Influence of covalent and non-covalent modification of graphene on the mechanical,thermal and electrical properties of epoxy/graphene nanocomposites: a review

Abstract

Graphene is emerged as a highly sought after reinforcing filler for epoxy matrix in view of its superior electrical, mechanical and thermal properties. Dispersion of low concentration of graphene can significantly enhance the epoxy/graphene nanocomposites properties. Dispersion of graphene in epoxy matrix depends on processing protocols used, and interfacial interaction between epoxy matrix and graphene. Interfacial interaction between epoxy matrix and graphene can be achieved by covalent and non-covalent modification of graphene. This paper comprehensively review the influence of different processing protocols adopted for the processing of epoxy/graphene nanocomposites, and its effect on mechanical, thermal and electrical properties. In addition, covalent and non-covalent strategies adopted for modification of graphene, and its influence on mechanical, thermal and electrical properties of epoxy/graphene nanocomposites are extensively discussed. The future challenges associated with graphene reinforced epoxy nanocomposites processing have been discussed.     

Effects of different parameters on thermal and mechanical properties of aminated graphene/epoxy nanocomposites connected by covalent: A molecular dynamics study

This paper is devoted to studying the thermal and mechanical properties of aminated graphene (AG)/epoxy nanocomposites connected by covalent bond using molecular dynamics (MD) simulation. The effects of crosslinking degree, mass fraction and functionalized graphene (FG) type on AG/epoxy nanocomposites are considered. The elasticity modulus (E), the glass transition temperature (T_g), the coefficient of thermal expansion (CTE) and the interfacial energy (E_int) are also investigated. The MD simulation results indicate that, when the mass fraction of AG is between 1.2% and 3.1% and crosslinking degree reaches about 70%, the E, T_g, E_int and CTE of AG/epoxy nanocomposites are significantly improved compared with those of pure epoxy and graphene/epoxy nanocomposites. The reason is that AG not only possesses some excellent thermodynamic properties of graphene, but also has the function of curing agent to crosslink with epoxy monomer to form the carbon-nitrogen (C–N) covalent bond. A better interfacial interaction between nanoparticles and epoxy is essential in enhancing the thermal and mechanical properties of nanocomposite materials, which will provide a microscopic theoretical basis for the study of epoxy nanocomposites.     

Giant permittivity of three phase polymer nanocomposites obtained by modifying hybrid nanofillers with polyvinylpyrrolidone

In this work, the combination of graphene decorated with graphene quantum dots (G-D-GQDs) and barium titanate (BaTiO₃) nanoparticles filled poly (vinyledene fluoride) (PVDF) nanocomposites are prepared using solvent casting method. The modification of G-D-GQDs and BaTiO₃ nanoparticles with polyvinyl pyrrolidone (PVP) show finer dispersion in PVDF matrix as compared to unmodified G-D-GQDs and BaTiO₃ nanoparticles in PVDF matrix. XRD of PVDF nanocomposites shows the formation of α and β form of PVDF crystals. The incorporation of the combination of PVP modified BaTiO₃ nanoparticles and G-D-GQDs in PVDF matrix show a decrease in crystallization temperature (T_c), percent crystallinity (X_c) and increase in thermal stability as compared to unmodified PVDF/BaTiO₃/G-D-GQDs nanocomposites, due to interaction of PVP modified nanoparticles with PVDF. Further, the incorporation of the combination of 20 wt.% BaTiO₃ nanoparticles and 3 wt.% G-D-GQDs in PVDF matrix show a giant dielectric constant. The giant dielectric constant is achieved due to accumulation of more charges across conductor-insulator interface, more numbers of microcapacitor formed and enhanced interfacial compatibility between BaTiO₃/G-D-GQDs with PVDF through PVP. The loss tangent (tan δ) of PVP modified G-D-GQDs and BaTiO₃ nanoparticles and its PVDF nanocomposites is low due to lower leakage current, which make the material suitable for various applications.     

