Investigation of thermal behaviour and mechanical property of the functionalised graphene oxide/epoxy resin nanocomposites

ABSTRACT

Graphite oxide (GO) and functionalised graphite oxide (FGO) were successfully prepared with -NH₂-terminated GO in the paper, and their chemical structures were characterised with Fourier transform infrared (FTIR), Energy-Dispersive X-ray Spectroscopy (EDS), UV spectrum analysis and XRD, their microstructures were researched by a scanning electron microscope (SEM) and a transmission electron microscope (TEM), and their thermal properties were characterised by TG. The result showed the carbon residue of FGO was 82.1% and the residual char of GO was 48%, the composite materials were prepared with curing for epoxy resin. The thermal stability, mechanical properties, and morphology after impacting tests of composite materials were investigated using thermogravimetric analysis, tensile and charpy impact tests and SEM. The result showed when the 0.2% FGO was filled into the epoxy, the tensile strength was 55.4?MPa, the impact strength was 17.3?KJ/m², the flexural strength was 82?MPa, and the flexural modulus was 2760?MPa. The mechanical properties of composite materials were higher than those of pure epoxy and improved the strength and toughness of epoxy nanocomposites.     

Silane-functionalized graphene oxide/epoxy resin nanocomposites: Dielectric and thermal studies

Improved dispersion of graphene oxide (GO) in the epoxy resin, as nanofiller, requires surface modification. Hence, functionalization of GO with small silane (GONSi) and bulky silane moieties (GOSi) has been carried out. Structural confirmation analysis of the prepared GO and modified forms have been performed using different analytical techniques. Cationic photocuring polymerization of pure aliphatic epoxy resin (CE) and loaded samples with GO, GOSi, or GONSi in amounts 0.5 and 1 wt % has been followed by FTIR. Loading of CE showed a passive effect for the modified filler on the conversion of the CE during photocuring, whereas the thermal stability of loaded epoxy resin is enhanced. Dielectric properties investigations revealed that the insulation feature of CE is not seriously reduced by the addition of GO or its modified forms. The secondary relaxation β process originating from the fluctuations of the side functional hydroxyl group can be described by the semi-empirical Cole–Cole function. The dielectric loss values are decreasing in the order GONSi > GOSi > GO > CE. Furthermore, it was found that the activation energy of the dynamic process is related to the conversion and to the ratio of the modified filler. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48253.     

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.     

氧化石墨烯改性环氧树脂涂料的制备及防腐性能

环氧树脂在溶剂蒸发过程中容易产生微孔,影响其防腐蚀性能。为了提高其对腐蚀介质的阻碍能力,本文采用密闭氧化法制备氧化石墨烯,再利用湿式转移法将氧化石墨烯水溶液分散在环氧树脂中,制备氧化石墨烯/环氧树脂防腐涂料。通过红外光谱（FTIR）、X射线衍射（XRD）和拉曼光谱（Raman）分析氧化石墨烯的结构变化,利用开路电位测试（OCP）、水接触角、腐蚀形貌和气体透过率分析氧化石墨烯/环氧树脂涂料的防腐性能。结果表明,氧化石墨烯/环氧树脂（GO/EP）涂料的开路电位和水接触角分别为0.181V和86.12°,与纯环氧树脂涂料相比,分别提高了0.066V和10.5°;当GO/EP浸泡在3.5%NaCl溶液中腐蚀20天后,表面仅产生了粗糙化,涂层稳定性好,屏障性能强;与EP涂层相比,GO/EP涂层的O₂和H₂O渗透率分别降低了51.2%和65.5%。     

Polyaniline nanorod adsorbed on reduced graphene oxide nanosheet for enhanced dielectric,viscoelastic and thermal properties of epoxy nanocomposites

In this work, polyaniline nanorod adsorbed on reduced graphene oxide (P@G) hybrid filler was prepared via in situ polymerization of aniline monomer in the presence of reduced graphene oxide as template. Fourier transform infrared, X-ray diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy images revealed the formation of P@G hybrid. The P@G hybrid was dispersed in dichlorobenzene and then introduced into epoxy resin at different loadings. The epoxy nanocomposites containing 9 wt% P@G hybrids (E/P@G9) exhibited a maximum DC conductivity of 1.34 × 10⁻⁵ S/cm that is eight orders higher compared to pure epoxy. At 10³ Hz, a dielectric constant (ε′) of 163 was attained for E/P@G9, nearly 34 times higher than pure epoxy. A percolation threshold of 4 vol% was observed for ε′. Dynamic mechanical studies showed that significant enhancement in storage modulus values were exhibited for 3 and 5 wt% of hybrids. The glass transition temperature showed a maximum shift of 10°C to higher temperatures at 3 wt% loading of P@G hybrids (E/P@G3). The tensile strength, Young's modulus, and impact strength of the E/P@G3 nanocomposites enhanced by 19.7, 72, and 12%, respectively. The thermal stability of the epoxy nanocomposites also enhanced with the addition of P@G hybrid.     

