The effect of surface modification with carbon nanotubes upon the tensile strength and Weibull modulus of carbon fibers

Carbon fibers are widely used as reinforcements in composite materials because of their high specific strength and modulus. Today, a number of ultrahigh strength polyacrylonitrile (PAN)-based (more than 6?GPa), and ultrahigh modulus pitch-based (more than 900?GPa) carbon fibers have been commercially available. In contrast, carbon nanotube (CNT) with the extremely high tensile strength have attracted attention as reinforcements. An interesting technique to modify the carbon fiber is CNT grafting on the carbon fiber surface. CNT-grafted carbon fibers offer the opportunity to add the potential benefits of nanoscale reinforcement to well-established fibrous composites to create micro-nano multiscale hybrid composites. In the present study, the tensile properties of CNT grown on T1000GB PAN- and K13D pitch-based carbon fibers have been investigated. Single filament tensile test at gauge lengths of 1, 5, and 25?mm were conducted. The effect of gauge length on tensile strength and Weibull modulus of CNT-grafted PAN- and pitch-based carbon fibers were evaluated. It was found that grafting of CNT improves the tensile strength and Weibull modulus of PAN- and pitch-based carbon fibers with longer gauge length (≥5?mm). The results also clearly show that for CNT-grafted and as-received PAN- and pitch-based carbon fibers, there is a linear relation between the Weibull modulus and the average tensile strength on log–log scale.     

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.     

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.     

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.     

A facile method for preparing CNT-grafted carbon fibers and improved tensile strength of their composites

Carbon nanotube (CNT)-grafted carbon fibers (CFs) have emerged as new reinforcements for improving the mechanical properties of CF-reinforced composites but such enhancement in macroscale composites has not been realized. This paper reports a facile method for preparing CNT-grafted CFs and improving the tensile strength of their composites. A CNT/polyacrylonitrile solution was sprayed onto the surface of the CF woven fabrics, and the CNTs were grafted by a thermal treatment at 300 °C. CNT-grafted CF composites were fabricated using the CNT-grafted CF woven fabrics using a vacuum-assisted resin transfer molding process with epoxy resin. The CNT-grafted CF composite exhibited 22% enhancement in the tensile strength compared to that of the pristine CF composite. Fracture surfaces of the CNT-grafted CF composites showed that the grafted CNTs obstructed the propagation of micro-cracks and micro-delamination around the CFs and also yarn boundaries, resulting in improved tensile strength of CNT-grafted CF composites.     

A method for the chemical anchoring of carbon nanotubes onto carbon fibre and its impact on the strength of carbon fibre composites

This article proposes an alternative way to use carbon nanotubes to improve the performance of carbon fibre-reinforced composites. A chemical process, based on esterification of surface groups, is used to anchor nanotubes onto carbon fibre surface. Anchored nanotubes form a network surrounding the carbon fibres. After CNT anchoring, the tow is impregnated with an epoxy resin and tensile tests are performed on this minicomposite sample. By enhancing matrix properties and fibre/matrix interface, the CNT network has a significant influence on the composite strength.     

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.     

Effect of electrophoretically deposited carbon nanotubes on the interface of carbon fiber reinforced epoxy composite

The interface between reinforcing fiber and matrix is a crucial element in composite performance. Homogeneous and interconnected carbon nanotubes (CNTs) were deposited onto the surface of carbon fibers to produce multiscale reinforcement by electrophoretic deposition (EPD). Single fiber tensile tests showed that the tensile strength and Weibull modulus of the resulting multiscale materials were increased by 16 and 41%, respectively. Compared with as-received carbon fibers, CNTs-deposited carbon fibers provided the decreased surface energy by 20% and the increased adhesion work by 22% using modified Wilhelmy method. Results from single fiber pull-out testing showed that a significant improvement (up to 68.8%) of interfacial shear strength was obtained for the composites containing by CNTs/Carbon fiber multiscale reinforcement. All results strongly suggest that EPD process can provide a feasible platform for improving interface properties of advanced composites.     

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).     