Effect of sodium alginate modification of graphene (by ‘anion-π’ type of interaction) on the mechanical and thermal properties of polyvinyl alcohol (PVA) nanocomposites

Layered aligned dispersion of graphene in graphene/polyvinyl alcohol (PVA) nanocomposites is prepared in the form of films through simple solution processing route. The results indicate that there exist an interfacial interaction between PVA and graphene because of hydrogen bonding. This is responsible for the change in structure of PVA (such as decrease in the level of crystallization) and exhibiting ductile PVA nanocomposite film with improved tensile modulus, tensile strength, and thermal stability. Moreover, to improve the mechanical properties of PVA nanocomposites, graphene is successfully modified using a non-covalent modifier, sodium alginate (SA) and there exist an ‘anion-π’ type of interaction in between SA and graphene. The modification results in finer dispersion of the graphene in PVA/SA-m-graphene nanocomposites. In addition, there exist a hydrogen bonding in between PVA and SA. This has resulted in the remarkable improvement in mechanical properties of PVA/SA-m-graphene nanocomposites as compared to pure PVA and PVA/graphene nanocomposites. The increase in mechanical properties of PVA/SA-m-graphene nanocomposites is achieved through better load transfer from graphene to polymer matrix, despite decrease in crystallinity of PVA. Improvement in tensile modulus and tensile strength is highest at 0.5 wt.% of SA-modified graphene in PVA/SA-m-graphene nanocomposites because of finer dispersion of graphene and is 62 and 40% higher than that of pure PVA. Addition of SA-modified graphene also improves the thermal stability of PVA/SA-m-graphene nanocomposites remarkably as compared to unmodified graphene PVA nanocomposites.     

Synthesis and Characterization of Poly(vinyl pyrrolidone)/Reduced Graphene Oxide Nanocomposite

Poly(vinyl pyrrolidone) (PVP)/reduced graphene oxide (RGO) nanocomposites were synthesized by reducing graphene oxide in the polymer matrix at different temperatures. The effects of the GO content on the properties of the nanocomposites were investigated by Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The degree of dispersion of GO in the PVP matrix was examined by field-emission scanning electron microscopy. The results showed that both GO and RGO were well dispersed in the PVP matrix. Under low filler content, the improvement of onset decomposition temperatures of PVP nanocomposites was not obviously observed, but the amounts of residual char of the PVP nanocomposites were clearly increased. In addition, the decomposition temperature peak values of the PVP nanocomposites were increased, while the peak was broadened.     

Processing and properties of carbon nanofibers reinforced epoxy powder composites

Commercially available CNFs (diameter 30–300 nm) have been used to develop both bulk and coating epoxy nanocomposites by using a solvent-free epoxy matrix powder. Processing of both types of materials has been carried out by a double-step process consisting in an initial physical premix of all components followed by three consecutive extrusions. The extruded pellets were grinded into powder and sieved. Carbon nanofibers powder coatings were obtained by electrostatic painting of the extruded powder followed by a curing process based in a thermal treatment at 200 °C for 25 min. On the other hand, for obtaining bulk carbon nanofibers epoxy composites, a thermal curing process involving several steps was needed. Gloss and mechanical properties of both nanocomposite coatings and bulk nanocomposites were improved as a result of the processing process. FE-SEM fracture surface microphotographs corroborate these results. It has been assessed the key role played by the dispersion of CNFs in the matrix, and the highly important step that is the processing and curing of the nanocomposites. A processing stage consisted in three consecutive extrusions has reached to nanocomposites free of entanglements neither agglomerates. This process leads to nanocomposite coatings of enhanced properties, as it has been evidenced through gloss and mechanical properties. A dispersion limit of 1% has been determined for the studied system in which a given dispersion has been achieved, as the bending mechanical properties have been increased around 25% compared with the pristine epoxy resin. It has been also demonstrated the importance of the thickness in the nanocomposite, as it involves the curing stage. The complex curing treatment carried out in the case of bulk nanocomposites has reached to reagglomeration of CNFs.     