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.     

Synthesis of modified graphene oxide and its improvement on flame retardancy of epoxy resin

In this work, the small molecule with double-phosphaphenanthrene structure was successfully grafted on the surface of graphene oxide (GO), which is called functionalized graphene oxide (FGO). The introduction of FGO improved the poor interfacial compatibility between graphene and epoxy matrix. And FGO could be used as the highly effective flame retardant. The thermogravimetric analysis results showed a significant improvement in the char yield of cured FGO/EP. When the content of FGO was 3 wt %, the limiting oxygen index value reached 30.4%. At the same time, the three-point bending and thermomechanical tests confirmed that the mechanical properties of the epoxy resin composites were improved. Based on the char analyses of SEM images and Raman spectroscopy, the flame retardant could promote the formation of a stable carbon layer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47710.     

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.     

氧化石墨烯-水性环氧树脂固化剂的制备及性能

以三乙烯四胺（TETA）,氧化石墨烯（GO）,环氧树脂E44、三羟甲基丙烷三缩水甘油醚（TPEG）、甲基聚氧乙烯环氧基醚（MEH）和γ-(2,3-环氧丙氧)丙基三甲氧基硅烷（KH560）为原料,采用原位聚合法首先将TETA与GO球磨分散,使TETA与GO通过共价键相连,然后依次滴加E44、TPEG、MEH和KH560合成氧化石墨烯-水性环氧树脂固化剂（TGO-WPEA）,再与环氧树脂乳液（Epikote-6520）复合制得氧化石墨烯改性水性环氧树脂防腐涂料（TGO-EP）。通过FTIR、XPS和XRD对纳米材料进行结构表征,采用电化学测试和盐雾实验对复合涂层TGO-EP的防腐性能进行了研究。结果表明,固化剂分子通过共价键连接到GO表面,改善了GO在环氧树脂中的分散稳定性和接枝率,提高了TGO-EP复合涂料对腐蚀介质的屏蔽性能。与EP涂层相比,其腐蚀电位从-0.267mV提高到-0.125mV,腐蚀电流密度从5.44×10-8减小到1.09×10-8 A/cm2;EIS测试表明,浸泡20d后,TGO-EP仍具有最高的低频阻抗。     

Effect of polythiourethane hardener modification on the behaviour of epoxy resin

Polythiourethanes based on oligomeric polymercaptans were employed as curing agent of epoxy resin. The epoxy matrices, in the form of castings, were characterized for their mechanical properties such as tensile strength, elongation at break and unnotched Charpy impact strength as per ISO methods. Mechanical studies indicated that the incorporation of polythiourethane into epoxy resin improves the toughness and flexibility with reduction in tensile strength for samples cured at ambient conditions and influences the mechanical and thermal properties according to its percentage content for samples cured at 130°C. The high increase of impact strength was explained by the development of two-phase morphology during the cure process. The results of this study indicate that both the stoichiometry of the curing mixture and the initial thermal condition are of critical importance in governing the curing mechanism, structure of the network, morphology and the final properties of epoxy/polythiourethane compositions.     

石墨烯改性对环氧树脂/碳纤维复丝拉伸性能的影响

采用直接分散法和上浆剂法分别制备了环氧树脂/碳纤维复丝,通过红外光谱、分光光度法等分析方法对处理的石墨烯的表面官能团及表面形貌进行表征,借助扫描电子显微镜对碳纤维表面进行微观形貌观察,研究了石墨烯改性对环氧树脂/碳纤维复丝界面性能的影响。结果表明:石墨烯表面成功地接枝了硅烷偶联剂KH-560;接枝硅烷偶联剂KH-560的石墨烯的环氧树脂/碳纤维复丝的拉伸性能优于未经改性的石墨烯的复丝;上浆法制得的环氧树脂/碳纤维复丝的拉伸性能优于分散法制得的复丝的拉伸性能;上浆剂法制备的石墨烯改性的环氧树脂/碳纤维复丝的断裂强力比未经过改性的未上浆的复丝的提高了48.6%,拉伸强度提高了30.4%,断裂伸长率提高了90.9%。     

