Enhanced interfacial strength and mechanical properties of carbon fiber composites by introducing functionalized silica nanoparticles into the interface

Introducing nanoparticles onto the surface of carbon fibers (CFs) is a useful method for enhancing the quality of fiber-matrix interface. In this work, a liquid sizing agent containing functionalized silica nanoparticles (SiO₂) was well prepared to improve interfacial strength and mechanical properties of composites. In order to enhance the dispersion of SiO₂ nanoparticles in sizing agent, SiO₂ nanoparticles were chemically grafted with 3-aminopropyltriethoxysilane (APS), and then silanized silica (SiO₂-APS) was introduced into the interphase by a conventional sizing process as well. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) confirmed the successful preparation of SiO₂-APS. Scanning electron microscopy (SEM) showed that a uniform distribution of SiO₂-APS on the fiber surface and the increased surface roughness. The sized fibers (CF/SiO₂-APS) exhibited a high surface free energy and good wettability based on a dynamic contact angle testing. Interfacial microstructure and mechanical properties of untreated and sized CFs composites were investigated. Simultaneous enhancements of interlaminar shear strength (ILSS) and impact toughness of CF/SiO₂-APS composites were achieved, increasing 44.79% in ILSS and 31.53% in impact toughness compared to those of untreated composites. Moreover, flexural strength and modulus of composites increased by 32.22 and 50.0% according to flexural test. In addition, the hydrothermal aging resistance of CF/SiO₂-APS composites has been improved significantly owing to the introduced Si-O-Si bonds at the interface.     

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.     

Effect of preform and carbon matrix on bending strength of Cf/Cu/C composites

Aiming to obtain composites with appropriate mechanical properties for pantograph sliders, copper mesh modified carbon/carbon (C_f/Cu/C) composites were prepared by chemical vapor infiltration (CVI) in C₃H₆ +?N₂ atmosphere and impregnation-carbonization (I-C) with furan resin. In this paper, C_f/Cu/C composites with two kinds of preforms and carbon matrixes were obtained. The effect of preforms and carbon matrixes on bending strength was investigated. The results indicated that the bending strength of carbon fiber/copper mesh reinforced pyrolytic carbon matrix composites was about 181.39–195.43?MPa, while that reinforced resin carbon matrix composites had the worst bending strength around 54.45–57.04?MPa, in terms of the same preform. The bending strength of C_f/Cu/C composites in the parallel orientation and vertical orientation were also similar. As for C_f/Cu/C composites with the same carbon matrix, the bending strength of C_f/Cu/C composites with non-woven fiber/fiber web/copper mesh type preform was higher than that with fiber web/copper mesh type preform. However, the bending strength of carbon fiber/copper mesh reinforced resin carbon matrix composites showed the opposite trend, and its reasons were analyzed and discussed taking advantage of the fracture mechanisms.     

Effect of deposited carbon nanotubes on interlaminar properties of carbon fiber‐reinforced epoxy composites using a developed spraying processing

Carbon fiber‐reinforced epoxy composites, with incorporated carboxylic multiwall carbon nanotubes (CNTs), were prepared using vacuum‐assisted resin infusion (VARI) molding, and the in‐plane and out‐of‐plane properties, including mode‐I (G_Ic) and mode‐II (G_IIc) interlaminar fracture toughness, interlaminar shear strength (ILSS), tensile, and flexural properties were measured. A novel spraying technique, which sprays a kind of epoxy resin E20 with high viscosity after spraying the CNTs, was adopted to deposit the CNTs on the surface of carbon fiber fabric. The E20 was used to anchor CNTs on the fabric surface, avoiding that the deposited CNTs were removed by the infusing resin during VARI process. The spraying processing, including spraying amount and spraying sequence, was optimized based on the distribution of CNTs on the fibers. After that, three composite specimen groups were fabricated using different carbon fiber fabrics, including as‐received, CNT‐deposited with E20, and CNT‐deposited without E20. The effects of CNTs on the processing quality and mechanical properties of carbon fiber‐reinforced polymer composites were studied. The experimental results show that all studied laminates have uniform thickness with designed values and no obvious defects form inside the laminates. Compared with the composite without CNTs, depositing CNTs with E20 increases by 24% in the average propagation G_Ic, by 11% in the propagation G_IIc and by 12% in the ILSS, while it preserves the in‐plane mechanical properties, However, depositing CNTs without E20 reduces interlaminar fracture toughness. These phenomena are attributed to the differences in the distribution of CNTs and the fiber/matrix interfacial bonding for different spraying processing. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Improving the interlaminar shear strength and thermal conductivity of carbon fiber/epoxy laminates by utilizing the graphene-coated carbon fiber

