Preparation of binary and hybrid epoxy nanocomposites containing graphene oxide and rubber nanoparticles: Fracture toughness and mechanical properties

Binary and hybrid epoxy nanocomposites modified with graphene oxide (GO) and core–shell rubbers (CSR) were synthesized via the solvent-exchange method. X-ray diffraction analysis and scanning electron microscopy of the samples showed a homogeneous dispersion of GO and CSR in the epoxy matrix. The tensile modulus and tensile strength of the samples modified with CSR decreased continuously with increasing CSR content; however, with the addition of only 0.05 phr GO to the neat epoxy and rubber-modified epoxy, these properties significantly increased. The use of GO and CSR individually improved the fracture toughness, but the impact of GO was greater. The simultaneous use of GO and CSR improved both the fracture toughness and the mechanical properties. Our investigation of the toughening mechanism indicated that crack deflection–bifurcation, crack pinning, and particle debonding–pullout in the presence of GO nanosheets and limited rubber particle cavitation contributed to fracture toughness improvement in the hybrid systems. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46988.     

High-performance epoxy nanocomposites via constructing rigid structured interphase with epoxy-rich graphene oxide

Epoxy resins, as the most important thermosetting matrix of carbon fiber reinforced polymer (CFRP) composites, are widely used in the structural field, but the highly intrinsic brittleness of epoxy resins greatly limits their application. Therefore, it is urgent to develop new method to prepare high-performance epoxy composites. In this research, GO riched with rigid short-chain structure epoxy group on its surface was synthesized by chemically grafting dopamine, hexachlorocyclotriphosphazene and glycidol successively. Then the modified nanofillers were incorporated into the epoxy matrix to prepare high-performance nanocomposites. The effect of epoxy-rich GO nanosheets as fillers on mechanical properties of aerospace grade epoxy was studied. The results revealed that the epoxy-rich GO could effectively optimize the performance of epoxy resins owing to forming the rigid structured interphase. The tensile strength and elongation at break of the nanocomposites were up to 113 MPa and 7.6% with 0.075 wt% additives, respectively, which greatly surpassed the value reported by the limited researches on strengthening epoxy with GO and its derivate nanofillers. Therefore, instructive idea and effective method were provided to obtain high-performance polymer nanocomposite matrix in this study.     

Effects of facile amine‐functionalization on the physical properties of epoxy/graphene nanoplatelets nanocomposites

Graphene nanoplatelets (GNPs) have excellent thermal, electrical, and mechanical properties. The incorporation of GNPs into a polymer can remarkably enhance the thermal and mechanical properties of the polymer especially when GNPs are well dispersed in the polymer matrix with strong interfacial bonding. Therefore, in this study, GNPs were amine‐functionalized by covalently bonding 4,4′‐methylene dianiline onto their surfaces via a facile synthetic route. The amine‐functionalization was confirmed by FTIR spectroscopy and TGA. Epoxy/GNPs nanocomposites were prepared and their curing behavior, thermomechanical properties and impact strength were investigated. The amine‐functionalization increased curing rate, storage modulus, thermal dimensional stability, and impact strength of the nanocomposites. The SEM images for the fracture surface of the nanocomposite with amine‐functionalized GNPs showed a smooth and ductile failure‐like surface, resulted from the improved interfacial bonding between GNPs and the epoxy matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42269.     

