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.     

Interface improvement of carbon fiber/methylphenylsilicone resin composites by fiber surface coating of polyhedral oligomeric silsesquioxanes

To enhance interfacial properties of carbon fibers (CFs)-reinforced methylphenylsilicone resin (MPSR) composites, we introduced an appropriate interface reinforced by trisilanolphenyl-polyhedral oligomeric silsesquioxanes (trisilanolphenyl-POSS) between CFs and MPSR with a liquid phase deposition strategy. Chemical bonds among silanol groups of trisilanolphenyl-POSS, hydroxyl-functionalized CF (CF–OH), and silanol end groups of MPSR in the coating were expected to be formed through condensation reaction during the prepared process. CFs with and without sizing treatment-reinforced MPSR composites were prepared by a compression molding method. X-ray photoelectron spectroscopy revealed that trisilanolphenyl-POSS particles enhanced the contents of fiber surface oxygen-containing groups and silicon-containing functional groups. Scanning electron microscopy and atomic force microscopy images showed that trisilanolphenyl-POSS nanoparticles have been introduced onto the fiber surface obviously and the surface roughness increased sharply. Dynamic contact angle analysis indicated that trisilanolphenyl-POSS-modified sizing agent could improve the fiber wettability and surface energy significantly. Short-beam bending test and impact toughness test results showed that the interlaminar shear strength and impact resistance of the sized CFs composites were enhanced greatly with increasing amplitudes of more than 35 and 27% in comparison with those of untreated CF composites, respectively. Cryo-fractured surface topographies of composites confirmed that interfacial adhesion between CFs and MPSR has been improved after sizing treatment. Meanwhile, the sizing treatment does not decrease single fiber tensile strength.     

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 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.     

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.     

Interfacial improvement of carbon fiber/epoxy composites using a simple process for depositing commercially functionalized carbon nanotubes on the fibers

An aqueous suspension deposition method was used to coat the sized carbon fibers T700SC and T300B with commercially carboxylic acid-functionalized and hydroxyl-functionalized carbon nanotubes (CNTs). The CNTs on the fiber surfaces were expected to improve the interfacial strength between the fibers and the epoxy. The factors affecting the deposition, especially the fiber sizing, were studied. According to single fiber-composite fragmentation tests, the deposition process results in improved fiber/matrix interfacial adhesion. Using carboxylic acid-functionalized CNTs, the interfacial shear strength was increased 43% for the T700SC composite and 12% for the T300B composite. The relationship between surface functional groups of the CNTs and the interfacial improvement was discussed. The interfacial reinforcing mechanism was explored by analyzing the surface morphology of the carbon fibers, the wettability between the carbon fibers and the epoxy resin, the chemical bonding between the fiber sizing and the CNTs, and fractographic observation of cross-sections of the composites. Results indicate that interfacial friction, chemical bonding and resin toughening are responsible for the interfacial improvement of nanostructured carbon fiber/epoxy composites. The mechanical properties of the CNT-deposited composite laminate were further measured to confirm the effectiveness of this strategy.     

Preparation of multiscale graphene oxide‐carbon fabric and its effect on mechanical properties of hierarchical epoxy resin composite

Graphene oxide (GO) was used to modify the surface of carbon fiber layers through electrophoretic deposition, forming a multiscale reinforcement fabric. By adjusting the experimental parameters, the resulting GO‐carbon fabric showed productive and homogenous distribution of thin and less‐agglomerate GO platelets on carbon fiber surface, remarkably enlarging the surface area and roughness of carbon fabric. To investigate the effect of GO sheets on composites, GO‐carbon fabric and carbon fabric‐reinforced hierarchical epoxy resin composites were respectively manufactured. Mechanical tests demonstrated that after introducing GO flakes on carbon fabric, both the flexural strength and interlaminar shear strength of composite had achieved an increase, especially the interlaminar shear strength rising by 34%. Through fractography analysis, it was found that in pure carbon fabric‐reinforced epoxy composite, the fiber/matrix debonding fracture mechanism predominated, while after the GO decoration on carbon fiber surface, the composite featured a stronger interfacial bonding, leading to the enhancement in mechanical properties of hierarchical epoxy resin composite. POLYM. COMPOS., 37:1515–1522, 2016. © 2014 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.     

Effect of fiber surface modification on the mechanical properties of sisal fiber‐reinforced benzoxazine/epoxy composites based on aliphatic diamine benzoxazine

Sisal fibers were incorporated into a mixture of benzoxazine and bisphenol A type epoxy resins to form a unidirectionally reinforced composite. Surface modifications of the sisal fibers were carried out with sodium hydroxide, γ‐aminopropyltrimethoxysilane, and γ‐glycidoxypropyltrimethoxysilane. The surface treatments led to changes in the morphology, chemical groups, and hydrophilicity of the fibers. The effect of the fiber surface treatments on the fiber–matrix interfacial adhesion and mechanical properties of the composites were also studied. The results showed that surface treatments with sodium hydroxide and a silane coupling agent led to improved fiber–matrix adhesion; this could be seen in the scanning electron micrographs of the fractured surfaces from mechanical testing and the reduction in the impact strength of the composites made from treated fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effects of chemical surface pretreatment on tensile properties of a single glass fiber and the glass fiber reinforced epoxy composite

