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.     

The influence of multiscale fillers on the rheological and mechanical properties of carbon-nanotube–silica-reinforced epoxy composite

Multiscale fillers were fabricated through synthesis of carbon nanotubes (CNTs) on silica microparticles by the use of chemical vapor deposition. Three types of catalyst precursors with different concentrations and reaction times were investigated to find the optimal conditions for CNT synthesis. The produced multiscale fillers of CNT–silica were incorporated within epoxy resin to fabricate a multiscale composite. Rheological analysis and tensile and impact tests were performed to study the effect of fillers on the structural properties of composites. The rheological results demonstrated a similar viscous behavior between CNT–silica suspensions and epoxy, which implies that there was no critical increase of viscosity. Significant improvements in the elastic modulus and tensile and impact strength were achieved for epoxy matrix filled with the optimal fraction of multiscale fillers. The reinforcing efficiency of multiscale fillers was evaluated by comparing the results of micromechanical models with experimental data.     

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.     

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.     

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.     

电子束固化复合材料界面

电子束固化复合材料界面粘结性能较低是急待解决的问题。利用阳极氧化技术和偶联剂涂层对碳纤维表面进行处理。处理前后的碳纤维表面性能利用SEM、XPS和接触角测试方法进行分析,通过层间剪切强度表征电子束固化复合材料界面粘结性能,并且与热固化复合材料进行对比。结果表明: 当碳纤维在酸性电解液中进行阳极氧化时,有利于提高电子束固化复合材料界面粘合性能,在碱性电解液中进行阳极氧化时, 则导致较低界面粘接性能。阳极氧化与偶联剂双重增效作用能够提高电子束固化复合材料界面粘合性能。     

Effects of emulsion sizing with nano-SiO<Subscript>2</Subscript> on interfacial properties of carbon fibers/epoxy composites

Nano-SiO₂ particles were used to modify epoxy emulsion sizing of carbon fibers to improve the interfacial properties of carbon fibers reinforced epoxy composites. The mechanical interfacial strength between fibers and matrix was investigated by the single fiber fragmentation test and the 3-point short beam shear test, respectively. Dynamic contact angle analysis (DCAA), X-ray photoelectron spectrometry (XPS) and atomic force microscopy (AFM) were performed on the carbon fibers with unmodified sizing and nano-SiO₂ modified sizing. The results indicated that modified sizing with nano-SiO₂ slightly increased the surface energy, the hydroxyl functional group and the surface roughness of carbon fibers compared to unmodified sizing, so that the interfacial shear strength (IFSS) of the single fiber composites and the interlaminar shear strength (ILSS) of composites were enhanced. SEM images of fracture sections of composites proved powerfully that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂ modified emulsion sizing treatment.     

Carbon and glass hierarchical fibers: Influence of carbon nanotubes on tensile,flexural and impact properties of short fiber reinforced composites

Dense carbon nanotubes (CNTs) were grown uniformly on the surface of carbon fibers and glass fibers to create hierarchical fibers by use of floating catalyst chemical vapor deposition. Morphologies of the CNTs were investigated using scanning electronic microscope (SEM) and transmission electron microscope (TEM). Larger diameter dimension and distinct growing mechanism of nanotubes on glass fiber were revealed. Short carbon and glass fiber reinforced polypropylene composites were fabricated using the hierarchical fibers and compared with composites made using neat fibers. Tensile, flexural and impact properties of the composites were measured, which showed evident enhancement in all mechanical properties compared to neat short fiber composites. SEM micrographs of composite fracture surface demonstrated improved adhesion between CNT-coated fiber and the matrix. The enhanced mechanical properties of short fiber composites was attributed to the synergistic effects of CNTs in improving fiber–matrix interfacial properties as well as the CNTs acting as supplemental reinforcement in short fiber-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.     

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.     