Chitosan–graphene oxide nanocomposites: Effect of graphene oxide nanosheets and glycerol plasticizer on thermal and mechanical properties

In this study, graphite oxide (GO) is synthesized from natural graphite flakes by the modified Hummers method. Characterization by Fourier transform infrared, X‐ray photoelectron, Raman and ultraviolet‐visible spectroscopies, X‐ray diffraction, and thermogravimetric analysis is conducted on GO to confirm the oxidation of graphite. Unplasticized and glycerol plasticized chitosan/graphene oxide (CS/GO) nanosheets nanocomposites with different GO loadings are prepared by solution casting. The combined effect of GO and glycerol on structure, thermal and mechanical properties of nanocomposite films is studied. GO nanosheets are well dispersed throughout the CS matrix due to the hydrogen bonding and electrostatic interactions between CS and GO nanosheets. The incorporation of GO within the CS matrix results in a decrease of the crystallinity, an improvement of thermal stability, and a significant enhancement of the stiffness and tensile strength that is emphasized by the glycerol. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45092.     

Effect of nitrile functionalized graphene on the properties of poly(arylene ether nitrile) nanocomposites

In this study, novel nitrile functionalized graphene (GN‐nitrile)/poly(arylene ether nitrile) (PEN) nanocomposites were prepared by an easy solution‐casting method and investigated for the effect of surface modification on the dielectric, mechanical and thermal properties. Graphene (GN) was first functionalized by introduction of nitrile groups onto the GN plane, which was confirmed by scanning electron microscopy, differential scanning calorimetry, Fourier transform infrared spectroscopy, thermogravimetric analysis and dispersibility research. Compared with pure GN, the grafted nitrile groups on the GN‐nitrile can interact with nitrile groups in PEN and lead to flat but better dispersion and stronger adhesion in/to the PEN matrix. Consequently, GN‐nitrile had a more significant enhancement effect on the properties of PEN. The dielectric constant of the PEN/GN‐nitrile nanocomposite with 5 wt% GN‐nitrile reaches 11.5 at 100 Hz, which is much larger than that of the pure PEN matrix (3.1). Meanwhile, dielectric loss is quite small and stable and the dielectric properties showed little frequency dependence. For 5 wt% GN‐nitrile reinforced PEN composites, increases of 17.6% in tensile strength, 26.4% in tensile modulus and 21 °C in T_d5% were obtained. All PEN/GN‐nitrile nanocomposite films can stand high temperature, up to 480 °C. Hence, novel dielectric PEN/GN‐nitrile nanocomposite films with excellent mechanical and thermal properties can be used as dielectric materials under some critical circumstances such as high wear and temperature. Copyright © 2012 Society of Chemical Industry     

Reinforcing effects of aminosilane-functionalized graphene on the tribological and mechanical behaviors of epoxy nanocomposites

In this study, aminopropyl trimethoxysilane as an interfacial modifier was introduced on the surface of graphene (Gr) nanoplatelets. The effects of the silane-modified graphene (SGr) loading (0, 0.05, 0.1, 0.3, and 0.5 wt %) and silane modification on the tensile, compressive, interlaminar shear stress (ILSS), and tribological properties of the epoxy-based nanocomposites were investigated. Out of these specimens, the highest values of ILSS and compressive strength were related to the 0.3 wt % SGr–epoxy nanocomposite. The addition of SGr enhanced the tensile strength and strain to failure only at low contents (i.e., 0.05 wt %). Also, the tensile and compressive moduli were improved, and the highest values were observed at a 0.5 wt % SGr loading. In addition, decreases of approximately 40 and 68% in the coefficient of friction and wear rate, respectively, were observed at a 0.3 wt % SGr loading. Enhanced tensile, compressive, ILSS, and wear properties in the SGr–epoxy specimens were observed compared to those in the Gr–epoxy specimens. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47410.     

