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.     

Preparation of a carbon nanotube/carbon fiber multi-scale reinforcement by grafting multi-walled carbon nanotubes onto the fibers

To prepare a carbon nanotube (CNT)/carbon fiber multi-scale reinforcement (MSR), multi-walled carbon nanotubes (MWCNTs) functionalized at the end caps with hexamethylene diamine (HMD) are grafted onto the surfaces of carbon fibers treated with acyl chloride. The surface element concentrations, surface functional groups and morphology of the MSR were examined by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XPS spectra indicate that sp² and sp³ carbon atoms are major components in the MSR surface, and the carbon fiber surface structure is not destroyed. There is 17.41% of C-NH_x in the surface of the MSR, which suggests that MWCNTs are covalently grafted onto carbon fiber surfaces. SEM shows that the grafted MWCNTs stick to the carbon fiber surface at different angles, and are uniformly distributed along the outer edges of the grooves in the fiber surface. The grafted MWCNTs are 50-200 nm in length and around 14 nm in diameter. It was found that the grafting increases the weight of carbon fiber by 1.2%, which implied that a considerable amount of MWCNTs were grafted onto carbon fiber surfaces.     

Covalent functionalization of carbon fiber with poly(acrylamide) by reversible addition–fragmentation chain transfer polymerization for improving carbon fiber/epoxy interface

A novel method was developed for grafting poly(acrylamide) (PAAM) on to the carbon fiber (CF) surface via reversible addition–fragmentation chain transfer (RAFT) polymerization to improve the interaction between carbon fibers and epoxy matrix in the composites system. The carbon fibers were first treated with nitric acid and γ‐methacryloxypropyltrimethoxy silane (KH570). Then, the PAAM was grafting onto the carbon fiber surface via RAFT polymerization. The resulted carbon fibers functionalized with PAAM (CF‐PAAM) were characterized by FTIR, XPS, and TGA, and the results revealed that CF‐PAAM were synthesized successfully. The introduction of PAAM chains could make the fiber surface rougher and introduce a large numbers of –NH₂ groups, which can improve the interfacial adhesion in the composites. The microbond test results showed that the interfacial shear strength (IFSS) of the composites reinforced by CF‐PAAM has been enhanced about 107%. POLYM. COMPOS., 38:27–31, 2017. © 2015 Society of Plastics Engineers     

Graphene oxide-anchored reactive sulfonated copolymer via simple one pot condensation polymerization: proton-conducting solid electrolytes

A rapid and efficient post-polymerization functionalization of poly(urea-co-urethane) (PUU) onto the graphene oxide (GO) nanosheets has been developed to produce super-acidic polymer/GO hybrid nanosheets. Thus, the surface of GO nanosheets were functionalized with 3-(triethoxysilyl)propyl isocyanate (TESPIC) from hydroxyl groups to yield isocyanate functionalized graphene oxide nanosheets. Then, sulfonated polymer/GO hybrid nanosheets were prepared by condensation polymerization of isocyanate-terminated pre-polyurea onto isocyanate functionalized graphene oxide nanosheets through the formation of carbamate bonds. FTIR and TGA results indicated that TESPIC modifier agent and poly(urea-co-urethane) were successfully grafted onto the GO nanosheets. The grafting efficiency of poly(urea-co-urethane) polymer onto the GO nanosheets was estimated from TGA thermograms to be 205.9%. Also, sulfonated polymer/GO hybrid nanosheets showed a proton conductivity as high as 3.7 mS cm^?1. Modification and morphology of GO nanosheets before and after modification processes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD).     

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     

The role of maleic anhydride functionalized graphene oxide in improving the interfacial properties of carbon fibre/bismaleimide composites

This work aims to assess the effect of maleic anhydride functionalized graphene oxide (MAH‐f‐GO) on the interfacial properties of carbon fibre/bismaleimide (BMI) composites by experimental and finite element (FE) methods. Transverse fibre bundle (TFB) specimens with different contents of MAH‐f‐GO nanoparticles were manufactured to investigate the interfacial strength of the carbon fibre/BMI composites. The fracture surface of the TFB specimens was examined by scanning electron microscopy to observe the morphologies of the fibre ? matrix interface. The coefficient of thermal expansion, cure shrinkage and elastic modulus were measured and included in the FE simulation. An FE analysis model was established to simulate the thermal residual stress distribution around the carbon fibre and to estimate the interfacial bonding strength of the TFB specimens. The combination of experimental and FE analysis results indicated that the addition of MAH‐f‐GO nanoparticles noticeably reduced the concentration of residual stress at the fibre ? matrix interface and enhanced the interfacial properties of the carbon fibre/BMI composites.© 2017 Society of Chemical Industry     