快速固化碳纳米管/苎麻纤维/环氧树脂复合材料层板的制备与性能

针对植物纤维/树脂基复合材料高性能化问题,本研究以羟基化碳纳米管/无水乙醇分散液预先浸渍苎麻纤维织物,得到了碳纳米管分散均匀的碳纳米管/苎麻纤维多尺度复合织物,并进一步以快速固化环氧树脂为基体,采用真空辅助树脂灌注成型工艺(VARI)制备了碳纳米管改性的苎麻纤维/环氧树脂基复合材料层板(PRFC)。研究结果表明,相比未采用碳纳米管改性的苎麻纤维/环氧树脂复合材料(RFC),PRFC的弯曲强度提高14.7%,冲击强度提高20.9%。相比碳纳米管预先分散于环氧树脂基体中制备的碳纳米管改性苎麻纤维/环氧树脂复合材料(MRFC),PRFC的力学性能提高更显著。同时,PRFC的吸湿性能比MRFC和RFC的明显降低。     

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.     

Inherent sensing and interfacial evaluation of carbon nanofiber and nanotube/epoxy composites using electrical resistance measurement and micromechanical technique

Inherent sensing of load, micro-damage and stress transferring effects were evaluated for carbon nanotube (CNT) and carbon nanofiber (CNF)/epoxy composites (with various added contents) by an electro-micromechanical technique, using the four-point probe method. Carbon black (CB)/epoxy composites, with conventional nanosize material added, were used for the comparison with CNT and CNF composites. Subsequent fracture of the carbon fiber in the dual matrix composites (DMC) was detected by acoustic emission (AE) and by the change in electrical resistance, ΔR due to electrical contacts of neighboring CNMs. Stress/strain sensing of the nanocomposites was detected by an electro-pullout test under uniform cyclic loading/subsequent unloading. CNT/epoxy composites showed the best sensitivity to fiber fracture, matrix deformation and stress/strain sensing, whereas CB/epoxy composite exhibited poorer sensitivity. From the apparent modulus (as a result of matrix modulus and interfacial adhesion), the stress transferring effects reinforced by CNT was highest among three CNMs. The thermodynamic work of adhesion, W_a as found by dynamic contact angle measurements of the CNT/epoxy composite as a function of added CNT content was correlated and found to be consistent with the apparent mechanical modulus. Uniform dispersion and interfacial adhesion appear to be key factors for improving both sensing and mechanical performance of nanocomposite. Thermally treated-CNF composites exhibited a slightly higher apparent modulus, whereas higher testing temperatures appeared to lower the apparent modulus.     

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。     

Optimum dispersion conditions and interfacial modification of carbon fiber and CNT–phenolic composites by atmospheric pressure plasma treatment

Electric resistance measurements were used to determine the optimal dispersion conditions for carbon nanotubes (CNTs) in phenolic resins. Plasma treatment is frequently used to modify carbon fiber surfaces to improve adhesion of the fibers to matrices. Such treatment might also influence carbon fiber tensile strength. In order to determine the effect of atmospheric pressure plasma treatment on carbon fiber tensile strength and interfacial bonding strength, change in tensile strength of the fiber was studied at different gage lengths before and after the plasma treatment. The wettability of carbon fibers was improved significantly after only 10 s of plasma treatment. Such plasma treatment resulted in a decrease in the advancing contact angle from 65° to 28°. Surface energies of carbon fiber and CNT–phenolic composites were measured using the Wilhelmy plate technique, indicating that the work of adhesion between plasma treated carbon fibers and CNT–phenolic composites was higher than it before plasma modification. The interfacial shear strength (IFSS) and apparent modulus were also increased by plasma treatment of the carbon fibers.     

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.     

Effects of silane-modified carbon nanotubes on flexural and fracture behaviors of carbon nanotube-modified epoxy/basalt composites

We investigated the effects of carbon nanotube (CNT) modification with silane on the flexural and fracture behaviors of modified carbon nanotube epoxy/basalt (CNT/epoxy/basalt) composites. Flexural and mode I fracture tests were performed using acid-treated and silane-treated CNT/epoxy/basalt composites, respectively. FT-IR analysis was conducted to determine the chemical change on the surface of basalt fiber due to the silane modification. After the fracture tests, the fracture surfaces of the CNT/epoxy/basalt composites were examined with scanning electron microscopy (SEM) to investigate the fracture mechanisms of the CNT/epoxy/basalt composites, depending on the CNT modification. The results show that the flexural modulus and strength of silane-treated CNT/epoxy/basalt composites are ～10% and ～14% greater, respectively, than those of acid-treated CNT/epoxy/basalt composites. The fracture toughness G_Ic of silane-treated CNT/epoxy/basalt composites was ～40% greater than that of acid-treated CNT/epoxy/basalt composites. SEM examination revealed that the improvement in the flexural and fracture properties of silane-treated CNT/epoxy/basalt composites occurred due to enhanced dispersion and interfacial interaction between the silane-modified CNTs and the epoxy.     

