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.     

Interfacially reinforced methylphenylsilicone resin composites by chemically grafting multiwall carbon nanotubes onto carbon fibers

Both silane and multiwall carbon nanotubes (CNTs) were grafted successfully onto carbon fibers (CFs) to enhance the interfacial strength of CFs reinforced methylphenylsilicone resin (MPSR) composites. The microstructure, interfacial properties, impact toughness and heat resistance of CFs before and after modification were investigated. Experimental results revealed that CNTs were grafted uniformly onto CFs using 3-aminopropyltriethoxysilane (APS) as the bridging agent. The wettability and surface energy of the obtained hybrid fiber (CF-APS-CNT) were increased obviously in comparison with those of the untreated-CF. The CF-APS-CNT composites showed simultaneously remarkable enhancement in interlaminar shear strength (ILSS) and impact toughness. Moreover, the interfacial reinforcing and toughening mechanisms were also discussed. In addition, Thermogravimetric analysis and thermal oxygen aging experiments indicated a remarkable improvement in the thermal stability and heat oxidation resistance of composites by the introduction of APS and CNTs. We believe the facile and effective method may provide a novel interface design strategy for developing multifunctional fibers.     

Interlaminar and intralaminar reinforcement of composite laminates with aligned carbon nanotubes

Three-dimensional reinforcement of woven advanced polymer–matrix composites using aligned carbon nanotubes (CNTs) is explored experimentally and theoretically. Radially-aligned CNTs grown in situ on the surface of fibers in a woven cloth provide significant three-dimensional reinforcement, as measured by Mode I interlaminar fracture testing and tension-bearing experiments. Aligned CNTs bridge the ply interfaces giving enhancement in both initiation and steady-state toughness, improving the already tough system by 76% in steady state (more than 1.5 kJ/m² increase). CNT pull-out on the crack faces is the observed toughening mechanism, and an analytical model is correlated to the experimental fracture data. In the plane of the laminate, aligned CNTs enhance the tension-bearing response with increases of: 19% in bearing stiffness, 9% in critical strength, and 5% in ultimate strength accompanied by a clear change in failure mode from shear-out failure (matrix dominated) without CNTs to tensile fracture (fiber dominated) with CNTs.     

Preparation and mechanical properties of carbon nanotube grafted glass fabric/epoxy multi-scale composites

In the present paper, carbon nanotubes (CNTs) were chemically grafted onto surfaces of the amino silane treated glass fabric by a novel chemical route for the first time to create 3D network on the glass fibers. The chemical bonding process was confirmed by Fourier transform infrared spectroscopy and scanning electron microscopy. The glass fabric/CNT/epoxy multi-scale composite laminates were fabricated with the CNT grafted fabrics using vacuum assisted resin infusion molding. Tensile tests were conducted on fabricated multi-scale composites, indicating the grafting CNTs on glass fabric resulted a decrease (11%) in ultimate tensile strength while toughness of the multi-scale composite laminates were increased up to 57%. Flexural tests revealed that the multi-scale composite laminates prepared with CNT grafted glass fabric represent recovering after first load fall. The interfacial reinforcing mechanisms were discussed based on fracture morphologies of the multi-scale composites.     

Application of continuously-monitored single fiber fragmentation tests to carbon nanotube/carbon microfiber hybrid composites

To assess the effect of carbon nanotube (CNT) grafting on interfacial stress transfer in fiber composites, CNTs were grown upon individual carbon T-300 fibers by chemical vapor deposition. Continuously-monitored single fiber composite (SFC) fragmentation tests were performed on both pristine and CNT-decorated fibers embedded in epoxy. The critical fragment length, fiber tensile strength at critical length, and interfacial shear strength were evaluated. Despite the fiber strength degradation resulting from the harsh CNT growth conditions, the CNT-modified fibers lead to a twofold increase in interfacial shear strength which correlates with the nearly threefold increase in apparent fiber diameter resulting from CNT grafting. These observations corroborate recently published studies with other CNT-grafted fibers. An analysis of the relative contributions to the interfacial strength of the fiber diameter and strength due to surface treatment is presented. It is concluded that the common view whereby an experimentally observed shorter average fragment length leads to a stronger interfacial adhesion is not necessarily correct, if the treatment has changed the fiber tensile strength or its diameter.     