Fracture behavior of carbon nanotube/carbon microfiber hybrid polymer composites

Growing carbon nanotubes (CNTs) on the surface of fibers has the potential to modify fiber–matrix interfacial adhesion, enhance composite delamination resistance, and possibly improve toughness. In the present study, aligned CNTs were grown upon carbon fabric via chemical vapor deposition. Continuously monitored single-fiber composite fragmentation tests were performed on pristine and CNT-grafted fibers embedded in epoxy, and single-laminate compact-tension specimens were tested for fracture behavior. A significant increase (up to 20 %) was observed in the interfacial adhesion, at the cost of a decrease in the fiber tensile strength. As a result, the maximum load of the composite was decreased, but its residual load-bearing capacity more than doubled. The likely sources of these effects are discussed, as well as their implications.     

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.     

Combination effect of physical drying with chemical characteristic of carbon nanotubes on through-thickness properties of carbon fiber/epoxy composites

The present work studied the combination effect of physical drying with chemical modification of carbon nanotubes (CNTs) on some through-thickness properties of carbon fiber/epoxy composites. Different drying methods of heat drying and freeze drying were utilized to affect CNT organization form in carbon fiber/CNTs preforms and composites: The adoption of heat-drying method made CNTs more inclined to form aggregates accompanied with randomly scattered CNTs, while continuous CNT networks could always be assembled when freeze drying method was employed. The formation mechanism of such CNT networks was discussed, and could be described as “freeze drying within confined space.” Chemical characteristic of CNTs was controlled by choosing different solutions of non-functionalized CNTs (NOCNTs) or hydroxyl-modified CNTs (OHCNTs). As a consequence, CNT networks modified composites, especially that with OHCNTs formed networks, displayed significantly better electrical performance than composites with CNT aggregates and scattered CNTs; NOCNT networks and scattered OHCNTs made the corresponding composites possess higher interlaminar shear strength (ILSS) value, whereas OHCNT networks impaired ILSS while enhancing flexural strength and modulus of composites.     

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.     

Preparation of CNT-hybridized carbon fiber by aerosol-assisted chemical vapor deposition

The purpose of this article is to find a way to prepare multiscale material, namely, carbon nanotube-hybridized carbon fiber (CNT/CF) with a low degradation of mechanical properties. Using a facile aerosol-assisted chemical vapor deposition method, a novel route was described to fabricate CNT/CF. The essential of this technique was in situ formation of catalyst (Fe) nanoparticles via pyrolysis of ferrocene–acetone aerosol right before CNTs growth. Through optimizing aerosol supply and process parameters, a uniform coverage of CNTs was successfully grafted onto the carbon fiber surface to obtain a multiscale (hierarchical) structure. The strong anchorage between the as-synthesized CNTs and carbon fiber substrate was confirmed by ultrasonic bath treatment. Compared with the as-received carbon fibers, single fiber tensile testing results demonstrated that the tensile strengths of CNT-hybridized carbon fiber slightly degraded within 10% at all the correspondingly given gauge lengths.     

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.     

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.     

Can carbon nanotubes grown on fibers fundamentally change stress distribution in a composite?

In carbon fiber reinforced polymer composites the onset of damage occurs at the fiber/matrix interface, where stress concentrations are the highest due to the property mismatch of the two materials. This article reports results of a modelling study indicating that carbon nanotubes (CNTs) grown on fibers are effective in suppressing stress concentrations at the fiber/matrix interface. In the case of high density CNT forests, they can even fundamentally change a profile of the interfacial stress. The study is performed using a novel two-scale finite element model of a nano-engineered composite based on the embedded regions technique.     

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.     

碳纳米管纤维/环氧树脂复合材料的界面剪切强度及微观结构

研究了碳纳米管纤维的微观结构和拉伸性能,并进一步分析了其与环氧树脂形成界面剪切强度及微观结构。采用单丝断裂试验测试了碳纳米管纤维/环氧树脂复合材料体系的界面剪切强度,结合单丝断裂过程中的偏光显微镜照片、复合材料的拉曼谱图和断口扫描电镜照片,研究了碳纳米管纤维/环氧树脂复合材料界面的微观结构。结果表明: 碳纳米管纤维/环氧树脂复合材料的界面剪切强度约为14 MPa;在碳纳米管纤维和环氧树脂形成界面的过程中,环氧树脂可以浸渍纤维,形成具有一定厚度的复合相,这种浸渍过程和界面相的形成都有利于碳纳米管纤维与基体之间的连接。     

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.