Molecular-level dispersion of graphene into epoxidized natural rubber: Morphology,interfacial interaction and mechanical reinforcement

The interfacial interaction of composites dominates the properties of polymeric/inorganic nanocomposites. Herein, epoxy and hydroxyl groups are introduced into the natural rubber (NR) molecular chains to anchor oxygenous functional groups on the surface of graphene oxide (GO) sheets and therefore enhance the interfacial interaction between GO and rubber. From the morphological observation and interaction analysis, it is found that epoxidized natural rubber (ENR) latex particles are assembled onto the surfaces of GO sheets by employing hydrogen bonding interaction as driving force. This self-assembly depresses restacking and agglomeration of GO sheets and leads to homogenous dispersion of GO within ENR matrix. The formation of hydrogen bonding interface between ENR and GO demonstrates a significant reinforcement for the ENR host. Compared with those of pure ENR, the composite with 0.7 wt% GO loading receives 87% increase in tensile strength and 8.7 fold increase in modulus at 200% elongation after static in-situ vulcanization.     

Effects of surface modification on rheological and mechanical properties of CNT/epoxy composites

Despite superior properties of carbon nanotubes (CNTs), physical properties of the CNT/epoxy composites are not improved significantly because interfacial bonding between the CNTs and the polymer matrix is weak. CNTs were treated by an acidic solution to remove impurities and modified subsequently by amine treatment or plasma oxidation to improve interfacial bonding and dispersion of nanotubes in the epoxy matrix. The functional groups on the surface of treated CNTs were investigated by X-ray photoelectron spectroscopy. The surface modified CNTs were embedded in the epoxy resin by ultra-sonication and the cured nanotube containing composites were characterized by field emission scanning electron microscopy. Rheological properties of nanotube containing epoxy resin and mechanical properties of the modified CNT/epoxy composites were improved because the modification of CNTs improved dispersion and interaction between the CNT and the epoxy resin.     

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     

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

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

Improvement of dispersion of carbon nanotubes in epoxy resin through pyrogallol functionalization

Multiwalled carbon nanotubes (MWNTs) were functionalized with pyrogallol. The functionalized MWNTs were well‐dispersed in the epoxy/curing agent/ethanol solution, as demonstrated by UV‐vis spectra and optical micrographs. Epoxy resin/MWNTs composites were prepared via solution mixing method. The cure behavior was characterized using differential scanning calorimetry. Pyrogallol‐functionalized carbon nanotubes (CNTs) reacted with the epoxy through the mediation reaction of pyrogallol with the curing agent, leading to the interfacial bonding between the functionalized carbon nanotubes (CNTs) and the resin matrix. Due to the excellent dispersion and interfacial bonding, the mechanical strength and electrical conductivity of the epoxy resin/CNTs composites have been improved. POLYM. ENG. SCI. 56:1079–1085, 2016. © 2016 Society of Plastics Engineers     

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     

Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties

Epoxy composites filled with both graphene oxide (GO) and diglycidyl ether of bisphenol-A functionalized GO (DGEBA–f–GO) sheets were prepared at different filler loading levels. The correlations between surface modification, morphology, dispersion/exfoliation and interfacial interaction of sheets and the corresponding mechanical and thermal properties of the composites were systematically investigated. The surface functionalization of DGEBA layer was found to effectively improve the compatibility and dispersion of GO sheets in epoxy matrix. The tensile test indicated that the DGEBA–f–GO/epoxy composites showed higher tensile modulus and strength than either the neat epoxy or the GO/epoxy composites. For epoxy composite with 0.25 wt% DGEBA–f–GO, the tensile modulus and strength increased from 3.15 ± 0.11 to 3.56 ± 0.08 GPa (∼13%) and 52.98 ± 5.82 to 92.94 ± 5.03 MPa (∼75%), respectively, compared to the neat epoxy resin. Furthermore, enhanced quasi-static fracture toughness (K_IC) was measured in case of the surface functionalization. The GO and DGEBA–f–GO at 0.25 wt% loading produced ∼26% and ∼41% improvements in K_IC values of epoxy composites, respectively. Fracture surface analysis revealed improved interfacial interaction between DGEBA–f–GO and matrix. Moreover, increased glass transition temperature and thermal stability of the DGEBA–f–GO/epoxy composites were also observed in the dynamic mechanical properties and thermo-gravimetric analysis compared to those of the GO/epoxy composites.     

