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 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.     

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.     

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.     

Effects of sizing materials on the properties of carbon fiber‐reinforced polyamide 6,6 composites

This article aims to study the effect of the sizing materials type on the mechanical, thermal, and morphological properties of carbon fiber (CF)‐reinforced polyamide 6,6 (PA 6,6) composites. For this purpose, unsized CF and sized CFs were used. Thermogravimetric analysis was performed, and it has been found that certain amounts of polyurethane (PU) and PA sizing agents decompose during processing. The effects of sizing agent type on the mechanical and thermomechanical properties of all the composites were investigated using tensile, Izod impact strength test, and dynamic mechanical analysis. Tensile strength values of sized CF‐reinforced composites were higher than that of unsized CF‐reinforced composites. PA and polyurethane sized CF‐reinforced composites exhibited the highest impact strength values among the other sized CF‐reinforced composites. PU and PA sized CF‐reinforced composites denoted higher storage modulus and better interfacial adhesion values among the other sizing materials. Scanning electron microscope studies indicated that CFs which were sized with PU and PA have better interfacial bonding with PA 6,6 matrix among the sized CFs. All the results confirmed that PA and PU were suitable for CF's sizing materials to be used for PA 6,6 matrix. POLYM. COMPOS., 34:1583–1590, 2013. © 2013 Society of Plastics Engineers     

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.     

Improving the interfacial properties of carbon fiber–epoxy resin composites with a graphene-modified sizing agent

We successfully prepared a graphene-modified carbon fiber (CF) sizing agent with good dispersity and stability by dispersing reduced graphene oxide (RGO) into an emulsion-type sizing agent. RGO was obtained by the reduction of graphene oxide (GO) with the help of gallic acid. The influence of the graphene-modified sizing agent on the interfacial properties of the CF–epoxy resin composites was investigated with microbond testing and the three-point bending method. The results show that optimized interfacial properties were achieved when the size of the modified graphene was less than 1 μm, the content of RGO was 20 ppm, and the pH value of the sizing agent was 10.5. The interfacial shear strength of the composites reached 92.3 MPa, which was 29.6% higher than that of the composites with unmodified CFs. Compared with commercial-CF-fabric-reinforced composites, the interlaminar shear strength of the composites treated with the RGO-modified sizing agent increased by 21.5%. Both the interfacial and interlaminar failure morphologies of the composites were examined with scanning electron microscopy (SEM). The results show that a large amount of residual resin adhered to the surfaces of the CFs treated with the RGO-modified sizing agent; this indicated good interfacial properties between the CFs and the resin matrix. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47122.     

Effects of surface treatment of carbon fiber: Tensile property,surface characteristics,and bonding to epoxy

In this article, effects of electrochemical oxidation and sizing treatment of PAN‐based carbon fibers (CFs) on the tensile properties, surface characteristics, and bonding to epoxy were investigated. As found, the electrochemical oxidation improves the tensile strength of single CF by 16.0%, due to weakening the surface stress concentration and smoothing the surface structure. Further sizing treatment shows a negligible effect on the tensile strength. Both oxidation and sizing treatments significantly improve the wettability and surface energies of CFs by introducing oxygen‐containing functional groups. Microbond test was conducted to characterize the interfacial shear strength (IFSS) between a single fiber and an epoxy droplet. The oxidation treatment increases IFSS slightly, which is due to the contradictory effects of the formation of chemical bonds between the resin and CFs, and the reduced mechanical interlocking. Further sizing treatment significantly enhances IFSS from 73.6 to 81.0 MPa, due to the formation of vast chemical bonds. Furthermore, the oxidation and sizing treatment can effectively reduce the degradation of IFSS to the hygrothermal ageing for the CF/epoxy system. POLYM. COMPOS., 37:2921–2932, 2016. © 2015 Society of Plastics Engineers     

Improving the interfacial and flexural properties of carbon fiber–epoxy composites via the grafting of a hyperbranched aromatic polyamide onto a carbon fiber surface on the basis of solution polymerization

Hyperbranched aromatic polyamide (HBP) was grafted successfully onto carbon fibers (CFs) on the basis of solution polymerization to enhance the interfacial adhesion strength of CF-reinforced epoxy resin composites. The microstructure and interfacial properties of the CFs before and after decoration were researched. The results indicate that HBP was deposited uniformly onto the CFs with γ-aminopropyl triethoxysilane as the bridging agent. The active groups, roughness, and surface energy of the modified fiber [hyperbranched aromatic polyamide grafted carbon fiber (CF–HBP)] increased visibly in comparison with those of the untreated CFs. The CF–HBP composites revealed simultaneous remarkable enhancements (65.3, 34.3, and 84.8%) in their interfacial shear strength, flexural strength, and modulus, respectively; this was attributed to the improvement in the fiber–epoxy interface through enhanced chemical interactions, mechanical interlocking, and wettability. These agreed with the scanning electron microscopy observations from the fracture surface morphologies of the composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47232.     