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.     

Interfacial properties and impact toughness of methylphenylsilicone resin composites by chemically grafting POSS and tetraethylenepentamine onto carbon fibers

Octaglycidyl polyhedral oligomeric silsesquioxane (gly-POSS) was successfully grafted on carbon fibers (CFs) surface to enhance interfacial properties and impact toughness of CFs reinforced methylphenylsilicone resin (MPSR) composites. After gly-POSS modification, POSS grafted CF (CF-POSS) with many epoxy functional groups was modified with tetraethylenepentamine (TEPA) to further enhance the interfacial strength. Atomic force microscopy (AFM) images showed that POSS and TEPA were grafted onto CFs surface uniformly and the surface roughness enhanced obviously. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed the chemical bonding nature between CFs and POSS, as well as between POSS and TEPA. POSS and TEPA modification could increase the fiber polarity, wettability and surface energy significantly. The interlaminar shear strength (ILSS) and impact toughness of composites showed a dramatic improvement, especially for grafting with POSS and further with TEPA (CF-POSS-TEPA). Additionally, the reinforcing and toughening mechanisms were also analyzed. Meanwhile, single fiber tensile strength (TS) had no decrease after modification.     

Carbon fiber/epoxy composite property enhancement through incorporation of carbon nanotubes at the fiber–matrix interphase – Part I: The development of carbon nanotube coated carbon fibers and the evaluation of their adhesion

A new method to realize the uniform coating of carbon nanotubes (CNTs) to carbon fibers (CFs) has been developed, which enables the scalable fabrication of CNT containing CF/epoxy composites. In this method, CNTs are treated by cationic polymers, then, the CNTs are coated to CFs by immersion into a CNT/water suspension. Good dispersion is achieved by repulsive force between positively charged CNTs and uniform coating of the CNTs is achieved by attractive forces between positively charged CNTs and negatively charged CFs. It is found that the use of specific cationic polymers including polyethyleneimine (PEI) results in stable CNT/water suspensions, and uniform coating of the CNTs. Single fiber fragmentation tests of the CF/epoxy composites were conducted to evaluate the strength of interface and interphase under shear loading. The results show that the combination of epoxy resin sizing and PEI treated CNT coating to CFs results in high interfacial shear strength.     

Interfacial shear strength of a glass fiber/epoxy bonding in composites modified with carbon nanotubes

In recent years, carbon nanotubes (CNTs) grown on fibers have attracted a lot of interest as an additional reinforcing component in conventional fiber-reinforced composites to improve the properties of the fiber/matrix interface. Due to harsh growth conditions, the CNT-grafted fibers often exhibit degraded tensile properties. In the current study we explore an alternative approach to deliver CNTs to the fiber surface by dispersing CNTs in the fiber sizing formulation. This route takes advantage of the developed techniques for CNT dispersion in resins and introduces no damage to the fibers. We focus on unidirectional glass fiber/epoxy macro-composites where CNTs are introduced in three ways: (1) in the fiber sizing, (2) in the matrix and (3) in the fiber sizing and matrix simultaneously. Interfacial shear strength (IFSS) is investigated using single-fiber push-out microindentation. The results of the test reveal an increase of IFSS in all three cases. The maximum gain (over 90%) is achieved in the composite where CNTs are introduced solely in the fiber sizing.     

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.     

Enhanced mechanical properties of multiscale carbon fiber/epoxy composites by fiber surface treatment with graphene oxide/polyhedral oligomeric silsesquioxane

Graphene oxide (GO) and polyhedral oligomeric silsesquioxane (POSS) grafted carbon fiber (CF) was demonstrated to reinforce the mechanical properties of fiber composites. Such a fiber composite was prepared by grafting POSS onto the CF surface using GO as the linkage. The presence of GO linkage and POSS could significantly enhance both the area and wettability of fiber surface, leading to an increase in the interfacial strength between fibers and resin. Compared with the desized CF composites, the grafted CF composites fabricated by compression molding method exhibited 53.05% enhancement in the interlaminar shear strength. The changed surface morphology, surface composition and surface energy were supposed to be related with the interfacial performance of unidirectional composites, as revealed by scanning electron microscopy, atomic force microscope, dynamic contact angle test and X-ray photoelectron microscopy charaterizations.     