Preparation and properties of acrylonitrile–butadiene rubber–graphene nanocomposites

The graphene oxide (GO) was prepared by sonication‐induced exfoliation from graphite oxide, which was produced by oxidation from graphite flakes with a modified Hummer's method. The GO was then treated by hydrazine to obtain reduced graphene oxide (rGO). On the basis of the characterization results, the GO was successfully reduced to rGO. Acrylonitrile–butadiene rubber (NBR)–GO and NBR–rGO composites were prepared via a solution‐mixing method, and their various physical properties were investigated. The NBR–rGO nanocomposite demonstrated a higher curing efficiency and a change in torque compared to the gum and NBR–GO compounds. This agreed well with the crosslinking density measured by swelling. The results manifested in the high hardness (Shore A) and high tensile modulus of the NBR–rGO compounds. For instance, the tensile modulus at a 0.1‐phr rGO loading greatly increased above 83, 114, and 116% at strain levels of 50, 100, and 200%, respectively, compared to the 0.1‐phr GO loaded sample. The observed enhancement was highly attributed to a homogeneous dispersion of rGO within the NBR matrix; this was confirmed by scanning electron microscopy and transmission electron microscopy analysis. However, in view of the high ultimate tensile strength, the NBR–GO compounds exhibited an advantage; this was presumably due to strong hydrogen bonding or polar–polar interactions between the NBR and GO sheets. This interfacial interaction between GO and NBR was supported by the marginal increase in the glass‐transition temperatures of the NBR compounds containing fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42457.     

Mechanical properties of graphene nanoplatelet/epoxy composites

Because of their high‐specific stiffness, carbon‐filled epoxy composites can be used in structural components in fixed‐wing aircraft. Graphene nanoplatelets (GNPs) are short stacks of individual layers of graphite that are a newly developed, lower cost material that often increases the composite tensile modulus. In this work, researchers fabricated neat epoxy (EPON 862 with Curing Agent W) and 1–6 wt % GNP in epoxy composites. The cure cycle used for this aerospace epoxy resin was 2 h at 121°C followed by 2 h at 177°C. These materials were tested for tensile properties using typical macroscopic measurements. Nanoindentation was also used to determine modulus and creep compliance. These macroscopic results showed that the tensile modulus increased from 2.72 GPa for the neat epoxy to 3.36 GPa for 6 wt % (3.7 vol %) GNP in epoxy composite. The modulus results from nanoindentation followed this same trend. For loadings from 10 to 45 mN, the creep compliance for the neat epoxy and GNP/epoxy composites was similar. The GNP aspect ratio in the composite samples was confirmed to be similar to that of the as‐received material by using the percolation threshold measured from electrical resistivity measurements. Using this GNP aspect ratio, the two‐dimensional randomly oriented filler Halpin–Tsai model adjusted for platelet filler shape predicts the tensile modulus well for the GNP/epoxy composites. Per the authors' knowledge, mechanical properties and modeling for this GNP/epoxy system have never been reported in the open literature. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nanostructured thermosetting epoxy systems modified with poly(isoprene‐b‐methyl metacrylate) diblock copolymer and polyisoprene‐grafted carbon nanotubes

Nanostructured thermosetting composites based on an epoxy matrix modified with poly(isoprene‐b‐methyl methacrylate) (PI‐b‐PMMA) block copolymer were prepared through PI block segregation. Morphological structures were examined by means of atomic microscopy force microscopy. As epoxy/pristine multi‐walled carbon nanotubes (MWCNT) systems were found to present big agglomerations, with a very poor dispersion of the nanofiller, epoxy/PI‐b‐PMMA/MWCNT systems were prepared by using polyisoprene‐grafted carbon nanotubes (PI‐g‐CNT) to enhance compatibility with the matrix and improve dispersion. It was found that the functionalization of MWCNT with grafted polyisoprene was not enough to totally disperse them into the epoxy matrix but an improvement of the dispersion of carbon nanotubes was achieved by nanostructuring epoxy matrix with PI‐b‐PMMA when compared with epoxy/MWCNT composites without nanostructuring. Nevertheless, some agglomerates were still present and the complete dispersion or confinement of nanotubes into desired domains was not achieved. Thermomechanical properties slightly increase with PI‐g‐CNT content for nanostructured samples, whereas for nonnanostructured epoxy/PI‐g‐CNT composites they appeared almost constant and even decreased for the highest nanofiller amount due to the presence of agglomerates. Compression properties slightly decreased with block copolymer content, while remained almost constant with nanofiller amount. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Functionalization of carbon nanotubes with (3‐glycidyloxypropyl)‐trimethoxysilane: Effect of wrapping on epoxy matrix nanocomposites