The poor interlaminar properties restrict the application of carbon fiber reinforced polymer (CFRP) composites. In this work, a novel method for fabricating a graded interface structure is developed to improve the through-thickness thermal conductivity of CFRP composites. High-strength graphene nano-plates (GnP) and phenolic resin (PF) were selected to deposit on the surface of carbon fiber to design a novel CF/Epoxy laminates, where a simultaneous improvement of interlaminar shear strength (ILSS) and through-thickness thermal conductivity was observed. With addition of 1 wt % of GnP-PF in CF, 37.04% increase of the ILSS, and 16.67% enhancement of thermal conductivity compared to the original CFRP. The mechanism for improvement of both ILSS and thermal conductivity was studied by scanning electron microscopy and nano-indentation, where a better interface formed by GnP-PF has been clearly observed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47061.     

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.     

Interfacial microstructure and strengthening mechanisms of Cf/Mg composite with double-layer interface

In order to overcome the interfacial incompatibility of carbon fiber reinforced magnesium matrix (C_f/Mg) composites, a double-layer interface (ZrO₂–MgO) is designed in this work. Carbon fiber was modified with ZrO₂ coating by sol-gel process. Microstructural examination reveals that MgO layer forms on the surface of ZrO₂ coating by ZrO₂ reacting with Mg during the composite fabrication. Such double-layer interface could inhibit Al₄C₃ and hence prevent fiber damage. Meanwhile, the wettability was improved for the reaction between ZrO₂ and Mg. Thus the tensile strength of ZrO₂-C_f/AZ91D composite was 68.0% higher than that of the unmodified one. Due to the fiber bundle pull-out, debonding and crack deflection, the toughness of C_f/Mg composite with double-layer interface is increased simultaneously.     

Tailoring Carbon Fiber/Carbon Nanotubes Interface to Optimize Mechanical Properties of Cf‐CNTs/SiC Composites

C_f/SiC composites were fabricated using fiber coatings including CNTs and matrix infiltration using the polymer impregnation and pyrolysis process. Interface between fiber and CNTs (CF/CNTs) was tailored to optimize mechanical properties of hybrid composites. The tailored interphases, such as Pyrocarbon (PyC) and PyC/SiC, protect fibers from degradation during the growth of CNTs successfully. Hybrid composites with well‐tailored CF/CNTs interface displayed significantly increased mechanical strength (352 ± 21 MPa) compared with that (34 ± 3 MPa) of composites reinforced with CNTs, which grown on carbon fibers directly. The interfacial bonding strength of hybrid composites was improved and optimized by tailoring the CF/CNTs interface. Interfacial failure modes were studied, and a firm interface bonding at the joint where CNTs grown was observed.     

Microstructure and mechanical properties of quasi-isotropic chopped fiber-reinforced PyC–SiC matrix composite prepared by novel nondamaging method

