The effect of carbon nanotubes on the damage development in carbon fiber/epoxy composites

The aim of this study is to investigate the effect of carbon nanotubes (CNTs) on the initiation and development of damage in a woven carbon fiber/epoxy composite under quasi-static tensile loading. The composite is produced using resin transfer moulding and contains 0.25 wt.% of CNTs in the matrix. The results in the fiber direction report no improvement of the Young’s modulus and a slight improvement of the strength and strain-to-failure. The most important result of the study is a notion that CNTs have a hindering effect on the formation of transverse cracks. The conclusion is drawn from a combined analysis of the acoustic emission measurements (reporting a pronounced shift of all damage development thresholds towards higher strains by more than 30%) and X-ray/SEM observations (revealing a lower crack density in the CNT modified composite). The same analysis also indicates that the mechanism of energy dissipation through transverse microcracking is partially replaced by another mechanism that promotes (distributed) damage through fiber debonding.     

Effects of fiber length on the tensile strength of epoxy/glass fiber and polyester/glass fiber composites

In discontinuous fiber-reinforced composites, the shear strength at the fiber–matrix interface plays an important role in determining the reinforcing effect. In this paper, a method was devised to accurately determine this shear strength, taking the strength distribution of glass fiber into consideration. Calculated strength values based on the shear strenght obtained by the method were in better agreement with the experimental observations than those calculated by employing the shear strength obtained on the assumption that the fiber strength was uniform. The tensile strength of composites increases with increasing aspect ratio of the reinforcing fibers. This trend is almost the same regardless of the kind of matrix, the nature of interfacial treatment, and the environmental temperature. When composites are reinforced with random-planar orientation of short glass fibers of 1.5 times the mean critical fiber length, the tensile strength of composite reaches about 90% of the theoretical strength of composites reinforced with continuous glass fiber. Reinforcing with glass fibers 5 times the critical length, the tensile strength reaches about 97% of theoretical. However, from a practical point of view, it is adequate to reinforce with short fibers of 1.5–2.0 times the mean critical fiber lenght.     

Interfacial improvement of carbon fiber/epoxy composites using a simple process for depositing commercially functionalized carbon nanotubes on the fibers

An aqueous suspension deposition method was used to coat the sized carbon fibers T700SC and T300B with commercially carboxylic acid-functionalized and hydroxyl-functionalized carbon nanotubes (CNTs). The CNTs on the fiber surfaces were expected to improve the interfacial strength between the fibers and the epoxy. The factors affecting the deposition, especially the fiber sizing, were studied. According to single fiber-composite fragmentation tests, the deposition process results in improved fiber/matrix interfacial adhesion. Using carboxylic acid-functionalized CNTs, the interfacial shear strength was increased 43% for the T700SC composite and 12% for the T300B composite. The relationship between surface functional groups of the CNTs and the interfacial improvement was discussed. The interfacial reinforcing mechanism was explored by analyzing the surface morphology of the carbon fibers, the wettability between the carbon fibers and the epoxy resin, the chemical bonding between the fiber sizing and the CNTs, and fractographic observation of cross-sections of the composites. Results indicate that interfacial friction, chemical bonding and resin toughening are responsible for the interfacial improvement of nanostructured carbon fiber/epoxy composites. The mechanical properties of the CNT-deposited composite laminate were further measured to confirm the effectiveness of this strategy.     

Improved interfacial adhesion in carbon fiber/epoxy composites through a waterborne epoxy resin sizing agent

A series of self‐emulsified waterborne epoxy resin (WEP) emulsions were used as surface sizing for carbon fibers (CFs) to improve the interfacial adhesion between the CF and epoxy matrix. In this work, the hydrogenated bisphenol‐A epoxy resin (HBPAE) was modified by polyethylene glycol (PEG) with molecular weights of 400, 800, 1000, 1500, 2000, 4000, and 6000 g/mol. The properties of the WEP emulsion were examined by Fourier transform infrared spectroscopy, dynamic light scattering, and transmission electron microscopy. The surface characteristics of sized CFs were evaluated using scanning electron microscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy. Afterwards, CF/EP composites were prepared and their fracture surface and interlaminar shear strength (ILSS) were examined. The results indicated that PEG2000 modified HBPAE sizing had the optimum emulsion stability and film‐forming ability. Meanwhile, the results also demonstrated that a continuous and uniform sizing layer was formed on the surface of CFs and the surface sizing was excellent in improving the chemical activity of CFs. Compared with unsized CFs, the O1s/C1s composition ratio was observed to increase from 11.51% to 33.17% and the ILSS of CF/EP composites increased from 81.2 to 89.7 MPa, exhibiting better mechanical property than that of commercial Takemoto S64 sized CFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44757.     

