Interfacial microstructure and properties of carbon fiber-reinforced unsaturated polyester composites modified with carbon nanotubes

To improve the interfacial properties in carbon fiber (CF)-reinforced unsaturated polyester (UP) composites, we directly introduced functionalized carbon nanotubes dispersed in the fiber sizing onto the fiber surface. For comparing the influence of polymer type on sizing effect, two different polymers (UP MR13006 and water-soluble epoxy (EP)) were used to prepare sizing agent. Morphology and surface energy of CFs were examined by scanning electron microscopy and dynamic contact angle analysis test. Tensile strength was investigated in accordance with ASTM standards. Mechanical properties of the composites were investigated by interlaminar shear strength (ILSS) and impact toughness. Test results indicate that TS, ILSS, and impact toughness were enhanced simultaneously. For UP matrix, the sizing agent containing UP has better reinforcing and toughening effect than the sizing agent containing water-soluble EP.     

Effect of various methods of pre-treatment of carbon fibers on the mechanical properties of PIP-based ceramics/carbon composites

The purpose of the work was to determine the conditions of CF preparation to obtain carbide composites with favorable mechanical response. The relationships between the interfacial properties of fiber/polymethylsiloxane composite, and mechanical properties of the resulting fiber/carbide composites were investigated. The CF/resin interfacial strength was modified by oxidation of CF surface with nitric acid, silanization, and depositing CNT or a pyrolytic carbon layer (PyC). The study of composite interphases (ILSS and SEM) and surface tests of the modified CF (XPS, FT-IR, wettability measurements) showed different nature of the bonding occurring at the fiber/resin and fiber/ceramics boundary. The CF silanization significantly improved the ILSS between CFs and resin by 38.5%, while reduced flexural properties of carbide composites. The most promising treatment method of CF for PIP-based ceramic composites was modification with PyC, which provided 2 times higher ILSS, 1.5 times higher flexural strength and improved work to fracture (WF) as compared to unmodified CF.     

Interfacial improvement of carbon fiber-reinforced methylphenylsilicone resin composites with sizing agent containing functionalized carbon nanotubes

A liquid sizing agent containing multiwall carbon nanotubes (MWCNTs) was prepared for carbon fiber (CF) reinforced methylphenylsilicone resin (MPSR) composite applications. In order to improve the dispersion of MWCNTs in the sizing agent and interfacial adhesion between CF and MPSR, MWCNTs and CF were functioned by the chemical modification with tetraethylenepentamine (TEPA) used as a MPSR curing agents. The CF before and after the sizing treatment-reinforced MPSR composites were prepared by a compression molding method. The microstructures, interfacial properties, and impact toughness of CF were systematically investigated. Experimental results revealed that a thin layer of MPSR coating containing functionalized MWCNTs (MWCNT-TEPA) was uniformly grafted onto the surface of CF. The sized CF-reinforced MPSR composite showed simultaneously remarkable enhancement in the interlaminar shear strength and impact toughness. Meanwhile, the tensile strength of CF had no obvious decrease after sizing treatment. In addition, the interfacial reinforcing and toughening mechanisms were also discussed. We believe that the facile and effective method in preparing multifunctional fibers provides a novel interface design strategy of carbon fiber composites for different applications.     

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.     

Improved fracture toughness of carbon fiber composite functionalized with multi walled carbon nanotubes

Woven carbon fiber (CF) laminae are functionalized in situ with carbon nanotubes (CNTs) to test the hypothesis that growing CNTs on CF (i.e., carbon fiber bundles or tow) would enhance the properties of polymeric carbon composites, specifically epoxy–carbon composites that are used in aerospace applications. The CNT as-grown on the woven CF were shown to substantially improve the fracture toughness of the cured composite on the order of 50%. This was accompanied by no loss in structural stiffness of the final composite structure. In fact, the flexural modulus increased approximately 5%. The significant increase in the fracture toughness as tested under the ASTM D 5528 standard indicates that the damage tolerance of a composite structure would benefit from the CNT material applied in this way. Our approach has allowed for significantly larger samples to be uniformly functionalized with CNTs than is reported elsewhere in the open literature. In addition, this work demonstrated CNT functionalization on flexible substrates that remains flexible after functionalization, whereas most CNT growth substrates are rigid in order to withstand the high (>800 °C) growth temperatures often encountered in CNT synthesis.     

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.     