In this work, quasi-isotropic chopped carbon fiber-reinforced pyrolytic carbon and silicon carbide matrix (C_f/C–SiC) composites and chopped silicon carbide fiber-reinforced silicon carbide matrix (SiC_f/SiC) composites were prepared via novel nondamaging method, namely airlaid process combined with chemical vapor infiltration. Both composites exhibit random fiber distribution and homogeneous pore size. Young's modulus of highly textured pyrolytic carbon (PyC) matrix is 23.01 ± 1.43 GPa, and that of SiC matrix composed of columnar crystals is 305.8 ± 9.49 GPa in C_f/C–SiC composites. Tensile strength and interlaminar shear strength of C_f/C–SiC composites are 52.56 ± 4.81 and 98.16 ± 24.62 MPa, respectively, which are both higher than those of SiC_f/SiC composites because of appropriate interfacial shear strength and introduction of low-modulus and highly textured PyC matrix. Excellent mechanical properties of C_f/C–SiC composites, particularly regarding interlaminar shear strength, are due to their quasi-isotropic structure, interfacial debonding, interfacial sliding, and crack deflection. In addition to the occurrence of crack deflection at the fiber/matrix interface, crack deflection in C_f/C–SiC composites takes also place at the interface between PyC–SiC composite matrix and the interlamination of multilayered PyC matrix. Outstanding mechanical properties of as-prepared C_f/C–SiC composites render them potential candidates for application as thermal structure materials under complex stress conditions.     

Direct measurement of grafting strength between an individual carbon nanotube and a carbon fiber

Hierarchical structures consisting of carbon nanotubes (CNTs) grafted onto a carbon fiber (CF) have the potential to improve the performance of fiber/polymer composites. The strength between a CNT and a CF is a key factor that influences the load-transfer behavior and inter-laminar properties. Here, we directly measured the grafting strength of a chemically bonded CNT–CF hierarchical structure by detaching individual CNT from the CF substrate and simultaneously recording the force–displacement characteristics in a scanning electron microscopy equipped with a nano-manipulator. We observed a relatively wide distribution of the maximum forces at complete detachment for different grafted CNTs, which ranges from below the van der Waals (vdW) force existing at the CNT–CF interface up to 7 times higher than that. For a typical configuration where a CNT is partially anchored on a CF, we obtained grafting strengths in the range of 5–90 MPa, which are dominated by the vdW force as well as other factors such as chemical bonding. Our results, based on the measurements at individual nanostructure level, might be useful for designing and fabrication of high performance hierarchical composites.     

Silane coupling agent modification on interlaminar shear strength of carbon fiber/epoxy/nano‐CaCo3 composites

Four different types of composites were prepared based on unmodified and modified epoxy matrices: (A) unmodified epoxy/carbon fiber composites, (B) modified epoxy/carbon fiber composites by silane coupling agent/nano‐CaCO₃ master batch, (C) modified epoxy/carbon fiber composites by nano‐CaCO₃ particles directly, and (D) modified epoxy/carbon fiber composites by nano‐CaCO₃ particles and silane coupling agent together. The interlaminar shear strength (ILSS) of the carbon fiber‐reinforced composites was investigated. The results show that the silane coupling agent/nano‐CaCO₃ master batch can increase the ILSS to the highest degree. Nevertheless, Sample D, i.e., modified by nano‐CaCO₃ particles and silane coupling agent together, even presents a decrease of the ILSS. The integration effect of silane coupling agent/nano‐CaCO₃ master batch was concluded. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Improved tensile strength of carbon fibers undergoing catalytic growth of carbon nanotubes on their surface

We demonstrate that the tensile strength of carbon fibers (CFs) can be increased by more than 14% by the catalytic growth of carbon nanotubes (CNTs) onto their surface. Repair to some of the damage incurred during the formation of catalyst nanoparticles, an increase in the carbon crystal size, and the formation of crosslinks of neighboring crystals by CNTs all occur during the chemical vapor deposition process, and are the main reasons for the improvement. The interfacial shear strength of the CFs is also shown to be significantly improved due to the CNTs grown on the CF surface.     

Microstructure and mechanical properties of continuous carbon fiber-reinforced ZrB2-based composites via combined electrophoretic deposition and sintering

A process combining electrophoretic deposition (EPD) with hot pressing (HP) was developed to fabricate continuous carbon fiber-reinforced ZrB₂-based composites (C_f/ZrB₂-based composites). ZrB₂-based ultra-high temperature ceramic (UHTC) particles were uniformly pre-coated on continuous carbon fibers via EPD. Then, the UHTC-coated carbon fibers were stacked and hot pressed to prepare the C_f/ZrB₂-based composites. Microstructure observations revealed that almost no micro-pores were found in the inter-bundle and intra-bundle regions of fibers after HP. The flexural strength, fracture toughness and the work of fracture of the C_f/ZrB₂-based composite were measured as 199 ± 26 MPa, 6.71 ± 1.29 MPa·m^1/2, and 754 ± 58 J/m², respectively. Based on the observations of non-brittle fracture behavior, fractured morphology and crack propagation, the enhanced fracture properties were mainly attributed to the multiple toughening mechanisms, such as fiber pull-out, fiber bridging, crack deflection and branching along the interfaces.     