The aim of this article is to determine the effect of surface pretreatments, prior to the silanization, on the structure and tensile properties of the glass fibers and their epoxy composites. Commercial glass fibers were washed with acetone to remove the soluble portion of sizing, calcinated for the removal of organic matter, activated for surface silanol regeneration, and silanizated with glycidoxypropyltrimethoxysilane (GPS). Tensile test was carried out. The morphology of pretreated glass fibers and the fracture surfaces of the epoxy composites were observed with a scanning electron microscope (SEM). The results revealed that both apparent modulus and strength of a single glass fiber and the glass fiber/epoxy resin composites strongly depend on the fiber surface pretreatments. The acetone treatment did not change appreciably the composition and tensile properties of glass fibers, but there was a weak interface between fibers and matrix. In calcinated and acid activated fibers, the two competitive effects was observed: (1) degradation of the fibers themselves and (2) improved interfacial adhesion between the glass fibers and the epoxy matrix, once the samples was silanizated. The ATR‐FTIR results show that the surface content of Si OH increases as reflected by the increasing of the Si O band, resulting in an interaction between silane coupling agent and glass fiber. POLYM. COMPOS., 91–100, 2016. © 2014 Society of Plastics Engineers     

氨气处理碳纤维 第II报 碳纤维表面和复合材料的性能

常压下,使碳纤维通过以氨气为气体介质的600℃热反应炉,反应停留时间为30s。采用三点短梁法和界面评价装置研究处理前后复合材料的层间剪切强度(ILSS)和界面剪切强度(IFSS),经氨气处理后二者分别提高了13.2%和32.1%。接触角测试结果表明:处理后碳纤维与水和环氧树脂的浸润性得到很大改善。采用扫描电子显微镜(SEM)研究处理前后碳纤维表面和复合材料断裂面形貌的变化,发现氨气处理对碳纤维表面形貌没有影响。力学性能测试数据表明,氨气处理不影响碳纤维的强度。     

Effect of silane coupling agents on basalt fiber–epoxidized vegetable oil matrix composite materials analyzed by the single fiber fragmentation technique

The fiber–matrix interfacial shear strength (IFSS) of biobased epoxy composites reinforced with basalt fiber was investigated by the fragmentation method. Basalt fibers were modified with four different silanes, (3‐aminopropyl)trimethoxysilane, [3‐(2‐aminoethylamino)propyl]‐trimethoxysilane, trimethoxy[2‐(7‐oxabicyclo[4.1.0]hept‐3‐yl)ethyl]silane and (3‐glycidyloxypropyl)trimethoxysilane to improve the adhesion between the basalt fiber and the resin. The analysis of the fiber tensile strength results was performed in terms of statistical parameters. The tensile strength of silane‐treated basalt fiber is higher than the tensile strength of the untreated basalt fiber; this behavior may be due to flaw healing effect on the defected fiber surfaces. The IFSS results on the composites confirm that the interaction between the fiber modified with coupling agents and the bio‐based epoxy resin was much stronger than that with the untreated basalt fiber. POLYM. COMPOS., 36:1205–1212, 2015. © 2014 Society of Plastics Engineers     

Evaluation of tribological performance of surface‐treated carbon fiber‐reinforced thermoplastic polyimide composite

The effect of surface treatment [rare earth solution (RES) and air oxidation] of carbon fibers (CFs) on the mechanical and tribological properties of carbon fiber‐reinforced polyimide (CF/PI) composites was comparatively investigated. Experimental results revealed that surface treatment can effectively improve the interfacial adhesion between carbon fiber and PI matrix. Thus, the flexural strength and wear resistance were significantly improved. The RES surface treatment is superior to air oxidation treatment in promoting interfacial adhesion between carbon fiber and PI matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

玄武岩纤维表面处理及其复合材料界面改性研究

为改善玄武岩纤维的织造性能及其复合材料的界面性能，本文采用表面偶联剂结合乳液型浆料上浆的方法对纤维进行表面处理，研究表明，采用乳液型浆料处理后，玄武岩纤维的织造性能得到显著改善，在上浆处理前对纤维进行表面偶联剂处理，可使玄武岩纤维／环氧复合材料的界面性能得到明显提高，从而实现了纤维织造性能与复合材料界面力学性能的共同改善。     

Effect of surface modification of aluminum nitride on electrical and thermal characterizations of thermosetting polymeric nanocomposites

Thermally conductive composites and nanocomposites composed of epoxy resin as base matrix and aluminum nitride (AlN) as micro and nanofiller have been studied at variable temperatures and loading of AlN. To improve the dispersion of the filler within the polymer matrix, AlN was surface modified with silane‐coupling agent. Thermogravimetric analysis confirmed the interfacial bonding of epoxy‐ and silane‐modified AlN. The dielectric properties of epoxy/AlN composites and nanocomposites have been studied at variable percentage of filler. Test result indicated an increase of thermal conductivity of the composites at 20 wt% of AlN. Also, silane‐treated composites exhibited improved electrical conductivity properties, whereas the electrical insulation property decreased in terms of dielectric strength and resistivity. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