Mechanical properties and interfacial characteristics of 2.5D SiNOf/BN wave-transparent composites

2.5D SiNO_f/BN wave-transparent composites were fabricated by borazine infiltration and pyrolysis route at 800 °C?1400 °C. The fracture behavior of the composites was investigated on the basis of the retained fiber strength, in-situ fiber and matrix mechanical properties, and fiber/matrix bonding strength. Nano-indentation were employed to determine the in-situ elastic modulus and hardness of the fiber and BN matrix, and single-fiber push-out experiments were performed to quantify the fiber/matrix bonding strength. The interfacial characteristics of the 800 °C?1200 °C fabricated composites were further studied in terms of physical bonding and chemical reaction. Physical bonding was resulted from thermal mismatch between the fiber and matrix, which induced compressive radial stress at the interface. The radial stress increased continuously with increasing fabrication temperature. Meanwhile, the TEM analysis confirmed chemical diffusion at the fiber/matrix interface, which further improved the interfacial bonding strength. The chemical reaction mechanism was proposed.     

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     

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     

Preparation and properties of dopamine reduced graphene oxide and its composites of epoxy

To improve the thermal and mechanical properties and further to expand its applications of epoxy in electronic packaging, reduced graphene oxide/epoxy composites have been successfully prepared, in which dopamine (DA) was used as reducing agent and modifier for graphene oxide (GO) to avoid the environmentally harmful reducing agents and address the problem of aggregation of graphene in composites. Further studies revealed that DA could effectively eliminate the labile oxygen functionality of GO and generate polydopamine functionalized graphene oxide (PDA‐GO) because DA would be oxidated and undergo the rearrangement and intermolecular cross‐linking reaction to produce polydopamine (PDA), which would improve the interfacial adhesion between GO and epoxy, and further be beneficial for the homogenous dispersion of GO in epoxy matrix. The effect of PDA‐GO on the thermal and mechanical properties of PDA‐GO/epoxy composites was also investigated, and the incorporation of PDA‐GO could increase the thermal conductivity, storage modulus, glass transition (T_g), and dielectric constant of epoxy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39754.     

Effect of Dodecyal Amine Functionalized Graphene on the Mechanical and Thermal Properties of Epoxy‐Based Composites

Simultaneous surface functionalization and reduction of graphene oxide (GO) was achieved by using dodecyl amine (DA) as surface modifying agent. The DA modified reduced GO (DA‐G) was used for subsequent preparation of DA‐G/epoxy composites by solution mixing. Fourier transform infrared spectroscopy analysis, X‐ray diffraction (XRD) and electrical conductivity measurements were conducted to establish the concurrent functionalization and reduction of GO. The effect of DA‐G on the epoxy composites at 0 to 0.75 wt% loadings was studied by investigating its static and dynamical mechanical properties. XRD study was performed to verify the dispersion of DA‐G in the epoxy polymer. Field emission scanning electron microscopy was used to investigate the fracture surface morphology of the composites and Transmission electron microscopy was employed to further confirm the dispersion of DA‐G in the matrix. It was found that the tensile strength of the composite was increased by 38.8% with the addition of 0.5 wt% of DA‐G. The good adhesion/interaction between DA‐G and epoxy resulted in the increase of storage modulus; however, glass transition temperature (T_g) value of the composites shifted to lower temperature in comparison to the neat epoxy. Thermogravimetric analysis showed small decrease in onset degradation temperature for the composites as compared to neat epoxy except for the composites containing 0.75 wt% of DA‐G. POLYM. ENG. SCI., 56:1221–1228, 2016. © 2016 Society of Plastics Engineers     

Epoxy composites based on amino‐silylated MMT: The role of interfaces and clay morphology

Epoxy‐based composites containing sodium montmorillonite (MMT) modified by silylation reaction with 3‐aminopropyltriethoxysilane (A1100) and N‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane (A1120) were prepared. The effect of MMT chemical functionalization, as well as inorganic content and dispersion method (i.e., sonication or combination of sonication and ball‐milling) on the morphology and mechanical and thermal properties of composites was thoroughly investigated by X‐ray diffraction analysis, dynamic mechanical and tensile static analysis, nanoindentation measurements and cone calorimeter tests. Morphological characterization showed that the MMT particles are only slightly intercalated by epoxy molecules. Tensile stress, elongation at failure, and toughness of the epoxy composites based on silylated MMT were found to be improved. The presence of 1 and 3% wt/wt of A1100 and A1120 silylated MMT clays allowed the tensile elastic modulus to increase respectively, of about 10 and 15% with respect to the pristine epoxy matrix. The overall results showed that (1) the silylation of MMT clays is a valuable method to improve the interfacial interaction between filler and epoxy matrix and (2) the interfacial interaction plays a role more significant than the clay morphology (i.e., the extent of clay intercalation/exfoliation) over the composite properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of Fiber Surface Modification on the Mechanical Performance of Isora-Polyester Composites

This paper reports the effect of chemical treatment on the mechanical properties of a natural fiber, isora, as reinforcement in unsaturated polyester resin. Isora fiber is separated from the bark of the Helicteres isora plant by a retting process. The short isora fiber surface was modified chemically by acetylation, benzoylation, silane and triton treatments to bring about improved interfacial interaction between the fiber and the polyester matrix. The modified surfaces were characterized by IR spectroscopy and SEM. The SEM studies were carried out to investigate the fiber surface morphology, fiber pull-out and fiber-polyester interface bonding. They showed the changes occuring on the fiber surface during chemical treatment. Properties like tensile strength, flexural strength and impact strength have been studied. The chemical modification of fiber improved fiber/matrix interaction as evidenced by the enhanced tensile and flexural properties. The lower impact properties of the composites, except triton-treated fiber composite, further point to the improved fiber/matrix adhesion, compared to the untreated fiber composites.     