The interfacial strength and fracture characteristics of ethanol and polymer modified carbon nanotube fibers in their epoxy composites

Carbon nanotube (CNT) fibers spun from CNT arrays were used as the reinforcement for epoxy composites, and the interfacial shear strength (IFSS) and fracture behavior were investigated by a single fiber fragmentation test. The IFSS between the CNT fiber and matrix strongly depended on the types of liquid introduced within the fiber. The IFSS of ethanol infiltrated CNT fiber/epoxy varied from 8.32 to 26.64 MPa among different spinning conditions. When long-molecule chain or cross-linked polymers were introduced, besides the increased fiber strength, the adhesion between the polymer modified fiber and the epoxy matrix was also significantly improved. Above all, the IFSS can be up to 120.32 MPa for a polyimide modified CNT fiber, one order of magnitude higher than that of ethanol infiltrated CNT fiber composites, and higher than those of typical carbon fiber/epoxy composites (e.g. 60–90 MPa). Moreover, the composite IFSS is proportional to the tensile strength and modulus of the CNT fiber, and decreases with increasing fiber diameter. The results demonstrate that the interfacial strength of the CNT fiber/epoxy can be significantly tuned by controlling the fiber structure and introducing polymer to optimize the tube–tube interactions within the fiber.     

Strengthening and stiffening carbon fiber epoxy composites by halloysite nanotubes,carbon nanotubes and silicon carbide whiskers

Low-cost natural halloysite (Hal) nanotubes (0.1 μm diameter) were effective for strengthening and stiffening continuous fiber epoxy composites, as shown for cross-ply carbon fiber (5 μm diameter, ~ 59 vol.%) epoxy nanocomposites under flexure, giving 17% increase in strength, 11% increase in modulus and 21% decrease in ductility. They were less effective than expensive multiwalled carbon nanotubes (0.02 μm diameter), which gave 25% increase in strength, 11% increase in modulus and 14% decrease in ductility. However, they were more effective than expensive silicon carbide whiskers (1 μm diameter), which gave 15% increase in strength, 9% increase in modulus and 20% decrease in ductility. Each filler, at ~ 2 vol.%, was incorporated in the composite at every interlaminar interface (interface between adjacent fiber laminae) by fiber prepreg surface modification. The flexural strength increase due to Hal nanotubes incorporation corroborated with the interlaminar shear strength increase. The measured values of the composite modulus agreed roughly with the calculated values based on the Rule of Mixtures. The interlaminar interface thickness was higher for the SiC whiskers case than the carbon nanotubes or Hal nanotubes case. The lamina thickness was not affected by the fillers. The composite density was 2% higher for the Hal nanotubes and SiC whiskers cases than the carbon nanotubes case.     

Preparation and properties of multi‐walled carbon nanotubes/carbon fiber/epoxy composites

Multi‐walled carbon nanotubes/carbon fiber (MWCNTs/CF) hybrid fillers are employed to prepare MWCNTs/CF/epoxy composites. Results reveal that a great improvement of the thermal conductivities of the epoxy composites with the addition of MWCNTs/CF hybrid fillers, and the thermal conductivity of the MWCNTs/CF/epoxy composites is 1.426 W/mK with 8 vol% treated MWCNTs/CF hybrid fillers (5 vol% MWCNTs + 3 vol% CF). Both the flexural and impact strength of the MWCNTs/CF/epoxy composites are increased firstly, but decreased with the excessive addition of MWCNTs. The flexural and impact strength of the MWCNTs/epoxy composites are optimal with 2 vol% MWCNTs. For a given MWCNTs/CF hybrid fillers loading, the surface treatment of MWCNTs/CF hybrid fillers can further increase the thermal conductivities and mechanical properties of the MWCNTs/CF/epoxy composites. POLYM. COMPOS., 35:2150–2153, 2014. © 2014 Society of Plastics Engineers     

Dispersion, interfacial interaction and re-agglomeration of functionalized carbon nanotubes in epoxy composites

The surface, interfacial and dispersion properties of carbon nanotubes (CNTs), and the mechanical properties of the CNT/epoxy composites affected by CNT functionalization are investigated. It is demonstrated that there exists strong correlations between amino-functionalization, dispersion, wettability, interfacial interaction and re-agglomeration behaviour of CNTs and the corresponding mechanical and thermo-mechanical properties of CNT/epoxy composites. The amino-functionalized CNTs exhibit higher surface energy and much better wettability with epoxy resin than the pristine CNTs, and the attached amine molecules arising from the functionalization effectively inhibit the re-agglomeration of CNTs during the curing of resin. These ameliorating effects along with improved interfacial adhesion between the matrix and functionalized CNTs through covalent bonds result in improved flexural and thermo-mechanical properties compared with those without functionalization.     

