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.     

Comparison of drying methods for the preparation of carbon fiber felt/carbon nanotubes modified epoxy composites

Carbon fiber felt with carbon nanotubes (CNTs) were prepared by immersing three-dimensional (3D) felt into CNT aqueous solution (with dispersant) followed by removing water with different drying methods. Epoxy resin was then introduced into the felt to obtain 3D fiber felt/CNTs modified epoxy composites. This paper highlights the effect of drying method on macro-morphologies of the felt, morphological dispersion of CNTs and some relevant properties of the composites, including electrical conductivity and flexural performance. The results demonstrate that compared to the commonly used heat drying method, freeze drying technique possesses obvious advantages for the fabrication of fiber felt/CNT modified epoxy 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.     

Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

Preparation of carbon nanotube/copper/carbon fiber hierarchical composites by electrophoretic deposition for enhanced thermal conductivity and interfacial properties

A facile electrophoretic deposition method was proposed to deposit copper (Cu) and carbon nanotubes (CNTs) on the surface of carbon fiber (CF) to improve the thermal conductivity and interfacial properties of carbon fiber-reinforced polymer (CFRP) composites. Surface morphologies, crystallographic properties, thermal conductivity, interlaminar shear strength (ILSS) and element distribution of the composites were characterized by scanning electron microscopy (SEM), X-ray diffraction, thermal constant analysis, short-beam bending tests and SEM energy-dispersive X-ray diffractometer (SEM–EDX), respectively. The results indicate that the presence of Cu and CNTs generated networks and bridges with each other, which produced continuous heat conduction pathways and significantly enhanced both the specific surface area and roughness of the fiber surface. These pathways obviously promoted an improvement in the thermal and interfacial properties. The thermal conductivity and ILSS of the CNTs–Cu–CF/epoxy composites increased by 292 and 39.5%, respectively, compared with CF/epoxy composites. Therefore, this method is anticipated to be utilized in the future fabrication of multifunctional CFRP composites.     

Exploiting carbon nanotube networks for damage assessment of fiber reinforced composites

An approach for damage inspection of composite structures utilizing carbon nanotubes (CNT) networks is investigated. CNT are dispersed in an epoxy using a processing technique compatible with commonly employed composite manufacturing techniques and subsequently used as matrix for a structural glass fiber reinforced composite. The developed electrical conductivity of the composite system is verified experimentally. The electrically conductive CNT network within the GFRP is exploited through distributed electrical voltage measurements to sense and, ultimately, locate damage in the plane of the composite plate. Damage in the form of cracks or delamination interrupts the continuity of the CNT network separating and isolating regions of the conductive network. Employing electric potential fields these changes can become measurable and can provide information for inversely locating the damage. Electrical Resistance Tomography (ERT) is formulated and experimentally applied to measure changes in the potential fields and deliver electrical conductivity change maps which are used to identify and locate changes in the CNT networks. These changes are correlated to capture the damage in the composite. Different damage modes are studied to assess the capabilities of the technique. The technique shows sensitivity to very small damages; less than 0.1% of the inspected area. The solution of the inverse ERT problem delivers a conductivity change maps which offers an effective localization with nearly 10% error and an inspection area suppression of around 75%. The proposed methodology to create CNT networks enables the application of ERT for Non-Destructive Evaluation of composite materials, previously not possible due to lack of conductivity, thus offering damage sensing and location capabilities even in-situ.     

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.     

Nanoscale structure and local mechanical properties of fiber-reinforced composites containing MWCNT-grafted hybrid glass fibers

Carbon nanotubes (CNTs) were grown from the surface of glass fibers by chemical vapor deposition, and these hybrid fibers were individually dispersed in an epoxy matrix to investigate the local composite structure and properties near the fiber surface. High-resolution transmission electron microscopy revealed the influence of infiltration and curing of a liquid epoxy precursor on the morphology of the CNT “forest” region, or region of high CNT density near the fiber surface. Subsequent image analysis highlighted the importance of spatially dependent volume fractions of CNTs in the matrix as a function of distance from the fiber surface, and nanoindentation was used to probe local mechanical properties in the CNT forest region, showing strong correlations between local stiffness and volume fraction. This work represents the first in situ measurements of local mechanical properties of the nano-structured matrix region in hybrid fiber-reinforced composites, providing a means of quantifying the reinforcement provided by the grafted nanofillers.     