Role of curing conditions and silanization of glass fibers on carbon nanotubes (CNTs) reinforced glass fiber epoxy composites

Curing behavior of amino-functionalized carbon nanotubes (ACNT) used as reinforcing agent in epoxy resin has been examined by thermal analysis. Experiments performed as per supplier’s curing conditions showed that modification of the curing schedule influences the thermo-mechanical properties of the nanocomposites. Specifically, the glass transition temperature (T_g) of ACNT-reinforced composites increased likely due to the immobility of polymer molecules, held strongly by amino carbon nanotubes. Further, a set of composites were prepared by implementing the experimentally determined optimal curing schedule to examine its effect on the mechanical properties of different GFRP compositions, while focusing primarily on reinforced ACNT and pristine nanotube (PCNT) matrix with silane-treated glass fibers. From the silane treatment of glass fibers in ACNT matrix composition it has been observed that amino silane is much better amongst all the mechanical (tensile and flexural) properties studied. This is because of strong interface between amino silane-treated glass fibers and modified epoxy resin containing uniformly dispersed amino-CNTs. On the other hand, PCNT GFRP composites with epoxy silanes demonstrated enhanced results for the mechanical properties under investigation which may be attributed to the presence of strong covalent bonding between epoxy silane of glass fiber and epoxy–amine matrix.     

Curing behavior and physical properties of an epoxy nanocomposite with amine-functionalized graphene nanoplatelets

Amine-functionalized graphene nanoplatelets (AGNPs) were prepared via an easy simple one-step process, treating graphite powder with 4-aminobenzoic acid in polyphosphoric acid, and then the effects of the AGNPs on the curing and physical properties of an epoxy resin were studied. The formation of the AGNPs was confirmed by scanning electronic microscopy (SEM), Fourier transform infrared spectroscopy, and thermogravimetric analyzer. Curing behavior of the epoxy/AGNPs nanocomposite was investigated by differential scanning calorimeter. The AGNPs made the epoxide curing reaction with amine groups slightly faster. The physical properties of the epoxy/AGNPs nanocomposite were investigated by dynamic mechanical analyzer, thermomechanical analyzer, and impact test. The AGNPs improved T_g by 21.4 °C, and storage modulus and impact strength of the epoxy resin 23 and 73%, respectively, much more effective than the graphite powder at the same filler loading of 1 phr. SEM images for the fracture surfaces of the epoxy/AGNPs nanocomposite showed improved interfacial bonding between the epoxy matrix and the nanofillers due to the amine functional groups of the AGNPs.     

Silane treatment of Fe3O4 and its effect on the magnetic and wear properties of Fe3O4/epoxy nanocomposites

In this study, the effect of silane treatment of Fe₃O₄ on the magnetic and wear properties of Fe₃O₄/epoxy nanocomposites was investigated. Fe₃O₄ nanopowders were prepared by coprecipitation of iron(II) chloride tetrahydrate with iron(III) chloride hexahydrate, and the surfaces of Fe₃O₄ were modified with 3-aminopropyltriethoxysilane. The magnetic properties of the powders were measured on unmodified and surface-modified Fe₃O₄/epoxy nanocomposites using SQUID magnetometer. Wear tests were performed on unmodified and surface-modified Fe₃O₄/epoxy nanocomposites under the same conditions (sliding speed: 0.18 m/s, load: 20 N).The results showed that the saturation magnetization (M_s) of surface-modified Fe₃O₄/epoxy nanocomposites was approximately 110% greater than that of unmodified Fe₃O₄/epoxy nanocomposites. This showed that the specific wear rate of surface-modified Fe₃O₄/epoxy nanocomposites was lower than that of unmodified Fe₃O₄/epoxy nanocomposites. The decrease in wear rate and the increase in magnetic properties of surface-modified Fe₃O₄/epoxy nanocomposites occurred due to the improved dispersion of Fe₃O₄ into the epoxy matrix.     

