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.     

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     

Properties of carbon fiber and composites modified with different‐sized graphene oxide sheets

The graphene oxide (GO) sheets with different size distributions were effectively separated by a centrifugation method. The exfoliated single‐layer structure and the size of GO sheets were verified by scanning electron microscopy (SEM), atomic force microscope (AFM), and metallurgical microscope, respectively. Two different‐sized GO sheets water suspensions were obtained, which were then directly dispersed in carbon fiber (CF) sizing agent, respectively. The influences of the different‐sized GO sheets on CF and CF composites were explored. The workability in later process of CF and CF surface morphology were characterized by abrasion resistance, fluffs and breakage, stiffness, and SEM. SEM micrographs demonstrated that a nonuniform distribution of the large‐sized GO was lapped on CF whereas the small‐sized GO was uniformly leaned on CF. The interlaminar shear strength of the small‐sized GO/CF reinforced composite could reaches the maximum value. It indicated that the interfacial region between CF and polymer matrix could be enhanced by adjusting the size of GO sheets. POLYM. COMPOS., 37:2719–2726, 2016. © 2015 Society of Plastics Engineers     

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.     

Preparation and performance of nano‐SiO2 stabilized Pickering emulsion type sizing agent for glass fiber

The nano‐SiO₂ particles modified by silane coupling agent A‐1100 were used for preparing the vinyl ester resin (VE) Pickering emulsion. The stable emulsion could be served as the film former of sizing agent for glass fiber (GF). The influence of the wettability and the addition amount of nano‐SiO₂ on the stability of film former emulsion was explored. The effect of nano‐SiO₂ Pickering emulsion type sizing agent on the properties of GF was investigated. SEM images show that there existed a layer of sizing agent film with nano‐SiO₂ particles evenly on the GF surface. The abrasion resistance of the sized GF reached 3,579 times and the stiffness was 69 mm. The strand integrity also performed well. The fracture strength of GF bundles treated by Pickering emulsion type sizing agent increased by 28.6% to 0.504 N/Tex compared with that of the unsized GF bundles. The interlaminar shear strength (ILSS) of GF/VE composites sized by self‐made sizing agent which contained nano‐SiO₂ has improved, compared to the unsized GF reinforced VE composite. POLYM. COMPOS., 37:334–341, 2016. © 2014 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.     

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     

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.     

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.     

电晕法处理超高相对分子质量聚乙烯纤维

用电晕法对超高相对分子质量聚乙烯纤维进行了表面处理。利用DPPH检测纤维表面自由基的产生和变化，并用XPS表面元素分析、SEM等方法探讨了纤维表面性能处理前后的变化。实验发现，通过电晕处理后，纤维复合材料的抗剪切强度从未处理的5．98MPa提高到14．3MPa。     

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.     

Effects of hygrothermal aging on the thermal–mechanical properties of vinylester resin and its pultruded carbon fiber composites

Hygrothermal aging was carried out on vinyl ester (VE) resin cast and its pultruded carbon fiber reinforced composite (CF/VE) by immersing them in distilled water at 65 and 95°C. Hygrothermal aging effects on the samples were studied in terms of thermal–mechanical properties, as well as moisture absorption behavior, interfacial adhesion, and transverse mechanical properties. Moisture absorption behaviors of the VE casts and the CF/VE composites were characterized as Fickian behavior. Dynamic mechanical thermal analysis (DMTA) tests showed that the tan δ peak temperatures of the VE casts and CF/VE composites decreased with immersion time at 65 and 95°C. Moreover, there existed a splitting in the tan δ peaks at 95°C, which was reversible and could be recovered by dehydration. Three‐point flexural test indicated that flexural strengths of both the VE casts and the composites decreased by hygrothermal aging with a trend related to their moisture absorption behaviors, while flexural modulus of the composites was less affected. The ILSS of the CF/VE composites was also depressed by deterioration in interfacial adhesion, which was proved by the interfacial adhesion parameters, A and α. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Mechanical properties of carbon fiber composites modified with graphene oxide in the interphase

The surface topographies of carbon fibers treated by sizing agents with different graphene oxide (GO) content were investigated by scanning electron microscopy. The surface elements compositions of carbon fibers were determined by X‐ray photoelectron spectrometer. The interfacial properties of composites were studied by interfacial shear strength. The thermo‐mechanical properties of two typical specimens (CF‐G0 and CF‐G1 composites) were investigated by dynamic mechanical thermal analysis. The results showed the introduction of GO sheets on carbon fibers surfaces effectively improved the mechanical properties of carbon fibers/epoxy composites. POLYM. COMPOS., 38:2425–2432, 2017. © 2016 Society of Plastics Engineers     

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.     