Vapor grown carbon fiber composites with epoxy and poly(phenylene sulfide) matrices

Vapor grown carbon fibers (VGCF, Pyrograf III™ from Applied Sciences, Inc.), with 100–300 nm diameters and ∽10–100 μm lengths, were formulated in various fiber volume fractions into epoxy (thermoset) and into poly(phenylene sulfide) (thermoplastic) composites. Increases in stiffness were observed as with previous VGCF/organic matrix composites. Large increases in flexural strengths were achieved in both systems demonstrating for the first time that discontinuous randomly oriented Pyrograf III™ can give strength increases and has substantial potential as a reinforcement in composites. Here-to-fore, addition of VGCF caused strength decreases. Voids, residual thermal strains (as the fiber surface area is ∽35 times greater than 7 μm-diameter PAN fiber), or uncertainties about fiber strength, fiber–matrix bonding and the degree of fiber dispersion, could cause losses of strength. Thermal conductivity properties of VGCF/ABS (acrylonitrile–butadiene–styrene from GE Plastics) and VGCF/epoxy composites with various fiber volume fractions were measured. Thermal conductivity increased with an increase in fiber volume fraction. However, these increases were not significant enough to make these VGCF fiber/organic matrix composites candidates for thermally conductive materials.     

Effects of CNT diameter on mechanical properties of aligned CNT sheets and composites

Drawing, winding, and pressing techniques were used to produce horizontally aligned carbon nanotube (CNT) sheets from free-standing vertically aligned CNT arrays. The aligned CNT sheets were used to develop aligned CNT/epoxy composites through hot-melt prepreg processing with a vacuum-assisted system. Effects of CNT diameter change on the mechanical properties of aligned CNT sheets and their composites were examined. The reduction of the CNT diameter considerably increased the mechanical properties of the aligned CNT sheets and their composites. The decrease of the CNT diameter along with pressing CNT sheets drastically enhanced the mechanical properties of the CNT sheets and CNT/epoxy composites. Raman spectra measurements showed improvement of the CNT alignment in the pressed CNT/epoxy composites. Research results suggest that aligned CNT/epoxy composites with high strength and stiffness are producible using aligned CNT sheets with smaller-diameter CNTs.     

Dynamic fracture of carbon nanotube/epoxy composites under high strain-rate loading

We investigate dynamic fracture of three types of multiwalled carbon nanotube (MWCNT)/epoxy composites and neat epoxy under high strain-rate loading (${10}^5''–''{10}^6$ s⁻¹). The composites include randomly dispersed, 1 wt%, functionalized and pristine CNT/epoxy composites, as well as laminated, ∼50 wt% CNT buckypaper/epoxy composites. The pristine and functionalized CNT composites demonstrate spall strength and fracture toughness slightly higher and lower than that of neat epoxy, respectively, and the spall strength of laminated CNT buckypaper/epoxy composites is considerably lower; both types of CNTs reduce the extent of damage. Pullout, sliding and immediate fracture modes are observed; the fracture mechanisms depend on the CNT–epoxy interface strength and fiber strength, and other microstructures such as the interface between CNT laminates. Compared to the functionalized CNT composites, weaker CNT–epoxy interface strength and higher fiber strength lead to a higher probability of sliding fracture and higher tensile strength in the pristine CNT composites at high strain rates. On the contrary, sliding fracture is more pronounced in the functionalized CNT composites under quasistatic loading, a manifestation of a loading-rate effect on fracture modes. Despite their helpful sliding fracture mode and large CNT content, the weak laminate–laminate interfaces play a detrimental role in fracture of the laminated CNT buckypaper/epoxy composites. Regardless of materials, increasing strain rates leads to pronounced rise in tensile strength and fracture toughness.