Fullerene–epoxy nanocomposites-enhanced mechanical properties at low nanofiller loading

In this study, we characterized the mechanical properties of fullerence (C₆₀) epoxy nanocomposites at various weight fractions of fullerene additives in the epoxy matrix. The mechanical properties measured were the Young’s modulus, ultimate tensile strength, fracture toughness, fracture energy, and the material’s resistance to fatigue crack propagation. All of the above properties of the epoxy polymer were significantly enhanced by the fullerene additives at relatively low nanofiller loading fractions (~0.1 to 1% of the epoxy matrix weight). By contrast, other forms of nanoparticle fillers such as silica, alumina, and titania nanoparticles require up to an order of magnitude higher weight fraction to achieve comparable enhancement in properties.     

Fabrication of Graphene Nanoplatelet/Epoxy Nanocomposites for Lightweight and High‐Strength Structural Applications

Graphene nanoplatelets (GNPs), the most important mass‐produced graphene, are fabricated as a mechanical reinforcement for epoxy matrix nanocomposites. Current performance of GNPs as a reinforcing filler is limited by their agglomeration and weak interfacial interaction with certain polymer matrices. Herein, an approach to produce noncovalently functionalized GNPs (F‐GNPs) is reported that can be extended to the industrial level of mass production. The one‐step functionalization process uses melamine, a low‐cost chemical, to improve the interfacial adhesion and dispersion in an epoxy matrix. The mechanical properties of nanocomposites prepared with the F‐GNP flakes are much better (94.3% and 35.3% enhancements in Young's modulus and tensile strength, respectively) than those of the unfilled pure epoxy. Experimental data are analyzed using the Halpin–Tsai model. The fabrication process developed in this paper provides a strategy to use GNPs at the industrial level in lightweight and high‐strength structural applications.     

Study of ionic solvent-free carbon nanotube nanofluids and its composites with epoxy matrix

A facile way to synthesis ionic solvent-free multi-walled carbon nanotubes (CNTs) (MWNTs) nanofluids has been introduced. Fourier transform infrared spectra and transmission electron microscope (TEM) were employed to study the surface structure of MWNTs in the nanofluids. The thermal property of the nanofluids was characterized by thermogravimetric analysis and differential scanning calorimetry. The stability of the nanofluids in the deionized water was obtained through UV–Vis absorption spectrum. Rotary rheometer was used to test the flow feature of the nanofluids. The results of conductivity indicate that the seepage threshold value of solvent-free nanofluids in water is about 0.408 vol.% (volume fraction). Meanwhile, it is found that the ionic nanofluids dispersed well in epoxy matrix. The mechanical properties, such as bend modulus, strength and impact toughness have been improved at the same time. TEM images can tell the great dispersion of solvent-free CNTs nanofluids in the epoxy matrix. It means that this kind of nanofluids will be excellent nanofiller in the nanocomposites.     

Characterization of PEO/PVP/GO nanocomposite solid polymer electrolyte membranes: microstructural,thermo-mechanical,and conductivity properties

Poly (ethylene oxide) (PEO)/polyvinylpyrrolidone (PVP) blended nanocomposite polymers, incorporating graphene oxide (GO) nano-sheets and embedded with NaIO₄ salt, were prepared using solution casting technique. The as-prepared nanocomposite electrolyte membranes were characterized by SEM, TEM, XRD, and Raman vibrational spectroscopic techniques to confirm the dispersion of GO nano-sheets and to understand the synergistic properties of GO/polymer interactions as a function of GO nano-sheets concentration. GO fillers incorporated electrolyte membranes demonstrated distinctive surface morphology composed of circular-shaped protuberances of different dimensions. The decrease of Raman intensity ratio (I_D/I_G) and in-plane crystallite size (L_a) values of the nanocomposites suggested the good dispersion and confinement of the GO nano-sheets. The optical properties of blend electrolyte films were studied as a function of GO filler concentration using optical absorption and diffuse reflectance spectra. In reference to PEO/PVP/NaIO₄, the resultant PEO/PVP/NaIO₄/GO (0.4% in weight) electrolyte membrane demonstrated both an increase in tensile strength of ca. 42% and in Young’s modulus of ca. 40%, improvements coupled with a maximum fractured elongation of 3%. Through impedance spectroscopy analysis, the role of the GO nano-sheets onto the room temperature conductivity properties of the prepared electrolyte membranes has been probed.     