Improvements in interfacial and heat-resistant properties of carbon fiber/methylphenylsilicone resins composites by incorporating silica-coated multi-walled carbon nanotubes

The multi-scale reinforcement and interfacial strengthening on carbon fiber (CF)-reinforced methylphenylsilicone resin (MPSR) composites by adding silica-coated multi-walled carbon nanotubes (SiO₂-CNTs) were investigated. SiO₂-CNT has been successfully prepared via the hydrolysis of tetraethoxysilane in the presence of acid-oxidized multi-walled carbon nanotubes. Transmission electron microscopy, X-ray diffraction, and Fourier Transform infrared spectroscopy were carried out to examine the functional groups and structures of CNTs. Then, SiO₂-CNT was incorporated into MPSR matrix to prepare CF/MPSR-based composites by the compression molding method. The effects of the introduced SiO₂-CNT on the interfacial, impact, and heat-resistant properties of CF/MPSR composites were evaluated by short-beam bend method, impact test, and thermal oxygen aging experiments, respectively. Experimental results revealed that the CF/MPSR composites reinforced with 0.5 wt% SiO₂-CNT showed a significant increase 34.53% in the interlaminar shear strength (ILSS) and 20.10% in impact properties. Moreover, the heat-resistant properties of composites were enhanced significantly by adding SiO₂-CNT hybrid nanoparticles. These enhancements are mainly attributed to the improved matrix performance resulted from the molecular-level dispersion of SiO₂-CNT in MPSR matrix and the strong interfacial adhesion between SiO₂-CNT and matrix resin, which are beneficial to improve the mechanical stress transfer from MPSR matrix to CFs reinforcement and alleviate stress concentrations.     

Simultaneous improvement in strength,toughness, and thermal stability of epoxy/halloysite nanotubes composites by interfacial modification

This work investigated the effect of silane modification of halloysite nanotubes (HNTs) on the mechanical properties of epoxy/HNTs nanocomposites. Three kinds of silane coupling agents, including 3‐(2‐aminoethyl)‐aminopropyltrimethoxysilane (AEAPS), (3‐glycidyloxypropyl)‐trimethoxysilane (GPTMS), and octyltriethoxysilane (OTES), were employed. It was shown that the modified HNTs exhibited a better dispersion in the epoxy matrix compared with pristine one. Because of strong interfacial interaction between AEAPS modified HNTs and the epoxy matrix, the nanocomposites exhibited the highest glass transition temperature and modulus among all the samples. On the other hand, AEAPS and GPTMS modified HNTs/epoxy nanocomposites showed enhanced tensile strength and toughness. The toughing mechanisms were identified by the SEM micrographs of the fracture surfaces of the different kinds of samples. In this study, simultaneous enhancement of strength, toughness, and thermal stability of epoxy by the modified HNTs provides a novel approach to produce high‐performance thermosets. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43249.     

Carbon nanotubes grafting PBO fiber: A study on the interfacial properties of epoxy composites

To improve the interfacial performance of poly[p‐phenylene benzobisoxazole] (PBO) fiber and epoxy resin, a modified multiwalled carbon nanotubes (MWCNTs‐Ecp) were used to achieve this purpose through grafting onto PBO fiber surface using a gamma ray radiation method. Experimental results indicated that the equilibrium wetting rate and equilibrium adsorption amount of the modified PBO fiber for epoxy resin and acetone were all higher than that of as received PBO fiber. The interfacial shear strength (IFSS) of single fiber composite increased from 31.4 to 77.5 MPa after modification. The fracture models of composites are changed from pure interfacial failure to combination failure of interface and resin interlayer. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of carbon nanotubes grown temperature on the fracture behavior of carbon fiber reinforced magnesium matrix composites: Interlaminar shear strength and tensile strength