In this work, multiwalled carbon nanotubes (MWCNT), after previous oxidation, are functionalized with excess (3‐glycidyloxypropyl)trimethoxysilane (GLYMO) and used as reinforcement in epoxy matrix nanocomposites. Infrared, Raman, and energy‐dispersive X‐ray spectroscopies confirm the silanization of the MWCNT, while transmission electron microscopy images show that oxidized nanotubes presented less entanglement than pristine and silanized MWCNT. Thickening of the nanotubes is also observed after silanization, suggesting that the MWCNT are wrapped by siloxane chains. Field‐emission scanning electron microscopy reveals that oxidized nanotubes are better dispersed in the matrix, providing nanocomposites with better mechanical properties than those reinforced with pristine and silanized MWCNT. On the other hand, the glass transition temperature of the nanocomposite with 0.05 wt % MWCNT‐GLYMO increased by 14 °C compared to the neat epoxy resin, suggesting a strong matrix–nanotube adhesion. The functionalization of nanotubes using an excess amount of silane can thus favor the formation of an organosiloxane coating on the MWCNT, preventing its dispersion and contributing to poor mechanical properties of epoxy nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44245.     

Preparation and properties of styrene‐butadiene rubber nanocomposites blended with carbon black‐graphene hybrid filler

Graphene has become an attractive reinforcing filler for rubber materials, but its dispersion in rubber is still a big challenge. In this work, a novel carbon black‐reduced graphene (CB‐RG) hybrid filler was fabricated and blended with styrene‐butadiene rubber (SBR) via simple two‐roll mill mixing. The prepared CB‐RG hybrids had a microstructure with small CB agglomerates adsorbed onto graphene surfaces. CB acted as a barrier preventing the RG sheets from restacking even after drying. Homogeneous dispersion of graphene sheets in SBR matrix was observed by the mechanical mixing method based on the application of the CB‐RG hybrid fillers. Dynamic mechanical analysis showed that Tg of the SBR/CB‐RG blend was higher than that of the SBR/CB blend indicating strong interfacial interactions between RG and SBR due to the high surface area of graphene and the π‐π interaction between SBR and graphene. The tensile properties of SBR/CB‐RG composites improved significantly and the volume resistivity decreased compared with the SBR/CB blends. The thermal stability of SBR composites filled with CB and CB‐RG showed slight difference. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41309.     

Enhanced interfacial interaction of epoxy nanocomposites with activated graphene nanosheets

The interfacial properties of epoxy nanocomposites reinforced by thermally exfoliated graphene nanosheets (TEG) and activated thermally exfoliated graphene nanosheets (a‐TEG) were compared. The specific surface area (SSA) of a‐TEG with well‐defined micro‐mesopore size distribution was 1000 m²/g, which was much higher that of TEG (550 m²/g). The interfacial interaction between a‐TEG and epoxy was stronger than that of TEG/epoxy owing to their higher SSA and pore size which was proved by dynamic mechanical analysis. As a result, the tensile strength of a‐TEG/epoxy was increased compared with that of TEG/epoxy for all concentrations. In particular, the tensile and flexural strength of a‐TEG/epoxy was increased up to 20 and 50% in comparison to that of TEG/epoxy at 0.05 wt % graphene, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41164.     