Effects of enhanced hydrogen bonding on the mechanical properties of poly (vinyl alcohol)/carbon nanotubes nanocomposites

In this study, poly (vinyl alcohol) (PVA) composites reinforced by multiwall carbon nanotubes (MWCNTs) functionalized with either phenolic hydroxyl groups (MWCNTs-f-OH) or PVP molecule (PVP@MWCNTs) were fabricated. The objective was to elucidate the effect of different MWCNTs surface functionalization on the mechanical properties of the nanocomposites. It was found that both of PVP@MWCNTs and MWCNTs-f-OH had a good dispersion in PVA matrix. However, the MWCNTs-f-OH had stronger effective interfacial interaction with PVA matrix than PVP@MWCNTs, owe to the formation of hydrogen bonds between MWCNTs-f-OH and PVA. The stress-strain measurements showed that the Young’s modulus and tensile strength of MWCNTs-f-OH/PVA with only 1.0 wt.% contents increased by 200 and 100% compare with that of PVA, respectively. The findings of this experimental study emphasized the critical role of MWCNTs surface morphology in determining the mechanical properties of nanocomposites, and shed new light on understanding and advancing the properties of carbon nanotube based composites.     

Investigation on thermal conductivity and physical properties of polythiophene/p-phenylenediamine-graphene oxide and polythiophene-co-poly(methyl methacrylate)/p-phenylenediamine graphene oxide composites

An efficient approach was employed to simultaneously functionalize and reduce the graphene oxide (GO) with p-phenylene diamine (PPD) using simple refluxing. There was a possibility of nucleophilic substitution of amino moieties of PPD with the epoxy groups of GO. The polythiophene (PTh) and polythiophene-co-poly(methylmethacrylate) (PTh-co-PMMA) nanocomposites with chemically modified GO were prepared using in situ polymerization technique. Two series of nanocomposites that is PTh/PPD-GO and PTh-co-PMMA/PPD-GO were designed. The nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, scanning electron microscopy (SEM), thermal conductivity, and electrical conductivity measurement. The FTIR spectra depicted the characteristic absorption peaks for the formation of copolymer and their composites with PPD-GO. The SEM micrographs showed that the PPD-GO nanosheets were homogeneously dispersed in copolymer matrix forming nano-granular morphology. The nanofluids were prepared by suspending modified GO particles inside the basefluid of polythiophene and PTh-co-PMMA. The thermal conductivity of nanocomposites was significantly improved even with low PPD-GO loading. The thermal conductivity of PTh-co-PMMA/PPD-GO with 1.5 wt.% filler was increased to 1.42 W/mK at a higher temperature. The XRD patterns confirmed the presence of chemical interactions between the copolymer and filler particles. The electrical conductivity of PTh-co-PMMA/PPD-GO was also found to increase in the range of 6.1 × 10^?3–2.5 × 10^?2 S/cm. Novel PTh-co-PMMA/PPD-GO-based nanocomposite is potentially significant in high-performance thermal systems.     

The Influence of the Geometric Shape of Carbon Nanoparticles on the Strength Properties of Nanocomposite Materials Obtained by Filling an Epoxy Matrix

Abstract

The effects of filling an epoxy matrix modified with “Viniflex” with carbon nanotubes, fullerene C₆₀, or graphene on the mechanical properties, surface morphologies and glass transition temperatures of the composite materials obtained after curing were studied. It was shown that the largest decrease in glass transition temperature and an increase in impact strength was achieved by the introduction of 0.1 mass% graphene. Filling with graphene and carbon nanotubes increased the bending strength while filling with C₆₀ fullerenes provided the greatest compressive strength and elasticity modulus. An explanation of the results was based on ideas about the relationship of the geometrical shape of the nanofiller to the load direction and features of the phase composition of the composite materials. It is suggested that the carbon nanomaterials had a template effect on the packing of the epoxy matrix chains.     