Dispersion, interfacial interaction and re-agglomeration of functionalized carbon nanotubes in epoxy composites

The surface, interfacial and dispersion properties of carbon nanotubes (CNTs), and the mechanical properties of the CNT/epoxy composites affected by CNT functionalization are investigated. It is demonstrated that there exists strong correlations between amino-functionalization, dispersion, wettability, interfacial interaction and re-agglomeration behaviour of CNTs and the corresponding mechanical and thermo-mechanical properties of CNT/epoxy composites. The amino-functionalized CNTs exhibit higher surface energy and much better wettability with epoxy resin than the pristine CNTs, and the attached amine molecules arising from the functionalization effectively inhibit the re-agglomeration of CNTs during the curing of resin. These ameliorating effects along with improved interfacial adhesion between the matrix and functionalized CNTs through covalent bonds result in improved flexural and thermo-mechanical properties compared with those without functionalization.     

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.     

Performance tuning of glass fiber/epoxy composites through interfacial modification upon integrating with dendrimer functionalized graphene oxide

In this study, glass fiber/epoxy composites were interfacially tailored by introducing polyamidoamine (PAM) dendrimer functionalized graphene oxide (GO) into epoxy matrix. Two different composites each containing varying loading fraction (0.5, 1.0, and 1.5 wt%) of GO and GO-PAM were fabricated via hot press processing. Composites were evaluated for interlaminar shear strength (ILSS), dynamic mechanical properties and thermal conductivity. The inclusion of 1.5 wt% GO-PAM resulted ~57.3%, ~42.7%, and ~54% enhancement in ILSS, storage modulus and thermal conductivity, respectively. Almost, ~71% reduction in coefficient of thermal expansion was also observed at same GO-PAM loading. Moreover, higher glass transition temperature was observed with GO-PAM addition. GO-PAM substantially improved fiber/matrix interfacial adhesion, which was witnessed through scanning electron microscopy. The enhanced thermo-mechanical performance was attributed to interfacial covalent interactions engendered by ring opening reaction between epoxy and amine moieties of PAM dendrimers. These multiscale composites with extraordinary functional properties can outperform conventional counterparts with improved reliability and performance.     

Tailoring Carbon Fiber/Carbon Nanotubes Interface to Optimize Mechanical Properties of Cf‐CNTs/SiC Composites

C_f/SiC composites were fabricated using fiber coatings including CNTs and matrix infiltration using the polymer impregnation and pyrolysis process. Interface between fiber and CNTs (CF/CNTs) was tailored to optimize mechanical properties of hybrid composites. The tailored interphases, such as Pyrocarbon (PyC) and PyC/SiC, protect fibers from degradation during the growth of CNTs successfully. Hybrid composites with well‐tailored CF/CNTs interface displayed significantly increased mechanical strength (352 ± 21 MPa) compared with that (34 ± 3 MPa) of composites reinforced with CNTs, which grown on carbon fibers directly. The interfacial bonding strength of hybrid composites was improved and optimized by tailoring the CF/CNTs interface. Interfacial failure modes were studied, and a firm interface bonding at the joint where CNTs grown was observed.     

On adhesion mechanisms and interfacial strength in acrylonitrile–butadiene–styrene/wood sawdust composites

Adhesion mechanisms and interfacial strengths of acrylonitrile–butadiene–styrene (ABS) copolymer/wood sawdust composites containing two different silane coupling agents [3-Methacryloxypropyl trimethoxysilane (KBM503) and N-2(aminoethyl)3-aminopropyl trimethoxysilane (KBM603)] were studied using the Fourier Transform Infrared (FTIR) technique and mechanical testing. The results suggested that increasing wood sawdust content tended to increase the modulus of the composites, but decreased the strength of the composites. Concentrations of 1.0 wt% KBM503 and 0.5 wt% KBM603 were recommended for the optimization of the mechanical properties of the composites, respectively. Up to the recommended dosages, KBM603 was more effective in terms of the improved interfacial strength of the composites. The adhesion mechanism performed by KBM503 involved dipole–dipole interaction at the ABS/sawdust interface, whereas that by KBM603 was associated with covalent chemical bonds at the interface. The improved interfacial strength of the composites was reduced by the increased amounts of wood sawdust particles.     

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