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     

Unsaturated polyester‐toughened epoxy composites: Effect of sisal fiber on thermal and dynamic mechanical properties

In the present study, the mechanical and thermal properties of sisal fiber‐reinforced unsaturated polyester (UP)‐toughened epoxy composites were investigated. The sisal fibers were chemically treated with alkali (NaOH) and silane solutions in order to improve the interfacial interaction between fibers and matrix. The chemical composition of resins and fibers was identified by using Fourier‐transform infrared spectroscopy. The UP‐toughened epoxy blends were obtained by mixing UP (5, 10, and 15 wt%) into the epoxy resin. The fiber‐reinforced composites were prepared by incorporating sisal fibers (10, 20, and 30 wt%) within the optimized UP‐toughened epoxy blend. Scanning electron microscopy was used to analyze the morphological changes of the fibers and the adhesion between the fibers and the UP‐toughened epoxy system. The results showed that the tensile and flexural strength of (alkali‐silane)‐treated fiber (30 wt%) ‐reinforced composites increased by 83% and 55%, respectively, as compared with that of UP‐toughened epoxy blend. Moreover, thermogravimetric analysis revealed that the (alkali‐silane)‐treated fiber and its composite exhibited higher thermal stability than the untreated and alkali‐treated fiber systems. An increase in storage modulus and glass transition temperature was observed for the UP‐toughened epoxy matrix on reinforcement with treated fibers. The water uptake behavior of both alkali and alkali‐silane‐treated fiber‐reinforced composites is found to be less as compared with the untreated fiber‐reinforced composite. J. VINYL ADDIT. TECHNOL., 23:188–199, 2017. © 2015 Society of Plastics Engineers     

Effect of annealing and silylation on the strength of melt-spun Ni–Mn–Ga fibres and their adhesion to epoxy

Single crystals of ferromagnetic Ni–Mn–Ga shape memory alloys show magnetic-field and stress induced twinning, leading to shape memory. Adaptive composites can thus be produced by embedding single crystalline particles or bamboo-structured Ni–Mn–Ga fibres into a polymer matrix. To guarantee a durable performance of these composites, adhesion between reinforcement phase and matrix should be quantified and optimised. The influence of annealing and surface treatment with an aminosilane of melt-spun Ni–Mn–Ga fibres on their strength and adhesion to an epoxy matrix was investigated using single fibre tension and fragmentation tests. Annealing of the melt-spun Ni–Mn–Ga fibres changed the surface from a “pimpled” to a smooth microstructure. This resulted in a reduced adhesion of the annealed fibres in comparison to the as-spun fibres embedded in an epoxy matrix. As-spun fibres exhibited an interfacial shear strength (IFSS) comparable to the shear strength of the epoxy matrix so that the silylation did not change the adhesion significantly. For the annealed fibres, the silane treatment improved the IFSS by 67%. Furthermore, the silylation increased the fracture strength of the Ni–Mn–Ga fibres due to surface flaw healing or forming of a protective surface coating.     

Interfacial properties in commingled yarn thermoplastic composites. Part I: Characterization of the fiber/matrix adhesion

The paper aims to assess the fiber/matrix interface and adhesion quality in commingled GF/PP composites by means of complementary experimental methods. For this purpose, different interfacial qualities were obtained by a modification of the sizing of the fiber reinforcement (polypropylene specific sizing, non-specific sizing and no sizing), and of the matrix (with or without coupling agent). Transverse tensile stress-strain curves have been recorded while monitoring acoustic emissions. An analysis of acoustic emission data associated with fracture surface examinations has helped explain the differences observed in mechanical properties and damage mechanisms, emphasizing the importance of the interphase in the performance of these new composites. Thus it has been shown that the association of three experimental investigation methods (transverse tension, acoustic emission, and fracture surface analysis) makes it possible to characterize both the glass/silane bond (so-called fiber/matrix interface) and the global fiber/matrix adhesion (addition of several different zones and interfaces). Polym. Compos. 25:577–588, 2004. © 2004 Society of Plastics Engineers.     

Interfacial studies on the surface modified aramid fiber reinforced epoxy composites

In this work, solutions of rare earth modifier (RES) and epoxy chloropropane (ECP) grafting modification method were used for the surface treatment of aramid fiber. The effect of chemical treatment on aramid fiber has been studied in a composite system. The surface characteristics of aramid fibers were characterized by Fourier transform infrared spectroscopy (FTIR). The interfacial properties of aramid/epoxy composites were investigated by means of the single fiber pull‐out tests. The mechanical properties of the aramid/epoxy composites were studied by interlaminar shear strength (ILSS). As a result, it was found that RES surface treatment is superior to ECP grafting treatment in promoting the interfacial adhesion between aramid fiber and epoxy matrix, resulting in the improved mechanical properties of the composites. Meanwhile, the tensile strengths of single fibers were almost not affected by RES treatment. This was probably due to the presence of reactive functional groups on the aramid fiber surface, leading to an increment of interfacial binding force between fibers and matrix in a composite system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4165–4170, 2006