Preparation of graphene/poly(vinyl alcohol) nanocomposites with enhanced mechanical properties and water resistance

The control and dispersal of graphene nanosheets in polymer hosts are challenges in the development of high‐performance graphene‐based nanocomposites due to the strong interlayer cohesive energy and surface inertia. Here we report a simple and practical approach to synthesize graphene‐reinforced poly(vinyl alcohol) (PVA) composite films by incorporating graphene oxide and graphene into PVA aqueous solution. The resulting nanocomposites revealed increases of up to 212% in tensile strength and 34% in elongation at break with only 0.5 wt% graphene content. Water absorption measurements showed that the water absorption ratio of the graphene/PVA composites decreased from 105.2 to 48.8%, and the barrier properties were obviously improved. Contact angle measurements showed that the composites were hydrophobic (θ > 90°) in contrast to the highly hydrophilic (θ < 90°) pure PVA. Copyright © 2011 Society of Chemical Industry     

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     

Electrical ac and dc behavior of epoxy nanocomposites containing graphene oxide

This article deals with the investigation of electrical properties of epoxy‐based nanocomposites containing graphene oxide nanofillers dispersed in the polymer matrix through two‐phase extraction. Broadband dielectric spectroscopy and dc electrical conductivity as a function of electric field have been evaluated in specimens containing up to 0.5 wt % of nanofiller. Nanocomposites containing pristine graphene oxide do not show significant changes of electrical properties. On the contrary, the same materials after a proper thermal treatment at 135°C, able to provoke the in situ reduction of graphene oxide, exhibit higher permittivity and electrical conductivity, without showing large decrease of breakdown voltage. Moreover, a nonlinear behavior of the electrical conductivity is observed in the range of electric fields investigated, i.e. 2–30 kV mm^?1. A new relaxation phenomenon with a very low temperature dependence is also evidenced at high frequency in reduced graphene oxide composites, likely associated to induced polarization of electrically conductive nanoparticles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41923.     

Preparation and characterization of epoxy nanocomposites containing surface‐modified graphene oxide

A three‐step grafting procedure has been used to graft the epoxy monomers (DER332) and the curing agents (diamino diphenyl methane (DDM), onto graphene oxide (GO) surface. The surface modification of GO has been performed by grafting of Jeffamine D‐2000, followed with subsequent grafting of DER332 and DDM, respectively. Fourier transform spectroscopy and thermogravimetric analysis indicate successful surface modification. The resulting modified GO, that is, (DED)‐GO, can be well dispersed in the epoxy monomers. The epoxy nanocomposites containing different GO contents can then be prepared through curing processes. The dispersion of GO in the nanocomposites is characterized by transmission electron microscopy. It is found that the tensile strength and elongation at break of epoxy nanocomposite with only 0.2 wt % DED‐GO are increased by 30 and 16% as compared with the neat epoxy resin, respectively. Dynamic mechanical analysis results show that 62% increase in storage modulus and 26°C enhancement in the glass transition temperature of the nanocomposite have been achieved with the incorporation of only 0.2 wt % of DED‐GO into the epoxy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40236.     

Characterization and performance of dodecyl amine functionalized graphene oxide and dodecyl amine functionalized graphene/high‐density polyethylene nanocomposites: A comparative study

Dodecyl amine (DA) functionalized graphene oxide(DA‐GO) and dodecyl amine functionalized reduced graphene oxide (DA‐RGO) were produced by using amidation reaction and chemical reduction, then two kinds of well dispersed DA‐GO/high‐density polyethylene (HDPE) and DA‐RGO/HDPE nanocomposites were prepared by solution mixing method and hot‐pressing process. Thermogravimetric, X‐ray photoelectron spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffractions, and Raman spectroscopy analyses showed that DA was successfully grafted onto the graphene oxide surface by uncleophilic substitution and the amidation reaction, which increased the intragallery spacing of graphite oxide, resulting in the uniform dispersion of DA‐GO and DA‐RGO in the nonpolar xylene solvent. Morphological analysis of nanocomposites showed that both DA‐GO and DA‐RGO were homogeneously dispersed in HDPE matrix and formed strong interfacial interaction. Although the crystallinity, dynamic mechanical, gas barrier, and thermal stability properties of HDPE were significantly improved by addition of small amount of DA‐GO or DA‐RGO, the performance comparison of DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites indicated that the reduction of DA‐GO was not necessary because the interfacial adhesion and aspect ratio of graphene sheets had hardly changed after reduction, which resulting in almost the same properties between DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39803.     

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.