Preparation and properties of water‐soluble‐type sizing agents for carbon fibers

A water‐soluble epoxy resin was synthesized by the reaction between novolac epoxy resin (F‐51) and diethanolamine. Then, the modified F‐51 was mixed with poly(alkylene glycol allyl glycidyl ether) as a film former of a sizing agent. A series of water‐soluble sizing agents for carbon fiber (CF) were prepared. The modified F‐51 was analyzed by Fourier Transform infrared spectroscopy. The surface morphology of the CF was characterized by scanning electron microscopy. The effects of the sizing agent on the handling characteristics were investigated by abrasion resistance, fluffs, and breakage and stiffness tests. The results show that the abrasion resistance of the sized CF increased by 114.5% and reached 2344 times and the mass of fabric hairiness decreased to 3.2 mg. The interlaminar shear strength (ILSS) test indicated that the interfacial adhesion of the composite could be greatly improved. The ILSS of the sized CF composite could reach a maximum value of 42.40 MPa. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39843.     

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.     

Microstructure and properties of carbon fiber sized with pickering emulsion based on graphene oxide sheets and its composite with epoxy resin

The Graphene oxide (GO) sheets were used for preparing the epoxy resin Pickering emulsion. The particle size and the zeta potential of the Pickering emulsion were measured to evaluate its stability. The stable emulsion could be served as the film former of sizing agent for carbon fiber (CF). The effect of the Pickering emulsion stabilized by GO sheets on the properties of CF and the interfacial adhesion property of CF reinforced composite were investigated. Scanning electron microscopy (SEM) images showed that there existed a layer of sizing agent film with GO sheets evenly on the CF surface. Abrasion resistance and stiffness values of CF were tested and the results indicated that the sized CF conformed to the requirement of CF handleability. The interlaminar shear strength (ILSS) test indicated that the interfacial adhesion of the composite could be greatly improved. The fracture surfaces of CF composites were examined by SEM after ILSS tests. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42285.     

Enhanced interfacial adhesion in carbon fiber/poly (acrylonitrile‐butadiene‐styrene) composite through fiber surface treatment by an emulsion sizing

To improve the interfacial adhesion between carbon fiber (CF) and poly(acrylonitrile‐butadiene‐styrene) (ABS) thermoplastic, an emulsion sizing whose film former was a terpolymer N‐phenylmaleimide‐styrene‐maleic anhydride (NSM)/ABS mixture was prepared. NSM, an efficient heat‐resistant modifier for ABS, could make the film former possess a superior heat resistance, which helped the sizing layer maintain integrity during the preparation of CF/ABS composite. Moreover, differential scanning calorimetry (DSC) results demonstrated that the glass transition temperature (T_g) of the NSM modified ABS achieved an improvement of 25.3°C. Particle size and distribution of the sizing agent were investigated to evaluate its stability. The FTIR spectrum obtained demonstrated that the chemical compositions of the sized CF got greatly changed and numerous functional groups appeared on sized CF. Abrasion resistance and fluffs of CF were tested and the results indicated that the sized CF obtained an appreciable enhancement in handleability. Interlaminar shear strength (ILSS) results revealed, after sizing, that the ILSS enhanced by 26.6%, due to the inserted sizing layer between CF and ABS matrix. POLYM. COMPOS., 37:2940–2949, 2016. © 2015 Society of Plastics Engineers     

Experimental evaluation of the interfacial properties of carbon nanotube coated carbon fiber reinforced hybrid composites

A floating catalyst chemical vapor deposition (CVD) unit was utilized to grow CNT onto the surface of carbon fiber (CF). The surface morphology of the resultant fibers, CNT population density and alignment pattern were found to be depended on the CNT growth temperature, growth time, and atmospheric conditions within the CVD chamber. In contrast to the neat‐CF reinforced composites, improved interfacial shear strength (IFSS) between CF and matrix were obtained when the surface of CF was coated by CNT. Particularly, CF treatment condition for CNT‐coating with 700°C reaction temperature and 30 min reaction time has shown a considerable increase in IFSS approximately of 45% over that of the untreated fiber from which it was processed. The proper justification of fiber–matrix adhesion featured by composite interfacial properties was explained through IFSS. POLYM. COMPOS., 36:1941–1950, 2015. © 2014 Society of Plastics Engineers     

Effects of carbon fiber modification with multiwall CNT on the electrical conductivity and EMI shielding effectiveness of polycarbonate/carbon fiber/CNT composites