Creep characterization of vapor‐grown carbon nanofiber/vinyl ester nanocomposites using a response surface methodology

The effects of selected factors such as vapor‐grown carbon nanofiber (VGCNF) weight fraction, applied stress, and temperature on the viscoelastic responses (creep strain and creep compliance) of VGCNF/vinyl ester (VE) nanocomposites were studied using a central composite design (CCD). Nanocomposite test articles were fabricated by high‐shear mixing, casting, curing, and post curing in an open‐face mold under a nitrogen environment. Short‐term creep/creep recovery experiments were conducted at prescribed combinations of temperature (23.8–69.2°C), applied stress (30.2–49.8 MPa), and VGCNF weight fraction (0.00–1.00 parts of VGCNF per hundred parts of resin) determined from the CCD. Response surface models (RSMs) for predicting these viscoelastic responses were developed using the least squares method and an analysis of variance procedure. The response surface estimates indicate that increasing the VGCNF weight fraction marginally increases the creep resistance of the VGCNF/VE nanocomposite at low temperatures (i.e., 23.8–46.5°C). However, increasing the VGCNF weight fraction decreased the creep resistance of these nanocomposites for temperatures greater than 50°C. The latter response may be due to a decrease in the nanofiber‐to‐matrix adhesion as the temperature is increased. The RSMs for creep strain and creep compliance revealed the interactions between the VGCNF weight fraction, stress, and temperature on the creep behavior of thermoset polymer nanocomposites. The design of experiments approach is useful in revealing interactions between selected factors, and thus can facilitate the development of more physics‐based models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42162.     

Preparation and properties of octadecylamine modified graphene oxide/styrene‐butadiene rubber composites through an improved melt compounding method

Octadecylamine modified graphene oxide/styrene‐butadiene rubber (GO‐ODA/SBR) composites are prepared by a novel and environmental‐friendly method called “Improved melt compounding”. A GO‐ODA/ethanol paste mixture is prepared firstly, and then blended with SBR by melt compounding. GO‐ODA sheets are uniformly dispersed in SBR as confirmed by scanning electron microscope, transmission electron microscopy, and X‐ray diffraction. The interfacial interaction between GO‐ODA and SBR is weaker than that between GO and SBR, which is proved by equilibrium swelling test and dynamic mechanical analysis. GO‐ODA/SBR show more pronounced “Payne effect” than GO/SBR composites, indicating enhanced filler networks resulted from the modification of GO with ODA. GO‐ODA/SBR composite has higher tensile strength and elongation at break than SBR and GO/SBR composite. The tensile strength and elongation at break for the composite with 5 parts GO‐ODA per hundred parts of rubber increase by 208% and 172% versus neat SBR, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42907.     

Conducting epoxy networks modified with non‐covalently functionalized multi‐walled carbon nanotube with imidazolium‐based ionic liquid

Multi‐walled carbon nanotube (MWCNT) was non‐covalently functionalized with room‐temperature ionic liquid (IL), 1‐butyl‐3‐methyl‐imidazolium tetrafluoroborate and blended with epoxy pre‐polymer (ER) with the assistance of ultrasonication in the presence of acetone as a diluting medium. The ability of IL in improving the dispersion of MWCNT in epoxy pre‐polymer was evidenced by transmission optical microscopy. The corresponding epoxy/MWCNT networks cured with anhydride displayed an increase of the electrical conductivity of around three orders of magnitude with the addition of IL in a proportion of MWCNT/IL = 1:5 mass ratio. The effect of IL on dynamic mechanical properties and thermal conductivity was also evaluated. The improved thermal and electrical properties was attributed to the better dispersion of MWCNT within the epoxy matrix by IL, evidenced by transmission electron microscopy of the ER/MWCNT networks cured with anhydride. Raman spectroscopy was also used to confirm the interaction between MWCNT and IL. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43976.     

In situ polymerization of bio‐based thermosetting polyurethane/graphene oxide nanocomposites

Novel bio‐based polyurethane/graphene oxide (GO) nanocomposites have been successfully synthesized from biorenewable epoxidized soybean‐castor oil fatty acid‐based polyols with considerable improvement in mechanical and thermal properties. The GO was synthesized via a modified pressurized oxidation method, and was investigated using Raman spectra, AFM and XPS, respectively. The toughening mechanism of GO in the bio‐based polyurethane matrix was explored. The elongation at break and toughness of polyurethane were increased by 1.3 and 0.8 times with incorporation of 0.4 wt % GO, respectively. However, insignificant changes in both mechanical strength and modulus were observed by adding GO. The results from thermal analysis indicated that the GO acts as new secondary soft segments in the polyurethane which lead to a considerable decrease in the glass transition temperature and crosslink density. The SEM morphology of the fracture surface after tensile testing showed a considerable aggregation of graphene oxide at concentrations above 0.4 wt %. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41751.     