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.     

Hybrid multi-scale epoxy composite made of conventional carbon fiber fabrics with interlaminar regions containing electrospun carbon nanofiber mats

Herein we report the development and evaluation of hybrid multi-scale epoxy composite made of conventional carbon fiber fabrics with interlaminar regions containing mats of electrospun carbon nanofibers (ECNs). The results indicated that (1) the interlaminar shear strength and flexural properties of hybrid multi-scale composite were substantially higher than those of control/comparison composite without ECNs; in particular, the interlaminar shear strength was higher by ∼86%; and (2) the electrical conductivities in both in-plane and out-of-plane directions were enhanced through incorporation of ECNs, while the enhancement of out-of-plane conductivity (∼150%) was much larger than that of in-plane conductivity (∼20%). To validate the data reduction procedure, a new shear stress formula was formulated for composite laminates, which took into account the effect of layup and inter-layers. The study suggested that ECNs could be utilized for the development of high-performance composites, particularly with the improved out-of-plan properties (e.g., interlaminar shear strength).     

Vibration damping characteristics of carbon fiber-reinforced composites containing multi-walled carbon nanotubes

Vibration damping characteristic of nanocomposites and carbon fiber reinforced polymer composites (CFRPs) containing multiwall carbon nanotubes (CNTs) have been studied using the free and forced vibration tests. Several vibration parameters are varied to characterize the damping behavior in different amplitudes, natural frequencies and vibration modes. The damping ratio of the hybrid composites is enhanced with the addition of CNTs, which is attributed to sliding at the CNT-matrix interfaces. The damping ratio is dependent on the amplitude as a result of the random orientation of CNTs in the epoxy matrix. The natural frequency shows negligible influence on the damping properties. The forced vibration test indicates that the damping ratios of the CFRP composites increase with increasing CNT content in both the 1st and 2nd vibration modes. The CNT-epoxy nanocomposites also show similar increasing trends of damping ratio with CNT content, indicating the enhanced damping property of CFRPs arising mainly from the improved damping property of the modified matrix. The dynamic mechanical analysis further confirms that the CNTs have a strong influence on the composites damping properties. Both the dynamic loss modulus and loss factor of the nanocomposites and the corresponding CFRPs show consistent increases with the addition of CNTs, an indication of enhanced damping performance.     

Effect of carbon nanotube waviness on the effective thermoelastic properties of a novel continuous fuzzy fiber reinforced composite

This paper deals with the investigation of the effect of carbon nanotube (CNT) waviness on the effective coefficient of thermal expansion (CTE) of a novel continuous fuzzy fiber reinforced composite (FFRC). This novel FFRC is composed of carbon fibers, sinusoidally wavy CNTs and epoxy matrix. The sinusoidally wavy CNTs are radially grown on the circumferential surfaces of the carbon fibers. Analytical micromechanics model based on the method of cells (MOC) approach is derived to investigate the influence of the waviness of CNTs on the effective CTEs of the FFRC. The present study reveals that if the amplitudes of the radially grown sinusoidally wavy CNTs are parallel to the axis of the carbon fiber then the thermoelastic properties of the FFRC are significantly improved over those of the FFRC being composed of straight CNTs.     

Fabrication and effective thermal conductivity of multi-walled carbon nanotubes reinforced Cu matrix composites for heat sink applications

A novel particles-compositing method was used for the first time to disperse different contents of multi-walled carbon nanotubes (CNTs) in micron sized copper powders, which were subsequently consolidated into CNT/Cu composites by spark plasma sintering (SPS). Microstructural observations showed that the homogeneous distribution of CNTs and dense composites could be obtained for 0–10 vol.% CNT contents. The CNT clusters were appeared in the powder mixture with 15 vol.% CNTs, which resulted in an insufficient densification of the composites. The effective thermal conductivity of the composites was analyzed both theoretically and experimentally. The addition of CNTs showed no enhancement in overall thermal conductivity of the composites due to the interface thermal resistance associated with the low phase contrast of CNT to copper and the random tube orientation. Besides, the composite containing 15 vol.% CNTs led to a rather low thermal conductivity due possiblely to the combined effect of unfavorable factors induced by the presence of CNT clusters, i.e. large porosity, lower effective conductivity of CNT clusters themselves and reduction of SPS cleaning effect. The CNT/Cu composites may be a promising thermal management material for heat sink applications.     