The effect of carbon fiber (CF) modification with multiwall carbon nanotube (CNT) on the electrical, mechanical, and rheological properties of the polycarbonate (PC)/CF/CNT composite was investigated. The CF and multiwall CNT (MWCNT) were treated with sulfuric acid and nitric acid (3:1 wt %) mixture, to modify the CF with the CNT. For the PC with acid-treated CNT (a-CNT) modified acid-treated CF (a-CF) (PC/a-CF/a-CNT) composite, the electrical conductivity, and the electromagnetic interference shielding effectiveness (EMI SE) showed the highest values, compared with those of the PC/a-CF and PC/a-CF/CNT composites. The EMI SE of the PC/a-CF (10 wt %)/a-CNT (0.5 wt %) composite was found to be 26 (dB at the frequency of 10.0 GHz, and the EMI SE was increased by 91.2%, compared to that of the PC/a-CF composite at the same amount of total filler content. Among the composites studied in this work, the PC/a-CF/a-CNT composite also showed the highest values of relative permittivity (ε_r) and dielectric loss factor. The above results suggest that the CF modification with the a-CNT significantly affected the electrical conductivity and EMI SE of the composite, and the hybrid fillers of the a-CNT and a-CF resulted in good electrical pathways in the PC/a-CF/a-CNT composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47302.     

Comparative study of EMI shielding effectiveness for carbon fiber pultruded polypropylene/poly(lactic acid)/multiwall CNT composites prepared by injection molding versus screw extrusion

The electrical conductivity and electromagnetic interference (EMI) shielding effectiveness of the composites of polypropylene/poly(lactic acid) (PP/PLA) (70/30, wt %) with single filler of multiwall carbon nanotube (CNT) or hybrid fillers of nickel‐coated carbon fiber (CF) and CNT were investigated. For the single filler composite, higher electrical conductivity was observed when the PP‐g‐maleic anhydride was added as a compatibilizer between the PP and PLA. For the composite of the PP/PLA (70/30)/CF (20 phr)/CNT (5 phr), the composite prepared by injection molding observed a higher EMI shielding effectiveness of 50.5 dB than the composite prepared by screw extrusion (32.3 dB), demonstrating an EMI shielding effectiveness increase of 49.8%. The higher values in EMI shielding effectiveness and electrical conductivity of the PP/PLA/CF (20 phr)/CNT (5 phr) composite seemed mainly because of the increased CF length when the composites were prepared using injection molding machine, compared with the composites prepared by screw extrusion. This result suggests that the fiber length of the conductive filler is an important factor in obtaining higher values of electrical conductivity and EMI shielding effectiveness of the PP/PLA/CF/CNT composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45222.     

The influence of addition of carbon nanotube and graphene platelets on characteristics of carbon/basalt fiber reinforced intra-ply hybrid composites

In this study, effects of addition of carbon nanotubes (CNTs) and graphene platelets (GPLs) on characteristics of carbon/basalt fiber reinforced intra-ply hybrid composites were investigated. The composites were fabricated using vacuum assisted resin infusion molding (VARIM) method in two types including bare and 0.1, 0.5 wt.% of GPL and CNT nanoparticles filled hybrid composites. Fabricated normal and multiscale composites were cut by water jet and mechanical properties of specimens were examined by tensile, flexural, SBS experiments. Therefore, the modulus of elasticity, flexural modulus, tensile and flexural strength and ILSS of bare and multiscale composites were compared. Thermomechanical properties of fabricated composites were evaluated by dynamic mechanic analyze (DMA), thermogravimetric analyze ( TGA) and thermal conductivity (TC) tests and storage modulus, loss modulus, damping ratio, glass transition temperature, weight loss and derivative weight loss were compared in fabricated normal and multiscale composites. Similarly, modal properties of fabricated composites such as natural frequency and damping factor were obtained by vibrational tests and compared in fabricated composites. According to the results, the addition of carbon-based nanoparticles improved the characteristics of carbon/basalt fiber intra-ply hybrid composites. The response of composites was directly proportional to the addition ratio of the carbon-based nanoparticles.     