Catalyst optimization and reduction condition of continuous growth of carbon nanotubes on carbon fiber surface

Carbon nanotubes (CNTs)/carbon fiber (CF) reinforcements were synthesized under different catalyst compositions and reduction conditions. The effects of the catalyst, reduction temperature and reduction time on the surface morphology, graphitization, and single filament tensile strength of the prepared CNTs/CF samples were investigated. When nickel was used as the catalyst and copper as the catalyst promoter, with the increase of copper concentration, the catalytic activity increased. Thus, the carbon source was consumed more completely, improving the abundance of CNTs with good graphitization. And the effect of repairing CF defects was more obvious, hence the single filament tensile strength accordingly increased. Besides, the increase of catalyst reduction temperature and reduction time intensified the etching of CF by catalyst, and decreased the single filament tensile strength of CF. With the deposition of CNTs, the tensile strength of CF was enhanced in varying degrees. When the concentration of cooper was 0.01 mol/L with the reduction time of 10 min and reduction temperature of 450 °C, CNTs/CF had the highest tensile strength, which can reach up to 4.51 GPa. We determined that bimetallic catalysts could adjust the catalytic activity of nickel. The change of reduction time and temperature would affect the quality of CNTs, which was helpful to obtain high quality CNTs on CF surface and improve the mechanical properties of CNTs/CF and its composites.     

Mechanical properties of carbon nanotube/carbon fiber reinforced thermoplastic polymer composite

Carbon nanotube (CNT)/carbon fiber (CF) hybrid fiber was fabricated by sizing unsized CF tow with a sizing agent containing CNT. The hybrid fiber was used to reinforce a thermoplastic polymer to prepare multiscale composite. The mechanical properties of the multiscale composite were characterized. Compared with the base composite (traditional commercial CF), the multiscale composite reinforced by the CNT/CF hybrid fiber shows increases in interlaminar shear strength (ILSS) and impact toughness. Laminate containing CNTs showed a 115.4% increase in ILSS and 27.0% increase in impact toughness. The reinforcing mechanism was also discussed by observing the impact fracture morphology. POLYM. COMPOS., 38:2001–2008, 2017. © 2015 Society of Plastics Engineers     

Preparation of emulsion‐type thermotolerant sizing agent for carbon fiber and the interfacial properties of carbon fiber/epoxy resin composite

A modified resin was synthesized through the reaction between dodecylamine and tetraglycidyldiaminodiphenylmethane (TGDDM), which was used as the film former of sizing agent for carbon fiber (CF). The sizing agents were prepared through phase inversion emulsification method. Fourier transform infrared spectroscopy (FTIR) was utilized to analyze the modified resin. Particle sizes of the sizing agents were tested to evaluate their stabilities. Differential scanning calorimetry (DSC) results demonstrated that the glass transition temperature (T_g) of the modified TGDDM is much higher than the T_g of the cured epoxy resin E‐44. The influences of the sizing treatment on CF were investigated by abrasion resistance, fluffs, and stiffness tests. The maximum abrasion resistance increased by 172.8%, compared with the abrasion resistance of the desized CF. Interlaminar shear strength (ILSS) results of the CF/TGDDM composites indicated that the interfacial adhesion between CF and matrix resin was greatly improved after CF was sized. The maximum ILSS value could obtain a 29.16% improvement, compared with the ILSS of the desized CF composite. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41882.     