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.     

Single Carbon Fibers with a Macroscopic‐Thickness, 3D Highly Porous Carbon Nanotube Coating

Carbon fiber (CF) grafted with a layer of carbon nanotubes (CNTs) plays an important role in composite materials and other fields; to date, the applications of CNTs@CF multiscale fibers are severely hindered by the limited amount of CNTs grafted on individual CFs and the weak interfacial binding force. Here, monolithic CNTs@CF fibers consisting of a 3D highly porous CNT sponge layer with macroscopic‐thickness (up to several millimeters), which is directly grown on a single CF, are fabricated. Mechanical tests reveal high sponge–CF interfacial strength owing to the presence of a thin transitional layer, which completely inhibits the CF slippage from the matrix upon fracture in CNTs@CF fiber–epoxy composites. The porous conductive CNTs@CF hybrid fibers also act as a template for introducing active materials (pseudopolymers and oxides), and a solid‐state fiber‐shaped supercapacitor and a fiber‐type lithium‐ion battery with high performances are demonstrated. These CNTs@CF fibers with macroscopic CNT layer thickness have many potential applications in areas such as hierarchically reinforced composites and flexible energy‐storage textiles.     

Effect of carbon nanotube (CNT) content on the mechanical properties of CNT-reinforced aluminium composites

The interest in carbon nanotubes (CNTs) as reinforcements for aluminium (Al) has been growing considerably. Efforts have been largely focused on investigating their contribution to the enhancement of the mechanical performance of the composites. The uniform dispersion of CNTs in the Al matrix has been identified as being critical to the pursuit of enhanced properties. Ball milling as a mechanical dispersion technique has proved its potential. In this work, we use ball milling to disperse up to 5 wt.% CNT in an Al matrix. The effect of CNT content on the mechanical properties of the composites was investigated. Cold compaction and hot extrusion were used to consolidate the ball-milled Al–CNT mixtures. Enhancements of up to 50% in tensile strength and 23% in stiffness compared to pure aluminium were observed. Some carbide formation was observed in the composite containing 5 wt.% CNT. In spite of the observed overall reinforcing effect, the large aspect ratio CNTs used in the present study were difficult to disperse at CNT wt.% greater than 2, and thus the expected improvements in mechanical properties with increase in CNT weight content were not fully realized.     

Microstructure and properties of polyurethane nanocomposites reinforced with methylene-bis-ortho-chloroanilline-grafted multi-walled carbon nanotubes

Methylene-bis-ortho-chloroanilline (MOCA), an excellent cross-linker widely used to prepare cured polyurethane (PU) elastomers with high performance, was used to modify a multi-walled carbon nanotube. PU/carbon nanotube (CNT) nanocomposites were prepared by incorporation of the MOCA-grafted CNT into PU matrix. Fourier transform infrared spectra have shown that the modified CNTs have been linked with PU matrix. The microstructure of composites was investigated by Field-Emission Scanning Electron Microscopy. The results of Dynamic Mechanical Thermal Analysis and Differential Scanning Calorimetry have investigated the grafted CNTs as cross-linker in the cured composites. The studies on the thermal and mechanical properties of the composites have indicated that the storage modulus and tensile strength, as well as glass transition temperature and thermal stability are significantly increased with increasing CNT content.     

Processing,characterization, and modeling of carbon nanotube-reinforced multiscale composites

Carbon fiber-reinforced epoxy composites modified with carbon nanotubes (CNTs) were fabricated and characterized. High-energy sonication was used to disperse CNTs in the resin, followed by infiltration of fiber preform with the resin/CNT mixture. The effects of sonication time on the mechanical properties of “multiscale” composites, which contain reinforcements at varying scales, were studied. A low CNT loading of 0.3 wt% in resin had little influence on tensile properties, while it improved the flexural modulus, strength, and percent strain to break by 11.6%, 18.0%, and 11.4%, respectively, as compared to the control carbon fiber/epoxy composite. While sonication is an effective method to disperse CNTs in a resin, duration, intensity, and temperature need to be controlled to prevent damages imposed on CNTs and premature resin curing. A combination of Halpin–Tsai equations and woven fiber micromechanics was used in hierarchy to predict the mechanical properties of multiscale composites, and the discrepancies between the predicted and experimental values are explained.     