Reaction of carbon fiber sizing and its influence on the interphase region of composites

What might happen with the interphase region of composite if the sizing agent cannot afford the attack of processing temperature and firstly reacted before its combination with the resin, is rarely reported. On the basis of this, herein, effects of sizing reaction on the interphase region of composite were investigated, as well as on the carbon fiber surface properties. It showed that the interfacial shear strength of carbon fiber/epoxy composite was improved after the sizing reaction. The interphase modulus was also increased with a thinner gradient distance. Further analysis indicated that the fiber surface roughness increased, the fiber wettability with the resin lowered, and the chemical reactions between sizing agent and resin reduced after 200°C/2 h treatment on carbon fiber. These results explained the change of the interphase region, which are meaningful for sizing optimization. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41917.     

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.     

Dynamic mechanical property and interlaminar shear strength of the carbon fabric reinforced polyetherimide composite based on the polyetherimide resin films

In this study, the laminates reinforced with the concentrated nitric acid or acetone treated carbon fabrics were prepared based on polyetherimide films with different thickness including 30 μm and 50 μm, respectively. 4 Harness Satin (4HS) and 5 Harness Satin (5HS) carbon fabrics were used as the reinforcements of the composite laminates. Three impact factors, including the polyetherimide film thickness, fabric treatment method and fabric type, were considered in this study. Interlaminar shear strength (ILSS) measurement shown that the thicker polyetherimide film (50 μm), 4HS carbon fabric and the nitric acid treatment of the fabric could be used to increase the ILSS value because of the improvement of the interfacial property for the laminate. The 50 μm thickness polyetherimide films used in the laminates improved the storage modulus, and decreased the glass transition temperatures (T _gs) by DMA or DSC. It was because that the better interfacial property and the stronger mobility of the polymer chain under the greater residual internal stress in the laminate was obtained with the increase of the polyetherimide film thickness. The nitric acid treatment of the fabric increased the T _gs measured by DMA and DSC, and decreased the tan δ peak values of the laminates because of the stronger interfacial adhesion between the fiber and the resin and the decreased mobility of the polymer chain. In addition, the effects of above three impact factors on the ILSS, storage modulus, loss modulus, tan δ and the T _g of the laminate were discussed in detail by ILSS, DMA and DSC measurement, respectively. POLYM. COMPOS., 38:663–672, 2017. © 2015 Society of Plastics Engineers     

The preparation of emulsion type sizing agent for carbon fiber and the properties of carbon fiber/vinyl ester resin composites

Vinyl ester resin emulsion type sizing agent (HMSA‐1) was synthesized by phase inversion emulsification method. Centrifugal sedimentation analysis, particle size analysis, Fourier transforms infrared spectroscopy (FTIR), and gel permeation chromatography were used to characterize HMSA‐1 and Japanese commercial sizing agents (JSA‐1 and JSA‐2). Meanwhile, abrasion resistance, fluffs and breakage, stiffness, scanning electron microscope (SEM) were used to analyze the workability in later process of carbon fiber and surface morphology. The results showed that HMSA‐1 could significantly improve handling characteristics of carbon fiber. SEM micrographs demonstrated that the sized carbon fiber had smooth surface. HMSA‐1 had better compatibility with vinyl ester resin. The interlaminar shear strength (ILSS) of HMSA‐1 sized carbon fiber/vinyl ester resin composite reached the maximum value of 45.96 MPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of Silane Coupling Agent on the Tensile Properties of Carbon Fiber-Reinforced Thermoplastic Polyimide Composites

Silane coupling agent SG-Si900 (SGS) modification and air-oxidation methods were used to improve the interfacial adhesion of the carbon fiber-reinforced polyimide (CF/PI) composite. The interfacial characteristics of the composites reinforced by the carbon fibers treated with different surface modification methods were comparatively investigated. Results showed that both SGS modification and air-oxidation method improved the adhesion between the reinforcement and matrix and SGS modification method was superior to air-oxidation method. For CF/PI composite the optimum interfacial adhesion was obtained at 0.3 wt% SGS concentration. The fracture surfaces of samples were investigated by scanning electronic microscopy (SEM) to analyze the effects of different surface treatment methods.