Effect of polyurethane sizing on carbon fibers surface and interfacial adhesion of fiber/polyamide 6 composites

Commercial epoxy sized carbon fibers (CFs) or unsized CFs have poor interfacial adhesion with polyamide 6 (PA6). Here, CFs are coated with polyurethane (PU) and their surface properties in terms of surface chemistry, contact angle, roughness, and morphology, are investigated. The results of Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy demonstrate PU sizing evidently increases the quantity of polar functional groups on the CFs surface. The surface energy of the PU sized fiber is calculated according to the Owens–Wendt method. Compared with unsized fibers, the contact angle of PU sized fibers is decreased while their total surface energy is increased, indicating superior wettability. Moreover, transverse fiber bundle tests are performed to determine the interfacial adhesion between the CFs and PA6 matrix. The transverse fiber bundle strength of unsized CF is measured to be 12.57 MPa. For PU sized CFs processed with sizing concentration of 1.2%, this value is increased to 24.35 MPa, showing an increase of more than 90%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46111.     

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.     

Interfacial shear strength in carbon fiber‐reinforced poly(phthalazinone ether ketone) composites

We studied interfacial shear strength (IFSS) in carbon fiber (CF)‐reinforced poly (phthalazinone ether ketone) (PPEK) composites system, with emphasis on the influence of forming temperature of composite and sizing agent on CFs. To obtain apparent IFSS of CF‐reinforced PPEK composites shaped at various forming temperatures ranged from 20 up to 370°C, microbond test was carried out at single‐fiber composites. Results of microbond test showed that apparent IFSS was directly proportional to the difference between the matrix solidification temperature (forming temperature) and the test temperature and approximately 80% of the apparent IFSS in CF/PPEK composite system was attributed to residual radial compressive stress at the fiber/matrix interface. By sizing CF with sizing agent, the wettability of the fiber by the matrix was improved and the final apparent IFSS was also improved. POLYM. COMPOS., 34:1921–1926, 2013. © 2013 Society of Plastics Engineers     

Effects of polyhedral oligomeric silsesquioxane coatings on the interface and impact properties of carbon‐fiber/polyarylacetylene composites

Two kinds of polyhedral oligomeric silsesquioxane (POSS) coatings were used for the modification of the interface in carbon fiber (CF) reinforced polyarylacetylene (PAA) matrix composites. The effects of the organic–inorganic hybrid POSS coatings on the properties of the composites were studied with short‐beam‐bending, microdebonding, and impact tests. The interlaminar shear strength and interfacial shear strength showed that the POSS coatings resulted in an interfacial property improvement for the CF/PAA composites in comparison with the untreated ones. The impact‐test results implied that the impact properties of the POSS‐coating‐treated composites were improved. The stiffness of the interface created by the POSS coatings was larger than that of the fiber and matrix in the CF/PAA composites according to the force‐modulation‐mode atomic force microscopy test results. The rigid POSS interlayer in the composites enhanced the interfacial mechanical properties with a simultaneous improvement of the impact properties; this was an interesting phenomenon in the composite‐interface modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5202–5211, 2006     

Mechanical properties of carbon fiber composites modified with nano-SiO2 in the interphase

The performance of carbon fibers-reinforced composites is dependent to a great extent on the properties of fiber–matrix interface. To improve the interfacial properties in carbon fibers/epoxy composites, nano-SiO₂ particles were introduced to the surface of carbon fibers by sizing treatment. Atomic force microscope (AFM) results showed that nano-SiO₂ particles had been introduced on the surface of carbon fibers and increase the surface roughness of carbon fibers. X-ray photoelectron spectroscopy (XPS) showed that nano-SiO₂ particles increased the content of oxygen-containing groups on carbon fibers surface. Single fiber pull-out test (IFSS) and short-beam bending test (ILSS) results showed that the IFSS and ILSS of carbon fibers/epoxy composites could obtain 30.8 and 10.6% improvement compared with the composites without nano-SiO₂, respectively, when the nano-SiO₂ content was 1 wt % in sizing agents. Impact test of carbon fibers/epoxy composites treated by nano-SiO₂ containing sizing showed higher absorption energy than that of carbon fibers/epoxy composites treated by sizing agent without nano-SiO₂. Scanning electron microscopy (SEM) of impact fracture surface showed that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂-modified sizing treatment. Dynamic mechanical thermal analysis (DMTA) showed that the introduction of nano-SiO₂ to carbon fibers surface effectively improved the storage modulus of carbon fibers/epoxy.     