Direct ink writing of chopped carbon fibers reinforced polymer-derived SiC composites with low shrinkage and high strength

The chopped carbon fiber reinforced SiC (C_f/SiC) composite has been regarded as one of the excellent high-temperature structural materials for applications in aerospace and military fields. This paper presented a novel printing strategy using direct ink writing (DIW) of chopped fibers reinforced polymer-derived ceramics (PDCs) with polymer infiltration and pyrolysis (PIP) process for the fabrication of C_f/SiC composites with high strength and low shrinkage. Five types of PDCs printing inks with different C_f contents were prepared, their rheological properties and alignment of carbon fiber in the printing filament were studied. The 3D scaffold structures and bending test samples of C_f/SiC composites were fabricated with different C_f contents. The results found that the C_f/SiC composite with 30 wt% C_f content has high bending strength (～ 7.09 MPa) and negligible linear shrinkage (～ 0.48%). After the PIP process, the defects on the C_f/SiC composite structures were sufficiently filled, and the bending strength of C_f/SiC composite can reach up to about 100 MPa, which was about 30 times greater than that of the pure SiC matrix without C_f. This work demonstrated that the printed C_f/SiC composites by using this method is beneficial to the development of the precision and complex high-temperature structural members.     

Design of a vane mixer with controlled extensional/shear strength ratio and its application for carbon fiber/polyamide 6 composites

In this work, a novel melt mixing method and its corresponding mixing device are developed. The extensional/shear strength ratio of the device can be controlled by adjusting its eccentricity. The structure and working principle of the device are introduced in detail. Carbon fiber (CF)/polyamide 6 (PA6) composites are prepared via this novel mixing device. The influences of eccentricity and mixing time on the morphology, CF length, thermal, mechanical, and electrical properties of CF/PA6 composites are studied. Scanning electron microscopy results show that CFs uniformly disperse in the matrix and interfacial adhesion between CFs and PA6 is improved. It is observed that CF length and its distributions can be optimized by changing eccentricity. The maximum average fiber length is about 351 μm. Differential scanning calorimetry results exhibit that the X_c increases 6.5% when eccentricity is 2 mm. Mechanical test results show tensile strength and modulus increase first and then decrease with the increasing eccentricities or mixing time. Electrical property measurement shows an obvious increase when eccentricity is 2 mm due to good fiber dispersion and long fiber retention length. The experimental results indicate that the novel mixing method and its corresponding apparatus provide an environment-friendly and effective way to prepare polymer-based composites.     

Grafting straight carbon nanotubes radially onto carbon fibers and their effect on the mechanical properties of carbon/carbon composites

Straight carbon nanotubes (CNTs) were grafted radially onto carbon fibers to produce hybrid materials that were used to reinforce carbon/carbon (C/C) composites. Mechanical property tests indicated that these C/C composites have improvements in out-of-plane and in-plane compressive strengths and interlaminar shear strength of 275%, 138% and 206%, respectively. They also have a large decrease in the anisotropy of mechanical properties, compared with pure C/C composites. This great improvement is the result of the simultaneous reinforcements to the fiber/matrix interface and the matrix provided by the grafted CNTs.     

Influence of oxygen plasma treatment parameters on the properties of carbon fiber

This study is focused on the impact of oxygen plasma treatment on properties of carbon fibers and interfacial adhesion behavior between the carbon fibers and epoxy resin. The influences of the main parameters of plasma treatment process, including duration, power, and flow rate of oxygen gas were studied in detail using interlaminar shear strength (ILSS) of carbon fiber composites. The ILSS of composites made of carbon fibers treated by oxygen plasma for 1 min, at power of 125 W, and oxygen flow rate of 100 sccm presented a maximum increase of 28% compared to composites made of untreated carbon fibers. Furthermore, carbon fibers were characterized by scanning electron microscopy (SEM), tensile strength test, attenuated total reflectance Fourier transform infrared (ATR-FTIR), and Raman spectroscopy analyses. It was found that the concentration of reactive functional groups on the fiber surface was increased after the plasma modification, as well the surface roughness, which finally improved the interfacial adhesion between carbon fibers and epoxy resin. However, high power and long exposure times could partly damage the surface of carbon fibers and decrease the tensile strength of filaments and ILSS of treated fiber composites.