碳纳米材料接枝碳纤维的复合材料界面增效研究进展

界面作为复合材料的重要组成部分,起着传递载荷的作用,影响复合材料的整体性能。碳纤维表面属于石墨乱层结构,微晶有序取向,惰性大,不易与树脂基体结合。对碳纤维进行适当的表面改性,增加纤维的比表面积、粗糙度和引入活性官能团,都能改善表面润湿情况,实现机械结合和化学结合,提高复合材料的界面性能。碳纳米材料接枝到碳纤维表面,是提高界面性能的有效方法之一。因此,对碳纳米管、氧化石墨烯接枝碳纤维的制备方法、界面增效设计以及界面增强机制的国内外研究现状进行综述和分析,在此基础上,展望了碳纳米材料接枝碳纤维表面和界面性能评价方法的研究趋势和前景。     

Carboxyl functionalization of carbon fibers through a grafting reaction that preserves fiber tensile strength

Composite materials can be enhanced by grafting a secondary material to a functional group on the surface of the reinforcing fibers to improve thermal, electrical or mechanical properties. Grafting secondary materials onto carbon fibers is often limited by the low reactivity of graphitic carbon and there is strong demand to create novel grafting methods with versatile functional groups. One desirable functional group is a carboxylic acid, which strongly interacts with many organic and inorganic materials. In this work, the surface of carbon fibers is functionalized by a reaction of naturally existing surface hydroxyl groups with isopropylidene malonate to graft terminal malonic esters, effectively creating a carboxyl functionalized surface. The reaction does not employ pre-oxidation to generate functional groups prior to grafting and is shown to preserve the tensile strength and morphology of the fiber. The surface functionalization is quantified by X-ray photoelectron spectroscopy, which shows that the relative surface coverage by carboxylic acid groups is increased from an initial 5.2% up to 9.2%. The effects of solvent, temperature, concentration and reaction time on the quantity of surface carboxylic acid groups are studied. This functionalization opens up new opportunities as a precursor reaction for further grafting reactions without sacrificing fiber strength.     

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.     

The Effect of Silane Surface Treatment of Carbon Fiber on the Tribological Properties of Bismaleimide(BMI) Composite

Silane surface modification method was used for the surface treatment of carbon fiber to improve the interfacial adhesion of the carbon fiber reinforced bismaleimide(BMI) composite. The surface characteristics of untreated and treated carbon fiber were characterized by Fourier transform infrared (FT-IR) spectroscope. The friction and wear properties of the BMI composites filled with differently surface treated carbon fibers(20 vol%), were investigated on a ring-on-block tribometer. Experimental results revealed that silane treatment largely reduced the friction and wear of CF/BMI composites. Scanning electron microscope (SEM) of worn surfaces of BMI composites showed that surface treated CF/BMI composite had the strongest interfacial adhesion.     

A novel method to graft carbon nanotube onto carbon fiber by the use of a binder

A novel method is developed for grafting multiwall carbon nanotubes (MWNTs) onto the surface of polyacrylonitrile‐based high strength (T300GB) carbon fiber. Functionalized MWNTs were well dispersed in the PVA solution and the carbon fiber was dip‐coated in this solution. After heat treatment of the coated carbon fiber under a nitrogen atmosphere, MWNTs with carboxyl groups were grafted onto the functionalized carbon fiber via chemical interaction. The resulting materials were characterized by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), Field emission scanning electron microscopy (FESEM), Raman spectrum and mechanical testing. FESEM observations revealed uniform coverage of carbon nanotubes on carbon fiber. The carbon fiber grafted with MWNTs improved the tensile strength by 12% with respect to the pristine carbon fiber. These results are supportive of good interfacial bonding between the carbon nanotubes (CNTs) and carbon fiber. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface modification of UHMWPE fibers by ozone treatment and UV grafting for adhesion improvement