Study on the semi-empirical model for the complex permittivity of carbon nanocomposite laminates in microwave frequency band

A semi-empirical model is proposed for the complex permittivity of composites containing electrical conductive carbon nanomaterials such as carbon black (CB), carbon nanofiber (CNF) and multi-walled carbon nanotube (CNT). The composites were fabricated with E-glass fabric/epoxy prepregs. The model is based on the percolation theory. The model is available for the composite of filler content over the percolation threshold and applicable within the high frequency band in which AC electrical conductivity of the composite is continuously proportional to the frequency. The proposed model is composed of the numerical equations of the scaling law in percolation theory and constants obtained from experiments to quantify the model. The model describes the complex permittivity as a function of frequency and filler content. The model was verified when compared with the measurements. The measurements for the complex permittivities of the composites were performed at the frequency band between 0.5 and 18.0 GHz using a vector network analyzer with a 7 mm coaxial air line.     

Interfacial and mechanical properties of epoxy composites containing carbon nanotubes grafted with alkyl chains of different length

Dispersion of the nano-fillers is important in the manufacture of high performance nanocomposites. Dispersion of silane treated CNT/epoxy composites was analyzed for various alkyl chain lengths. Difference in mobility of alkyl chains of different length affects the excluded free volume and repulsive forces. An optimal chain length was observed to impart maximum mechanical and impact properties. Differences in the dispersion of CNT due to alterations in alkyl chain lengths were determined using electrical resistance measurement. Spreading of CNT/epoxy rearranged the CF tow resulting in a change in electrical resistance ratio (CERR) and the differences in alkyl chain length effected CNT spreading. Dispersion and wetting conditions with different alkyl chain lengths resulted in changes in CERR, ILSS and other proprieties. The butyl chain length was optimal of the alkyl chain lengths studied. This is attributed to the butyl chains known good mobility and steric repulsion effects compared to longer alkyl chain lengths.     

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 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.     

Interfacial load transfer in carbon nanotube/ceramic microfiber hybrid polymer composites

Growing carbon nanotubes (CNTs) on the surface of fibers has the potential to modify fiber–matrix interfacial adhesion, enhance the composite delamination resistance, and possibly improve its toughness and any matrix-dominated elastic property as well. In the present work aligned CNTs were grown upon ceramic fibers (silica and alumina) by chemical vapor deposition (CVD) at temperatures of 650 °C and 750 °C. Continuously-monitored single fiber composite (SFC) fragmentation tests were performed on pristine as well as on CNT-grown fibers embedded in epoxy. The critical fragment length, fiber tensile strength at critical length, and interfacial shear strength were evaluated. Significant increases (up to 50%) are observed in the fiber tensile strength and in the interfacial adhesion (which was sometimes doubled) with all fiber types upon which CNTs are CVD-grown at 750 °C. We discuss the likely sources of these improvements as well as their implications.     

Evaluation and visualization of the percolating networks in multi-wall carbon nanotube/epoxy composites

In this study, epoxy-based nanocomposites containing multi-wall carbon nanotubes (CNTs) were produced by a calendering approach. The electrical conductivities of these composites were investigated as a function of CNT content. The conductivity was found to obey a percolation-like power law with a percolation threshold below 0.05 vol.%. The electrical conductivity of the neat epoxy resin could be enhanced by nine orders of magnitude, with the addition of only 0.6 vol.% CNTs, suggesting the formation of a well-conducting network by the CNTs throughout the insulating polymer matrix. To characterize the dispersion and the morphology of CNTs in epoxy matrix, different microscopic techniques were applied to characterize the dispersion and the morphology of CNTs in epoxy matrix, such as atomic force microscopy, transmission electron microscopy, and scanning electron microscopy (SEM). In particular, the charge contrast imaging in SEM allows a visualization of the overall distribution of CNTs at a micro-scale, as well as the identification of CNT bundles at a nano-scale. On the basis of microscopic investigation, the electrical conduction mechanism of CNT/epoxy composites is discussed.     

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.