWCNTs composite. This is explained by the organic groups of 3-MPTS grafted onto the surface of MWCNTs.     

Surface structures of PAN-based carbon fibers and their influences on the interface formation and mechanical properties of carbon-carbon composites

Defects and microvoids in the surface region not only influenced the tensile strength and strain of carbon fibers but also affected the interface formation with pyrocarbon. The interface formation in carbon-carbon composites was closely correlated to rearrangement of carbon atoms and the evolution of surface structure of carbon fiber. Half-open elliptic microvoids or edge planes at the fiber surface were beneficial to the mechanical interlocking as well as chemical bonding with pyrocarbon, contributing to a compatible interface with high interlaminar shear strength of the composites. The closed microvoids in the surface region of carbon fiber would hardly open up to bond with pyrocarbon, which brought negative effects to the mechanical properties of composites. Carbon fiber without obvious microvoids or surface defects tended to have better tensile strain but form weak interface with pyrocarbon, leading to a better pseudo-ductility and ability to absorb more fracture energy under load.     

Grain size effect on the strengthening behavior of aluminum-based composites containing multi-walled carbon nanotubes

Strengthening efficiency of multi-walled carbon nanotubes (MWCNTs) is investigated for aluminum-based composites with grain sizes ranging from ∼250 to ∼65 nm. The strength of composites is significantly enhanced proportional to an increase of the MWCNT volume. However, the increment differs depending on deformation mode of the matrix. The strengthening efficiency of MWCNTs in ultrafine-grained composites is comparable with that predicted by the discontinuous fiber model, whereas the efficiency becomes half of the theoretical prediction as grain size is reduced below ∼70 nm. For nano-grained aluminum, activities of forest dislocations diminish and dislocations emitted from grain boundaries are dynamically annihilated during the recovery process, providing a weak plastic strain field around MWCNTs. The observation may provide a basic understanding of the strengthening behavior of nano-grained metal matrix composites.     

Odako growth of dense arrays of single-walled carbon nanotubes attached to carbon surfaces

A novel process is demonstrated whereby dense arrays of single-walled carbon nanotubes (SWNT) are grown directly at the interface of a carbon material or carbon fiber. This growth process combines the concepts of SWNT tip growth and alumina-supported SWNT base growth to yield what we refer to as “odako” growth. In odako growth, an alumina flake detaches from the carbon surface and supports catalytic growth of dense SWNT arrays at the tip, leaving a direct interface between the carbon surface and the dense SWNT arrays. In addition to being a new and novel form of SWNT array growth, this technique provides a route toward future development of many important applications for dense aligned SWNT arrays. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Effects of functional group of carbon nanotubes on mechanical properties of carbon fibers

The effects of surface functionalization of carbon nanotubes (CNTs) on the mechanical properties of carbon fibers (CFs) have been investigated. The surface functionalization of CNTs was carried out with a diazonium reagent. Compared to pure PAN, only the fluoro phenyl functionalized CNTs (F-Ph-CNT) incorporated PAN composites showed a significant increase up to 22 °C of T_g and displayed the second peak due to the interfacial interaction between F-Ph-CNT and PAN. Among the samples, 0.5wt% of F-Ph-CNT reinforced CFs exhibited a 46% increase in tensile strength (4.1 GPa) and a 37% increase in modulus (302 GPa), respectively compared to that of pure CFs.     

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.