Synthesis and Curing Kinetics of UV-Curable Waterborne Bisphenol-S Epoxy-Acrylate/Polyurethane-Acrylate/Methylacryloylpropyl-POSS Nanocomposites

In order to prepare waterborne UV-curable polyurethane-acrylate (PUA) /epoxyl-acrylate (ERA) nanocomposites, the PUA, bisphenol-S epoxy acrylate (BPSEA) and methylacryloylpropyl polyhedral oligomeric silsesquioxanes (MAP-POSS) were synthesized. UV-curable BPSEA/PUA/MAP-POSS nanocomposites were prepared. The curing process, kinetics, and properties of the nanocomposites were investigated by Fourier transform infrared spectrometer (FTIR), differential scanning calorimeter (DSC) and dynamic mechanical analyzer (DMA). The base-acid resistance ability, adhesive strength, and hardness of coating films were determined. The results showed that these nanocomposites could be cured by both UV-light irradiation and a thermal free radical polymerization. Under the UV-light irradiation, they could be cured basically completely in about 20 min. The thermal free radical curing reaction could be described by a two-parameter autocatalytic ?esták-Berggren (S-B) model. The dynamic mechanical loss peak temperature, T_p, of the cured nanocomposites increased with increasing MAP-POSS content up to 8 wt%, an enhancement of 5.8°C over the pure BPSEA/PUA system, and then decreased. Films of the nanocomposites also had better base-acid resistance ability and hardness than pure BPSEA/PUA.     

Magnetic and electromagnetic absorption properties of FeNi alloy nanoparticles supported by reduced graphene oxide

FeNi alloy nanoparticles (NPs) supported by reduced graphene oxide (RGO) (FeNi/RGO nanocomposites) were successfully synthesized through in‐situ reduction. Large amounts of sphere‐like FeNi NPs are uniformly deposited on the RGO nanosheets. The magnetic hysteresis measurement reveals the ferromagnetic behavior of the nanocomposites at room temperature. According to the electromagnetic (EM) characteristics, the FeNi/RGO nanocomposites show outstanding EM absorption properties in the 2–18 GHz range, as evidenced by the wide effective absorption bandwidth (up to 3.3 GHz, with reflection loss R_L < –10 dB) and a minimal R_L (–32 dB) at 12.4 GHz with a thickness of 1.5 mm. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal properties of graphene and multilayer graphene: Applications in thermal interface materials

We review the thermal properties of graphene and multilayer graphene, and discuss graphene’s applications in thermal management of advanced electronics and optoelectronics. A special attention is paid to the use of the liquid-phase-exfoliated graphene and multilayer graphene as the fillers in the thermal interface materials. It has been demonstrated that addition of an optimized mixture of graphene and multilayer graphene to the composites with different matrix materials produces the record-high enhancement of the effective thermal conductivity at the small filler loading fraction (f≤10 vol%). The thermal conductivity enhancement due to the presence of graphene in the composites has been observed for a range of matrix materials used by industry. The hybrid composites where graphene is utilized together with metallic micro- and nanoparticles allow one to tune both the thermal and electrical conductivity of these materials. Theoretical considerations indicate that the graphene-based thermal interface materials can outperform those with carbon nanotubes, metal nanoparticles and other fillers owing to graphene’s geometry, mechanical flexibility and lower Kapitza resistance at the graphene–base material interface.     

Influence of SiC Electron Acceptor–Donor Modification on Thermal and Physical Properties of Carbon Fiber/SiC/Epoxy Composites

In this work, the effects of electron acceptor–donor modification on the surface properties of SiC were investigated in the mechanical interfacial properties of carbon fibers-reinforced SiC-impregnated epoxy matrix composites. The surface properties of the SiC were determined according to acid/base values and FT-IR, and contact angle measurements. The thermal and mechanical interfacial properties of the composites were evaluated using a thermogravimetric analysis, critical strain energy release rate mode II (G _IIC), and impact strength testing. As a result, the electron acceptor-treated SiC had a higher acid value and polar component in surface free energy than did the untreated SiC or the electron donor-treated SiC. The G _IIC and impact strength mechanical interfacial properties of the composites had been improved in the specimens treated by acidic solutions due to the good wetting and a high degree of adhesion with electron donor characteristic epoxy resins.