Mechanical behavior of Kevlar/basalt reinforced polypropylene composites

In this study, mechanical behavior of thermoplastic composites reinforced with two-dimensional plain woven homogeneous and hybrid fabrics of Kevlar/basalt yarns was studied. Five types (two homogeneous and three hybrids) of composite laminates were manufactured using compression molding technique with polypropylene (PP) resin. Static tensile and in-plane compression tests were carried out to evaluate the mechanical properties of the laminates. The tension and in-plane compression tests had shown that the composites with the combination of Kevlar and basalt yarns present better tensile and in-plane compressive behavior as compared to their base composites. Improvement in the properties such as elastic modulus, strength and failure strain in both tension and in-plane compression was observed due to the hybridization. Numerical simulations were performed in ABAQUS/Standard by implementing a user-defined material subroutine (VUMAT) based on Chang-Chang criteria. Good agreement between the experimental and numerical simulations was achieved in terms of damage patterns.     

Reinforcing brittle and ductile epoxy matrices using carbon nanotubes masterbatch

In this study, the mechanical and thermal properties of epoxy composites using two different forms of carbon nanotubes (powder and masterbatch) were investigated. Composites were prepared by loading the surface-modified CNT powder and/or CNT masterbatch into either ductile or brittle epoxy matrices. The results show that 3 wt.% CNT masterbatch enhances Young’s modulus by 20%, tensile strength by 30%, flexural strength by 15%, and 21.1 °C increment in the glass transition temperature (by 34%) of ductile epoxy matrix. From scanning electron microscopy images, it was observed that the CNT masterbatch was uniformly distributed indicating the pre-dispersed CNTs in the masterbatch allow an easier path for preparation of CNT-epoxy composites with reduced agglomeration of CNTs. These results demonstrate a good CNT dispersion and ductility of epoxy matrix play a key role to achieve high performance CNT-epoxy composites.     

Influence of carbon nanotube-polymeric compatibilizer masterbatches on morphological, thermal, mechanical, and tribological properties of polyethylene

Study was made of the effect of multiwall carbon nanotubes (MWCNTs) and polymeric compatibilizer on thermal, mechanical, and tribological properties of high density polyethylene (HDPE). The composites were prepared by melt mixing in two steps. Carbon nanotubes (CNTs) were melt mixed with maleic anhydride grafted polyethylene (PEgMA) as polymeric compatibilizer to produce a PEgMA-CNT masterbatch containing 20 wt% of CNTs. The masterbatch was then added to HDPE to prepare HDPE nanocomposites with CNT content of 2 or 6 wt%. The unmodified and modified (hydroxyl or amine groups) CNTs had similar effects on the properties of HDPE-PEgMA indicating that only non-covalent interactions were achieved between CNTs and matrix. According to SEM studies, single nanotubes and CNT agglomerates (size up to 1 μm) were present in all nanocomposites regardless of content or modification of CNTs. Addition of CNTs to HDPE-PEgMA increased decomposition temperature, but only slight changes were observed in crystallization temperature, crystallinity, melting temperature, and coefficient of linear thermal expansion (CLTE). Young’s modulus and tensile strength of matrix clearly increased, while elongation at break decreased. Measured values of Young’s moduli of HDPE-PEgMA-CNT composites were between the values of Young’s moduli for longitudinal (E₁₁) and transverse (E₂₂) direction predicted by Mori-Tanaka and Halpin-Tsai composite theories. Addition of CNTs to HDPE-PEgMA did not change the tribological properties of the matrix. Because of its higher crystallinity, PEgMA possessed significantly different properties from HDPE matrix: better mechanical properties, lower friction and wear, and lower CLTE in normal direction. Interestingly, the mechanical and tribological properties and CLTEs of HDPE-PEgMA-CNT composites lie between those of PEgMA and HDPE.     

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.