Starch‐graphene oxide bionanocomposites prepared through melt mixing

Bionanocomposites (BNCs) of waxy corn starch, glycerol, and graphene oxide (GO) or graphite oxide (GrO) were prepared by melt mixing. First, the GrO was pre‐exfoliated in a water solution using ultrasound at 1 wt %. Small‐angle X‐ray scattering was used to determinate the interlaminar separation of GrO and transmission electron microscopy, Fourier infrared spectroscopy, and thermogravimetric analysis were used to characterized the GrO. Next, BNCs were characterized by X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and mechanical property measurements. A complete exfoliation of GrO was obtained in the waxy corn matrix. Amorphous X‐ray patterns of the BNCs were observed, indicating that the exfoliated GO avoid the retrogradation of starch. According to scanning electron microscopy results, the BNCs showed an irregular texture and a good dispersion of GO, while thermoplastic starch showed a smooth morphology with a fragile structure. The BNCs exhibited higher thermal stability than thermoplastic starch. The tensile strength and the Young's modulus increased by 140% and 230% at a GO loading levels of 0.5% due to good interfacial interactions of GO and the waxy corn starch matrix. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46037.     

Physicochemical and antibacterial properties of chitosan‐polyvinylpyrrolidone films containing self‐organized graphene oxide nanolayers

Chitosan films have a great potential to be used for wound dressing and food‐packaging applications if their physicochemical properties including water vapor permeability, optical transparency, and hydrophilicity are tailored to practical demands. To address these points, in this study, chitosan (CS) was combined with polyvinylpyrrolidone (PVP) and graphene oxide (GO) nanosheets (with a thickness of ～1 nm and lateral dimensions of few micrometers). Flexible and transparent films with a high antibacterial capacity were prepared by solvent casting methods. By controlling the evaporation rate of the utilized solvent (1 vol % acidic acid in deionized water), self‐organization of GO in the polymer matrix was observed. The addition of PVP to the CS/GO films significantly increased their water vapor permeability and optical transmittance. A blue shift in the optical absorption edge was also noticed. Thermal analysis coupled with Fourier transform infrared spectroscopy suggested that the superior thermal stability of the nanocomposite films was due to the formation of hydrogen bonds between the functional groups of chitosan with those of the graphene oxide. An improved bactericidal capacity of the nanocomposite films against gram‐positive Staphylococcus aureus and gram‐negative Escherichia coli bacteria was also observed. Highly flexible, transparent (opacity of 6.95), and antimicrobial CS/25 vol % PVP/1 wt % GO films were prepared. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43194.     

Graphene oxide reinforced chitosan/polyvinylpyrrolidone polymer bio‐nanocomposites

Bio‐nanocomposite films based on chitosan/polyvinylpyrrolidone (CS/PVP) and graphene oxide (GO) were processed using the casting/evaporation technique. It has been found that the three components of bio‐nanocomposites can be easily mixed in controlled conditions enabling the formation of thick films with high quality, smooth surface and good flexibility. Structural and morphological characterizations showed that the GO sheets are well dispersed in the CS/PVP blend forming strong interfacial interactions that provide an enhanced load transfer between polymer chains and GO sheets thus improving their properties. It has been found that the water resistance of the CS/PVP blend is improved, and the hydrolytic degradation is limited by addition of 0.75 and 2 wt % GO. The modulus, strength, elongation and toughness of the bio‐nanocomposites are together increased. Herein, the steps to form new bio‐nanocomposite films have been described, taking the advantage of the combination of CS, PVP and GO to design the aforementioned bio‐nanocomposite films, which allow to have extraordinary properties that would have promising applications as eventual packaging materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41042.     