The design of an interfacial structure is particularly important for load transfer in composites. In this paper, different amounts of carbon nanotubes (CNTs) were grafted onto the carbon fiber (CF) surface by adjusting grown temperature using injection chemical vapor deposition (ICVD). The prepared CF preform grafted with CNTs (CNTs-CF) were used to reinforce magnesium alloy by squeeze casting process. The microstructures were analyzed by means of optical microscope (OM) and scanning electron microscope (SEM), and the interlaminar shear strength (ILSS) and tensile strength of the composites were determined by double-notch shear test and tensile test. The results indicated that moderate ILSS was more conducive to improving the tensile properties of carbon fiber reinforced magnesium matrix (C_f/Mg) composites. Compared with C_f/Mg, the tensile strength of composite with CNTs increased by about 80%. For C_f/Mg composites grafted with CNTs, CNTs had the effects of delaying crack propagation and increasing energy consumption by the pull-out and bridging mechanism, which were the main reasons for improving the strength. The analysis of shear fracture surface showed that the crack propagation path can be optimized by adjusting the amounts of grafted CNTs. The presence of CNTs affects the stress distribution and consequently the crack initiation as well as the crack propagation.     

Effect of carbon nanotubes on the curing and thermomechanical behavior of epoxy/carbon nanotubes composites

The processing of carbon nanotube based nanocomposites is one of the fastest growing areas in materials research due to the potential of significantly changing material properties even at low carbon nanotube concentrations. The aim of our work is to study the curing and thermomechanical behavior of carbon nanotube/epoxy nanocomposites that are critical from an application standpoint. Multiwall carbon nanotubes–epoxy composites are prepared by solvent evaporation based on a commercially available epoxy system and functionalized multiwalled carbon nanotubes. Three weight ratio configurations are considered (0.1, 0.5, and 1.0 wt%) and compared to both the neat epoxy to investigate the nano‐enrichment effect. We focus here on the modification of the curing behavior of the epoxy polymer in the presence of carbon nanotubes. It has been observed that introducing the multiwall carbon nanotubes delays the polymerization process as revealed by the modification of the activation energy obtained by differential scanning calorimetry. The viscoelastic response of the nanocomposites was studied from the measurements of storage modulus and the loss factor using dynamic mechanical analysis to evaluate the effect of the interface in each matrix/carbon nanotube system with changing matrix mobility. These measurements provide indications about the increase in the storage modulus of the composites, shift in the glass transition temperature due to the restriction of polymer chain movement by carbon nanotubes. POLYM. COMPOS., 35:441–449, 2014. © 2013 Society of Plastics Engineers     

Improvement in interfacial shear strength and fracture toughness for carbon fiber reinforced epoxy composite by fiber sizing

Carbon fiber was sized by a thermoplastic polymer solution mixed with a compatible amine monomer. The effect of sizing agent on tensile strength was studied by single fiber strength testing. Interfacial properties of re‐sized carbon fiber/epoxy composite were investigated, with special emphasis on the improvement in both interfacial shear strength and interfacial fracture toughness. The interfacial fracture toughness of composites was characterized by calculating the effective interphase fracture energy rate through the information obtained from the force–displacement curve in the micro‐bond test. Fracture topography of micro‐bond specimen was observed to discuss the interfacial fracture mechanism. POLYM. COMPOS., 35:482–488, 2014. © 2013 Society of Plastics Engineers     

Effect of hygrothermal conditioning on compressive strength after impact in carbon fiber/epoxy composites

Carbon fiber-reinforced polymers have been widely applied in structural parts and components in several sectors, in addition to being constantly used in environments with the presence of humidity and high temperatures, which can affect their density, hardness, and rigidity. In this work, the influence of hydrothermal conditioning on carbon fiber (CF)/epoxy composites was investigated using three types of epoxy resin and two different CF fabric reinforcements, that is, plain weave and eight harness satin (8HS) arrangements. The CF/epoxy composites were subjected to compression after impact (CAI) test by 28 and 40 J energy and then exposed to hydrothermal conditioning for 8 weeks. After the CAI tests, the visual analysis of all composites presented microbuckling mechanisms. The composites tested with 40 J energy absorbed only 2% more moisture compared with the other composites, nonimpacted, and tested with 28 J, indicating that the impact damage did not cause delamination between the layers of the composites, which could facilitate the absorption of water. All composites analyzed showed resistance to CAI even after exposure to humidity, with decreases ranging from 2.8% to 23.8% about the unconditioned specimens. The decrease in CAI also shows the influence of the type of epoxy matrix and the arrangement of the CF in fabrics.     