In this study, the surface of ultra-high-molecular-weight-polyethylene (UHMWPE) fibers was modified by ozone pretreatment, followed by ultraviolet (UV) grafting, to enhance the interfacial properties of UHMWPE fibers/rubber composites. The fibers were first pretreated by ozone to introduce oxygen-functional groups. The graft polymerization of glycidyl methacrylate (GMA) onto the ozone-treated fibers was implemented by UV irradiation. The effects of time and GMA concentration on the grafting efficiency were investigated. The modified fibers were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS). The XPS and FTIR results revealed that GMA was successfully grafted onto the fibers with epoxy groups. SEM images confirmed that a continuous layer of poly-(GMA) (PGMA) was grafted onto the fibers. The interfacial adhesion force of UHMWPE fibers with rubber matrix was characterized by H pullout testing, which showed that the maximum force the fibers/rubber composites increased by 79% over that of the untreated fibers.     

Composites of allyl glycidyl ether modified polyethylene and cellulose

Linear medium density polyethylene (LMDPE) was functionalized with allyl glycidyl ether (AGE) in an internal laboratory mixer in the presence of peroxide. AGE is a bifunctional monomer, which forms unstable and energetically rich macroradicals. Upon increasing the peroxide content chain scission and grafting yield were favored. The degree of functionalization was determined by means of a calibration function for Fourier-transformed infrared spectroscopy (FTIR). Grafting AGE onto LMDPE led to a small loss of crystallinity, as evidenced by differential scanning calorimetry (DSC) and X-ray diffractometry analyses. Composites of LMDPE or functionalized LMDPE-AGE and cellulose were prepared in the mixer with filler contents ranging from 20 to 50 wt%. Composites of AGE functionalized LMDPE and filler content higher than 30 wt% presented tensile properties superior to that observed for composites with unmodified LMDPE. Scanning electron microscopy (SEM) on the composites fracture surface evidenced good interfacial adhesion between LMDPE-AGE and cellulose fibers.     

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

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

Interfacial adhesion of plasma‐treated carbon fiber/poly(phthalazinone ether sulfone ketone) composite

Interfacial adhesion between fiber and matrix has a strong influence on composite mechanical performance. To exploit the reinforcement potential of the fibers in advance composite, it is necessary to reach a deeper understanding on the relation between fiber surface treatment and interfacial adhesion. In this study, air plasma was applied to modify carbon fiber (CF) surface, and the capability of plasma grafting for improving the interfacial adhesion in CF/thermoplastic composite was discussed and also the mechanism for composite interfacial adhesion was analyzed. Results indicated that air plasma treatment was capable of increasing surface roughness as well as introducing surface polar groups onto CF; both chemical bonding and mechanical interaction were efficient in enhancements of interlaminate shear strength of CF/PPESK composite, while mechanical interaction has a dominant effect on composite interfacial adhesion than chemical bonding interaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Controlled atom transfer radical polymerization of MMA onto the surface of high-density functionalized graphene oxide

We report on the grafting of poly(methyl methacrylate) (PMMA) onto the surface of high-density functionalized graphene oxides (GO) through controlled radical polymerization (CRP). To increase the density of surface grafting, GO was first diazotized (DGO), followed by esterification with 2-bromoisobutyryl bromide, which resulted in an atom transfer radical polymerization (ATRP) initiator-functionalized DGO-Br. The functionalized DGO-Br was characterized by X-ray photoelectron spectroscopy (XPS), Raman, and XRD patterns. PMMA chains were then grafted onto the DGO-Br surface through a ‘grafting from’ technique using ATRP. Gel permeation chromatography (GPC) results revealed that polymerization of methyl methacrylate (MMA) follows CRP. Thermal studies show that the resulting graphene-PMMA nanocomposites have higher thermal stability and glass transition temperatures (T_g) than those of pristine PMMA.     