碳纳米管在炭纤维表面的可控自组装

采用催化化学气相沉积法将碳纳米管(CNTs)原位生长于炭纤维(CF)表面并自组装成不同形貌的CNTs/CF杂化结构。使用扫描电子显微镜、拉曼光谱仪对制备的纳米/微米杂化结构进行微观形貌分析和结构表征。结果显示,随着温度的升高,碳纳米管在炭纤维表面由均匀分布状态转变为取向生长状态,并且长度及石墨化程度均不断增加。结合碳纳米管结构参数的变化,使用纳米悬臂梁模型解释了这一杂化结构的形成机理。模型分析表明,杂化结构的形貌转变是由不同温度下在炭纤维表面生长的碳纳米管的结构参数不同所造成的,因此可以通过调整相关结构参数控制碳纳米管在炭纤维表面的自组装过程。     

The role of grafting force and surface wettability in interfacial enhancement of carbon nanotube/carbon fiber hierarchical composites

The grafting force of carbon nanotube (CNT) on carbon fiber (CF) and the wettability of CF surface were experimentally studied, where hierarchical CNT/CF reinforcement was prepared using chemical vapor deposition (CVD). Then, their effects on interfacial improvement were experimentally and theoretically investigated. The results show that the CNT/CF grafting force is so strong, more than 5 μN, and CNT/CF attachment can sustain the fracture of the CNTs. This is expected to be contributed to the improvement of interfacial properties. However, the deposited catalyst deteriorates the wettability, which could seriously degrade the interfacial properties. As a result, experimental results from the micro-droplet test show that there is only a 30% increase in the interfacial shear strength of hierarchical CNT/CF reinforced composite comparing with that of as-received CF reinforced composite. An analytical model was developed to predict the effects of CNT/CF grafting force on interfacial improvement, and the predicted results are in agreement with the experimental one.     

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     

Improved tensile properties of carbon nanotube modified epoxy and its continuous carbon fiber reinforced composites

Carbon nanotubes (CNTs) were used to improve the tensile properties of an epoxy resin and its continuous carbon fiber (CF) reinforced composites. Micrography picture showed that CNTs has been well incorporated into the composites, and made the fracture cross section more rougher through sharing the stress. For the CNT/epoxy composite, the tensile strength and modulus both increased upon the CNT addition, and at a CNT volume concentration of 2.0%, the maximum enhancements in the tensile strength and modulus were achieved as 26.7% and 21.5%, respectively. For the CNT‐CF/epoxy composite, the maximum enhancement in tensile strength was achieved as 11.6% at a CNT volume concentration of 1.0% and then decreased with the further increase of the CNT addition, but the tensile modulus increased monotonically upon the CNT addition. POLYM. COMPOS., 36:1664–1668, 2015. © 2014 Society of Plastics Engineers     

Effects of novolac resin modification on mechanical properties of carbon fiber/epoxy composites

The epoxy resin matrix of carbon fiber (CF)‐reinforced epoxy composites was modified with novolac resin (NR) to improve the matrix‐dominated mechanical properties of composites. Flexural strength, interlaminar shear strength (ILSS), and impact strength were measured with unfilled, 7 wt% NR, 13 wt% NR, and 18 wt% NR filled to epoxy to identify the effect of adding NR on the mechanical properties of composites. The results showed that both interfacial and impact properties of composites were improved except for flexural property. The largest improvement in ILSS and impact strength were obtained with 13 wt% loading of NR. ILSS and impact strength were improved by 7.3% and 38.6%, respectively, compared with the composite without NR. The fracture and surface morphologies of the composite specimens were characterized by scanning electron microscopy. Intimate bonding of the fibers and the matrix was evident with the content of 7–13 wt% NR range. Decrease of crosslinking density and formation of NR transition layer were deduced with adding NR. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Improving delamination resistance of carbon fiber reinforced polymeric composite by interface engineering using carbonaceous nanofillers through electrophoretic deposition: An assessment at different in-service temperatures

In this article, modification of carbon fiber surface by carbon based nanofillers (multi-walled carbon nanotubes [CNT], carbon nanofibers, and multi-layered graphene) has been achieved by electrophoretic deposition technique to improve its interfacial bonding with epoxy matrix, with a target to improve the mechanical performance of carbon fiber reinforced polymer composites. Flexural and short beam shear properties of the composites were studied at extreme temperature conditions; in-situ cryo, room and elevated temperature (−196, 30, and 120°C respectively). Laminate reinforced with CNT grafted carbon fibers exhibited highest delamination resistance with maximum improvement in flexural strength as well as in inter-laminar shear strength (ILSS) among all the carbon fiber reinforced epoxy (CE) composites at all in-situ temperatures. CNT modified CE composite showed increment of 9% in flexural strength and 17.43% in ILSS when compared to that of unmodified CE composite at room temperature (30°C). Thermomechanical properties were investigated using dynamic mechanical analysis. Fractography was also carried out to study different modes of failure of the composites.