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     

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.     

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.     

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     

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     

Temperature effect on interfacial bonding property of single‐carbon fiber/epoxy resin composite

The changes in interfacial fracture energy of three kinds of commercially sized carbon fiber (CF)/epoxy resin composites in the range from ambient temperature to 130°C were investigated using the single‐fiber fragmentation test to evaluate the heat resistance of the interphase. The effects of CF sizing on the interfacial bonding property were studied using desized CF/epoxy resin composites. Thermogravimetric analysis and differential scanning calorimetry of the combination of sizing and matrix were employed to investigate the role of sizing on the variations in the fiber/matrix interfacial property under elevated temperature. The interfacial fracture energy values of all the studied CF composites were found to decrease quickly during the initial stage of temperature rise and drop gradually at higher temperature. At elevated temperature, the desized CF composites had higher heat resistance than the corresponding sized fiber composites. The differences in the interfacial heat resistance among the three kinds of CF composites and the difference in the interfacial thermal stability between the sized and the desized fiber composites were related to different glass transition temperatures of the interphases. The interaction between sizing and the matrix and the chain motion of the crosslink structure of the interphase has been suggested to determine the interfacial heat resistance. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

环氧树脂上浆剂对PAN基碳纤维性能的影响

分别以KD-213,YD-128环氧树脂、复合环氧树脂及油酸酰胺改性的复合环氧树脂(改性环氧树脂)为主体的上浆剂对聚丙烯腈基碳纤维(PANCF)进行上浆,对上浆纤维的加工性能、表面形貌及其界面剪切强度(IFSS)进行了研究。结果表明:上浆剂改善了PANCF的耐磨性、毛丝量、耐水性及其复合材料的IFSS。其中改性环氧树脂上浆剂为最佳,可在PANCF表面形成一层完整的柔韧性光滑薄膜,上浆后的PANCF的耐磨次数为1887,毛丝量为0.14mg,吸水率小于等于0.005%,复合材料IFSS较未上浆纤维提高38.5%,达87.26GPa。     

Influence of epoxy sizing of carbon‐fiber on the properties of carbon fiber/cyanate ester composites

The high modulus carbon fiber (M40J) sized by epoxy resin E51 and E20 reinforced bisphenol A dicyanate (2,2′‐bis(4‐cyanatophenyl) isopropylidene resin composite was prepared in order to investigate the influence of epoxy sizing of the fiber on the properties of the composite. Differential scanning calorimetry (DSC) and fourier transforms infrared (FTIR) analysis showed that epoxy resin have catalytic effect on cure reaction of cyanate ester. Mechanical properties of the composite revealed that M40J fiber sized by epoxy resin could improve the flexural strength and interlaminar shear strength of M40J/bisphenol A dicyanate composites. The micro‐morphology of the composite fractures was studied by means of scanning electron microscopy (SEM). Reduced flaws were observed in the M40J‐bisphenol A dicyanate interface when the sized fiber was used. Water absorption of the composites was also investigated. It was found that the water absorption descended at the initial boiling stage (12 h). POLYM. COMPOS, 27: 591–598, 2006. © 2006 Society of Plastics Engineers     

Resin modification on interlaminar shear property of carbon fiber/epoxy/nano‐CaCO3 hybrid composites

Epoxy resin was modified by adding a silane coupling agent/nano‐calcium carbonate master batch. Then, samples of binary carbon fiber/epoxy composites and ternary fiber/nano‐CaCO₃/epoxy were prepared by hot press process. The interlaminar shear strength (ILSS) of the carbon fiber/epoxy composites was investigated and the results indicate that introduction of the treated nano‐CaCO₃ enhances ILSS obviously. In particular, the addition of 4 wt% nano‐CaCO₃ leads to 36.6% increase in the ILSS for the composite. The fracture surfaces of the carbon fiber/epoxy composites and the mechanical properties of epoxy resin cast are examined and both of them are employed to explain the change of ILSS. The results show that the change of ILSS is primarily due to an increase of the epoxy matrix strength and an increase of the fiber/epoxy interface. The bifurcation of propagating cracks, stress transfer, and cavitation are deduced for the reasons of strengthening and toughening effect of nano‐CaCO₃ particles. POLYM. COMPOS., 38:2035–2042, 2017. © 2015 Society of Plastics Engineers     

Effect of an epoxy‐based bonding agent on the cure characteristics and mechanical properties of short‐nylon‐fiber‐reinforced acrylonitrile–butadiene rubber composites