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     

Effects of silanization of C/C composites and grafting of h-BN fillers on the microstructure and interfacial properties of CVI-based C/C-BN composites

A low-density carbon/carbon (C/C) composite/silane coupling agent/hexagonal boron nitride (h-BN) hybrid reinforcement was prepared by grafting polyethyleneimine (PEI)-encapsulated modified h-BN fillers onto a carbon fiber surface using 3-aminopropyltriethoxysilane (APS) as the connection to improve the distribution uniformity of h-BN fillers in quasi-three-dimensional reinforcements and the interfacial properties between the fibers/pyrocarbon (PyC) in the C/C-BN composites obtained after densification by chemical vapor infiltration (CVI). The microstructure and chemical components of the hybrid reinforcement were investigated. The transmission electron microscopy (TEM) sample was prepared using a focused-ion beam (FIB) for the h-BN/PyC interfacial zone. The interlaminar shear strength (ILSS) and impact toughness were analyzed to inspect the composites’ interfacial properties. The results show that APS and h-BN are uniformly grafted on the fiber surface in the chopped fiber web inside the C/C composite without a density gradient, and agglomeration occurred and significantly increasing the fiber surface roughness. The highly ordered h-BN basal plane may affect the order degree of PyC near the h-BN/PyC interface. The addition of h-BN reduces the PyC texture near it, causing the annular cracks to disappear gradually. The lower PyC texture and the rougher fiber surface strengthen the interfacial bond of the fiber/matrix. Consequently, the ILSS strength of the C/C-BN composites first increases and then decreases as the h-BN filler content increases and is always higher than that of the C/C composite, while the addition of h-BN fillers weakens its impact toughness. When the h-BN content in the C/C-BN composite is 10 vol%, the ILSS of the C/C-BN composites was 15.6% higher than that of the C/C composites. However, when the h-BN content is excessive (15 vol%), the densely grafted h-BN will bridge each other, reducing the subsequent CVI densification efficiency to form a loose interface, causing a decrease in the shear strength.     

Grafting of a liquid crystal polymer on carbon fibers

Covalent grafting of mesogenic chains on carbon fiber surfaces was attempted as part of a study on composite materials containing liquid crystal polymer matrices. Grafting in these composite systems is viewed not only as a mechanism to achieve interfacial bonding but also as an approach to modify the interphase physical structure. The synthetic approach to grafting involved the in-situ polymerization of monomers in the presence of functionalized fibers in order to grow chains covalently attached to the fibers. The chemical mechanism may be viewed as the “transesterification of car boxy lated fibers” with acetylated monomers. The monomers used were pimelic acid, p-acetoxybenzoic acid and diacetoxy hydroquinone which are known to yield upon condensation a chemically aperiodic nematic polymer. Evidence for grafting was obtained from X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis on fibers retrieved from composite samples. Interestingly, SEM micrographs of fractured composite specimens containing the mesogen-grafted fibers reveal excellent wetting and interfacial bonding of a liquid crystalline matrix on the carbon surfaces. Based on theoretical considerations for end-adsorbed macromolecules and the nematogenic nature of the grafted chains we infer that dense layers of adsorbed polymer may form at the interfaces studied. From a materials point of view the in situ growth of liquid crystal polymer chains on fibers may offer mechanisms to control composite properties through both bonding and molecular orientation in interfacial regions.     

Amino‐functionalization of carbon fibers through electron‐beam irradiation technique

Amino‐functinonalized carbon fibers were achieved via electron‐beam (EB) irradiation in Diethylenetriamine (DETA) solution and triethylene tetramine (TETA) solution at 200 kGy. Different graft monomer concentrations were investigated to find the optimal concentration of each graft monomer. X‐ray photoelectron spectroscopy, scanning electron microscopy, and Raman spectroscopy were applied to investigate chemical composition and functional groups, topography and disorder degree of amino‐functionalized carbon fibers surface. Meanwhile, adsorption ability and interfacial adhesion between modified carbon fibers and epoxy resin were determined by TGA and interlaminar shear strength (ILSS). It is found that amino‐functionalized carbon fibers which had rougher and more active surface performed better adsorption ability on epoxy resin than untreated fibers. The optimal ILSS values of carbon fiber (treated with DETA and TETA) reinforced composites were 21.37 MPa and 18.28 MPa, which were much higher than that of untreated fiber reinforced composites. The comprehensive results demonstrated that in this condition, the optimal grafting concentrations of both DETA and TETA were 1.5 mol/L. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40274.