Improvement of interfacial interactions in CF/PEEK composites by an s-PSF/graphene oxide compound sizing agent

The interfacial interactions of carbon fiber (CF)-reinforced polymer composites is a key factor affecting the overall performance of the material. In this work, we prepared a sulfonated poly(ether sulfone)–graphene oxide mixed sizing agent to modify the interface of CF/PEEK composites and improve the interfacial properties between the PEEK matrix and CF. Results showed that the mechanical and interfacial properties of CF/PEEK composites are improved by the sizing agent. Specifically, the flexural strength, flexural modulus and interlaminar shear strength of the materials reached 847.29 MPa, 63.77 GPa, and 73.17 MPa, respectively. Scanning electron microscopy confirmed markedly improved adhesion between the resin matrix and fibers. This work provides a simple and effective method for the preparation of high-performance CF/PEEK composites, which can improve the performance of composites without degrading the mechanical property of pristine CF.     

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.     

Nanoscale toughening of carbon fiber‐reinforced epoxy composites through different surface treatments

Interests in improving poor interfacial adhesion in carbon fiber‐reinforced polymer (CFRP) composites has always been a hotspot. In this work, four physicochemical surface treatments for enhancing fiber/matrix adhesion are conducted on carbon fibers (CFs) including acid oxidation, sizing coating, silane coupling, and graphene oxide (GO) deposition. The surface characteristics of CFs are investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, interfacial shear strength, and interlaminar shear strength. The results showed that GO deposition can remarkably promote fiber/matrix bonding due to improved surface reactivity and irregularity. In comparison, epoxy sizing and acid oxidation afford enhancement of IFSS owing to effective molecular chemical contact and interlocking forces between the fiber and the matrix. Besides, limited covalent bonds between silane coupling and epoxy matrix cannot make up for the negative effects of excessive smoothness of modified CFs, endowing them inferior mechanical properties. Based on these results, three micro‐strengthening mechanisms are proposed to broadly categorize the interphase micro‐configuration of CFRP composite, namely, “Etching” “Coating”, and “Grafting” modifications, demonstrating that proper treatments should be chosen for combining optimum interfacial properties in CFRP composites. POLYM. ENG. SCI., 59:625–632, 2019. © 2018 Society of Plastics Engineers     

Improving mechanical and thermal properties of short carbon fiber/polyamide 6 composites through a polydopamine/nano-silica interface layer

Carbon fiber (CF) reinforced matrix composites have been applied widely, however, the interfacial adhesion of composites is weak due to smooth and chemically inert of CF surface. To solve this problem, A polydopamine/nano-silica (PDA-SiO₂) interfacial layer on carbon fiber surface was constructed via polydopamine and nano- SiO₂ (CF-PDA-SiO₂) by a facile and effective method to reinforce polyamide 6 composites (CFs/PA6). The effects of PDA-SiO₂ interfacial layer on crystallization structure and behavior, thermal properties, and mechanical properties of CFs/PA6 composites were investigated. Furthermore, interfacial reinforcement mechanism of composites has been discussed. This interfacial layer greatly increased the number of active groups of CF surface and its wettability obviously. The tensile strength of CF-PDA-SiO₂/PA6 composites increased by 28.09%, 19.37%, and 26.22% compared to untreated-CF/PA6, CF-PDA/PA6, and CF-SiO₂/PA6 composites, respectively, which might be caused by the increased interfacial adhesion between CF and PA6 matrix. The thermal stability, crystallization temperature, crystallinity, and glass transition temperature (T_g) of CF-PDA-SiO₂/PA6 composites improved correspondingly, attributing to the heterogeneous nucleation of nano-SiO₂ in the crystalline area and hydrogen bonds with molecular chains of PA6 in the amorphous area. This work provides a novel strategy for the construction of interfaces suitable for advanced CF composites with different structures.     

Improved interfacial adhesion in carbon fiber/poly (ether ether ketone) composites with the sulfonated poly (ether ether ketone) sizing treatment

A water-soluble sulfonated poly (ether ether ketone) (SPEEK) sizing agent is prepared and applied to improve the interfacial adhesion of carbon fiber/poly (ether ether ketone) (CF/PEEK) composites. The surface morphology, surface roughness, surface chemistries, and surface free energy of SPEEK sized CF are obtained to understand the sizing effect. The results reveal the increased surface free energy and surface roughness of SPEEK sized CF. In addition, a chemical reaction between the CF surface and sizing layer is proved based on the results of XPS, IR, and ¹H NMR. The interfacial structure of CF/PEEK composites is further ascertained by AFM and the appearance of gradient interface could be verified for SPEEK sized CF/PEEK composites. The formation of the gradient interface is due to the chemical reaction between the CF and sizing agent as well as the improved compatibility between the sized CF and matrix, which benefits the improvement of interfacial adhesion.     

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.