The cure characteristics and mechanical properties of short‐nylon‐fiber‐reinforced acrylonitrile–butadiene rubber composites with and without an epoxy resin as a bonding agent were studied. The epoxy resin was a good interfacial‐bonding agent for this composite system. The minimum torque showed a marginal increase with the resin concentration. The maximum–minimum torque showed only a marginal change with the resin. The scorch time decreased with the fiber concentration and resin content. The tensile strength and abrasion resistance were improved and the tear resistance and resilience were reduced with the resin concentration. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 532–539, 2006     

聚丙烯腈基碳纤维用环氧树脂上浆剂的比较

用两种环氧树脂上浆剂对国产聚丙烯腈基碳纤维进行上浆,测试和比较了两种环氧树脂上浆剂对聚丙烯腈(PAN)基碳纤维耐磨性、与水接触角、表面能等性能以及拉伸强度、伸长率、层间剪切强度(ILSS)等力学性能的影响。上浆剂中主体成分环氧树脂相对分子质量不是影响碳纤维层间剪切强度的决定性因素。     

Influence of carbon fiber surface treatments on the structure and properties of conductive carbon fiber/polyethylene films

Effects of carbon fiber (CF) surface modification on the crystalline structure and both electrical and mechanical properties of conductive CF/high‐density polyethylene (HDPE) films were studied. Three different types of surface‐treated CF, epoxy‐sized, unsized, and sized but thermally treated, were considered. It was found that the uniformity of the transcrystalline zone around CF and the overall crystallinity of the polyethylene matrix decreased when epoxy‐sized CF was used. Epoxy‐sized CF caused a significant reduction not only in electrical resistivity and temperature coefficient of resistivity (TCR) but also tensile strength and coefficient of linear thermal expansion (CLTE) of composite films compared with that of unsized or sized CF that was thermally treated. We observed the systematic changes of TCR and CLTE values in accordance with CF surface modification and CF content in composite films. It was concluded that thermal expansion of the polymer matrix is the main reason for the positive TCR of CF/HDPE films. As the most probable reasons for decreased resistivity and strength of the CF/HDPE films with epoxy‐sized CF, the diffusion of epoxy sizing agent into the polyethylene matrix and the formation of loosened semiconductive interphase structure in the film are considered. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2040–2048, 2002; DOI 10.1002/app.10500     

The effect of hydroxyl‐terminated polybutadiene‐grafted carbon fiber on the impact performance of carbon fiber–epoxy resin composites

Carbon fiber (CF) containing 1.4 and 2.1 mmol/g of —COOH and —OH groups, respectively, was functionalized by using an excess of tolylene‐2,4‐diisocyanate. The NCO‐modified CF was submitted to a graft reaction with hydroxyl‐terminated polybutadiene (HTPB). The HTPB‐grafted carbon fiber was employed as reinforcing agent for epoxy resin‐based composites. The presence of the flexible HTPB at the interface between the fiber and the matrix resulted in a substantial improvement on impact strength. Additional improvement on toughness was achieved by using epoxy matrix containing dispersed phase of HTPB. The composite morphology was also studied by scanning electron microscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1424–1431, 1999     

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     

Effect of sizing on interfacial adhesion of commercial high strength carbon fiber‐reinforced resin composites

The influence of sizing agent on interfacial shear strength (IFSS) of carbon fiber/epoxy (CF/EP) and carbon fiber/bismaleimide (CF/BMI) was investigated. Since sizing agent can alter physicochemical properties of CF surface, possible affecting factors, including sizing reactivity, chemical reactions between sizing and resin, wettability of fiber with resin, fiber surface roughness, and chemical composition of fiber surface, were discussed. It is found that contact angle of fiber with resin and sufficient chemical reactions between sizing and resin reveal strong correlation with the interfacial adhesion of CF/EP and CF/BMI, while the effect of surface roughness and the amount of oxygen on the fiber surface are relatively weak. Due to EP type of the composition, the sizing agent tends to improve the wettability of CF with EP, while goes against for the fiber with BMI. POLYM. COMPOS., 254–261, 2016. © 2014 Society of Plastics Engineers     

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     

活性胺改性双酚A型环氧树脂在玻璃纤维细纱中的应用

采用化学方法将二乙醇胺接枝在双酚A型环氧树脂的骨架上,以冰醋酸作为中和剂,制备了改性水性环氧树脂。在大量的试验基础上,确定了最佳的合成配比及工艺条件。以此改性双酚A型环氧树脂为助成膜剂的浸润剂产品赋予了细纱优良的集束性、耐磨性;同时满足制品的加工要求,在退解、捻线制造过程中减少毛丝,提高了玻璃纤维细纱产品的质量。     

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