Formation of a carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube hybrid reinforcement and its effect on the interfacial properties of carbon fiber/epoxy composites

A carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube (CF–POSS–CNT) hybrid reinforcement was prepared by grafting CNTs onto the carbon fiber surface using octaglycidyldimethylsilyl POSS as the linkage in an attempt to improve the interfacial properties between carbon fibers and an epoxy matrix. X-ray photoelectron spectroscopy, scanning electron microscopy, dynamic contact angle analysis and single fiber tensile testing were performed to characterize the hybrid reinforcements. Interlaminar shear strength (ILSS), impact toughness, dynamic mechanical analysis and force modulation atomic force microscopy were carried out to investigate the interfacial properties of the composites. Experimental results show that POSS and CNTs are grafted uniformly on the fiber surface and significantly increase the fiber surface roughness. The polar functional groups and surface energy of carbon fibers are obviously increased after the modification. Single fiber tensile testing results demonstrate that the functionalization does not lead to any discernable decrease in the fiber tensile strength. Mechanical property test results indicate the ILSS and impact toughness are enhanced. The storage modulus and service temperature increase by 11 GPa and 17 °C, respectively. POSS and CNTs effectively enhance the interfacial adhesion of the composites by improving resin wettability, increasing chemical bonding and mechanical interlocking.     

Effects of environmental exposure on fiber/epoxy interfacial shear strength

The TRI microbond technique for direct determination of fiber/resin interfacial shear strength in composites has been used for investigation the influence of environmental conditions on adhesive bonding in certain systems. The small dimensions involved in the method facilitate uniform exposure and short exposure times. We have observed significant changes in both average shear strength and in shear strength distributions on exposing aramid/epoxy and glass/epoxy microbond assemblies to steam or hot water. Shear strength dropped to a plateau value in both cases, the reduction being more drastic with the glass fiber. Vacuum drying restored shear strength completely in aramid/epoxy microassemblies, even when the surface of the aramid fiber had been chemically modified, but there was only partial regeneration of bond strength with the glass/epoxy system.     

Measuring effective interfacial shear strength in carbon fiber bundle polymeric composites

Adhesion in composite materials is often quantified using the single fiber fragmentation (SFF) test. While this method is believed to provide accurate values for the fiber–matrix interfacial shear strength (IFSS), these may not accurately reflect the macroscopic mechanical properties of specimens consisting of tows of thousands of tightly spaced fibers embedded in a resin matrix. In these types of specimens, adhesion may be mitigated by fiber twisting and misalignment, differences in the resin structure in the confined spaces between the fibers and, most importantly, by any incompleteness of the fiber wetting by the resin. The present work implements fiber band fragmentation (FBF) testing to obtain effective interfacial shear strengths, whose values reflect the importance of these factors. The fiber fragmentation in these specimens is tracked through the counting and sorting of acoustic emission (AE) events occurring during the tensile testing of the specimen and yields the average critical fiber fragment length. AE results, in conjunction with stress-strain data, show that fiber breakage events occur at acoustic wavelet amplitudes substantially greater than those generated by fiber/matrix debonding. Kelly–Tyson analysis is applied, using the measured critical fiber fragment length together with known values for the fiber diameter and tensile strength to yield the effective IFSS. FBF tests are performed on carbon fiber/poly(vinyl butyral) (PVB) dog-bone fiber-bundle systems, and effective IFSS values substantially lower than those typically reported for the single fiber fragmentation testing of similar systems are obtained, suggesting the importance of multi-fiber effects and incomplete fiber wetting.     

多壁碳纳米管／环氧树脂复合材料性能研究

采用物理机械方法与化学方法相结合的手段,制备了多壁碳纳米管（MWNTS）／环氧树脂（Epoxy）复合材料。通过力学拉伸试验测试了MWNTs/Epoxy复合材料拉伸强度和拉伸模量与MWNTS添加量的关系,利用扫描电镜（SEM）分析了MWNTS／Epoxy复合材料的拉伸断面,并用表面电阻测试仪对所制备的碳纳米管复合材料进行了电学性能测试。结果表明：经过化学酸化的方法处理后的MWNTS在复合材料中的分散得到了改善,力学性能也得到了明显的提高,但酸处理后的复合材料的电学性能明显低于未处理的复合材料。