In situ fast polymerization of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites

A series of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites (GNS/PMMA) is successfully prepared by an in situ fast polymerization method with graphene weight fractions from 0.1 to 2.0 wt %. In situ polymerization is effective in well dispersing of GNS in matrixes and suitable for both low and high content of GNS. The synthesis processes of polymer composites could be simplified and fast by using industrial grade graphene. The GNS fillers are found to disperse homogeneously in the PMMA matrix. The maximum electrical conductivity of the composites achieves 0.57 S m^?1, with an extremely low percolation threshold of 0.3 wt %. The electrical conductivities are further predicted by percolation theory and found to agree well with the experimental results. The results indicate that the microstructures, thermal, electrical, and mechanical properties of PMMA polymer are significantly improved by adding a low amount of graphene nanosheets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43423.     

A liquid‐like multiwalled carbon nanotube derivative and its epoxy nanocomposites

Multiwall carbon nanotubes (MWCNTs) with liquid‐like behavior at room temperature were prepared with sulfonic acid terminated organosilanes as corona and tertiary amine as canopy. The liquid‐like MWCNT derivative had low viscosity at room temperature (3.89 Pa s at 20°C) and exhibited non‐Newtonian shear‐thinning behavior. The weight fraction of MWCNT in the derivative was 16.72%. The MWCNT derivative showed very good dispersion in organic solvents, such as ethanol and acetone. The liquid‐like MWCNT derivative was incorporated into epoxy matrix to investigate the mechanical performance of the nanocomposites and the distribution of MWCNTs in the matrix. When the liquid‐like MWCNT derivative content was up to 1 wt %, the flexural strength and impact toughness of composites were 12.1 and 124% higher than the pure epoxy matrix, respectively. Transmission electron microscope (TEM) confirmed the very good dispersion of the liquid‐like MWCNT derivative in epoxy matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2217–2224, 2013     

Probing the reinforcing mechanism of graphene and graphene oxide in natural rubber

Natural rubber (NR) containing graphene (GE) and graphene oxide (GO) were prepared by latex mixing. The in situ chemically reduction process in the latex was used to realize the conversion of GO to GE. A noticeable enhancement in tensile strength was achieved for both GO and GE filled NR systems, but GE has a better reinforcing effect than GO. The strain‐induced crystallization was evaluated by synchrotron wide‐angle X‐ray diffraction. Increased crystallinity and special strain amplification effects were observed with the addition of GE. The incorporation of GE produces a faster strain‐induced crystallization rate and a higher crystallinity compared to GO. The entanglement‐bound tube model was used to characterize the chain network structure of composites. It was found that the contribution of entanglement to the conformational constraint increases and the network molecular parameters changes with the addition of GE and GO, while GE has a more evident effect than GO. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of cellulose–graphene oxide aerogels with N‐methyl morpholine‐N‐oxide as a solvent

Cellulose–graphene oxide (GO) aerogel composites were successfully prepared from cellulose and GO dispersed in N‐methyl morpholine‐N‐oxide monohydrate, a nontoxic and environmentally friendly solvent, after a freeze‐drying process. Because of the strong interactions between the numerous oxygen‐containing groups located on the surface of GO and the functional groups of the cellulose molecules, the GO monolayers were well dispersed in the three‐dimensional porous structure of the cellulose aerogels. With the addition of 10 wt % GO, the swelling ratios and water contents of the composite cellulose–GO aerogels increased from 468 to 706% and from 82.4% to 87.6%, respectively. The corresponding maximum decomposition temperatures also increased from 335 to 353 °C with increasing GO content from 0 to 10%; this indicated that the thermal stability of the cellulose–GO aerogels was enhanced. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46152.