Effect of the C/O ratio in graphene oxide materials on the reinforcement of epoxy-based nanocomposites

The effect of the C/O ratio of graphene oxide materials on the reinforcement and rheological percolation of epoxy-based nanocomposites has been studied. As-prepared graphene oxide (GO) and thermally-reduced graphene oxide (TRGO) with higher C/O ratios were incorporated into an epoxy resin matrix at loadings from 0.5 to 5 wt %. Tensile testing revealed good reinforcement of the polymer up to optimal loadings of 1 wt %, whereas agglomeration of the flakes at higher loadings caused the mechanical properties of the composites to deteriorate. The level of reduction (C/O) of the graphene oxide filler was found to influence the mechanical and rheological properties of the epoxy composites. Higher oxygen contents were found to lead to stronger interfaces between graphene and epoxy, giving rise to higher effective Young's moduli of the filler and thus to superior mechanical properties of the composite. The effective modulus of the GO in the nanocomposites was found to be up to 170 GPa. Furthermore, rheological analysis showed that highly oxidized graphene flakes did not raise the viscosity of the epoxy resin significantly, facilitating the processing considerably, of great importance for the development of these functional polymeric materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 281–291     

Simulation of the adhesion properties of the polyethylene/carbon nanotube interface

The properties of a polyethylene matrix in contact with carbon nanoinclusions, such as carbon nanotubes and graphene plates, are studied via the molecular-dynamics method. Ultimate shear stresses for the polyethylene/graphene interface are calculated, and the effect of the filler aspect ratio on the nanocomposite elastic modulus is considered.     

High-yield synthesis of few-layer graphene flakes through electrochemical expansion of graphite in propylene carbonate electrolyte

High-yield production of few-layer graphene flakes from graphite is important for the scalable synthesis and industrial application of graphene. However, high-yield exfoliation of graphite to form graphene sheets without using any oxidation process or super-strong acid is challenging. Here we demonstrate a solution route inspired by the lithium rechargeable battery for the high-yield (>70%) exfoliation of graphite into highly conductive few-layer graphene flakes (average thickness <5 layers). A negative graphite electrode can be electrochemically charged and expanded in an electrolyte of Li salts and organic solvents under high current density and exfoliated efficiently into few-layer graphene sheets with the aid of sonication. The dispersible graphene can be ink-brushed to form highly conformal coatings of conductive films (15 ohm/square at a graphene loading of <1 mg/cm(2)) on commercial paper.     

Rice Husk‐derived Hierarchical Micro/Mesoporous Carbon–Silica Nanocomposite as Superior Filler for Green Electronic Packaging Material

In this study, a carbon‐controllable hierarchical micro/mesoporous carbon–silica material derived from agricultural waste rice husk was easily synthesized and utilized as filler in an epoxy matrix for electronic packaging applications. Scanning electron microscopy, thermogravimetric analysis, and N₂ adsorption/desorption isotherms were used to characterize the morphology, thermal stability, carbon content, and porous structural properties, respectively, of the as‐obtained carbon–silica material, namely rice husk char (RHC ). As a filler material, the uniformly dispersed RHC filler in the epoxy/RHC composite was easily prepared through hydrogen bonding of the silanol group of silica with the epoxy matrix. For electronic packaging applications, the thermal conductivity and thermomechanical properties (storage modulus and coefficient of thermal expansion) of the epoxy/RHC composites improved with increasing carbon content. Moreover, loading of the 40% RHC filler substantially enhanced the storage modulus of the epoxy/RHC composite (5735 MPa ) compared to the epoxy with 40% commercial silica filler (3681 MPa ). Considerable commercial potential is expected for the carbon–silica composite because of the simple synthesis process and outstanding performance of the prepared packaging material.     

Reactive copolymer functionalized graphene sheet for enhanced mechanical and thermal properties of epoxy composites

Uniform dispersion of graphene nanosheets (GNS) in a polymer matrix with strong filler–matrix interfacial interaction, preserving intrinsic material properties of GNS, is the critical factor for application of GNS in polymer composites. In this work, a novel reactive copolymer VCz–GMA containing carbazole and epoxide group was designed, synthesized and employed to noncovalently functionalize GNS for preparing epoxy nanocomposites with enhanced mechanical properties. The presence of carbazole groups in VCz–GMA enables the tight absorption of copolymer on to graphene surface via π–π stacking interaction, as evidenced by Raman and fluorescence spectroscopy, whereas the epoxide segments chemically reacts with the epoxy matrix, improving the compatibility and interaction of graphene with epoxy matrix. As a result, the VCz–GMA–GNS/epoxy composite showed a remarkable enhancement in both mechanical and thermal property than either the pure epoxy or the graphene/epoxy composites. The incorporation of 0.35 wt % VCz–GMA–GNS yields a tensile strength of 55.72 MPa and elongation at break of 3.45, which are 42 and 191% higher than the value of pure epoxy, respectively. Increased glass transition temperature and thermal stability of the epoxy composites were also observed. In addition, a significant enhancement in thermal conductivity was achieved with only 1 wt % VCz–GMA–GNS loading. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2776–2785     

Shape memory effect and mechanical properties of graphene/epoxy composites

Graphene/epoxy shape memory composites were fabricated with graphene from a simple and low cost method of chemical oxidation-reduction process. The fine and homogeneous dispersion of graphene throughout the epoxy matrix with different graphene mass fraction were prepared and their properties were investigated. It was found that storage elastic modulus rose with the increase of graphene mass fraction, which indicated that the recovery stress of graphene/epoxy composites would be greater than that of the pure epoxy. The graphene/epoxy composites with lower content graphene showed a good shape memory effect and a recovering speed superior to the pure epoxy.     

Comparative study of the mechanical and wear performance of short carbon fibers and mineral particles (Wollastonite,CaSiO3) filled epoxy composites

To improve the mechanical and tribological performance, two kinds of wollastonite fillers (fine or coarse) and short carbon fibers (5–15 vol %) were, respectively, incorporated into an epoxy resin. Fine wollastonite fillers remarkably enhanced the flexural modulus, strength, and toughness of the resin at some filler contents (i.e., 10 vol %) simultaneously, while coarse wollastonite fillers and short carbon fibers impaired most of mechanical properties except the modulus. The small particle size, low aspect ratio as well as the good adhesion to the epoxy matrix of the fine wollastonite particles are believed to be responsible for the improved strength and toughness. Tribological tests were performed under sliding and low amplitude oscillating wear conditions. All fillers enhanced the wear resistance and reduced the sliding coefficient of friction but to a different extent. Under sliding wear conditions, fine wollastonite particle‐filled epoxy displayed the highest wear resistance because of the formation of an effective transfer film and the low abrasiveness of the fillers. Under low amplitude oscillating wear conditions, both wollastonite fillers showed much higher wear resistance than short carbon fibers regardless of the filler content. The better adhesion between the wollastonite fillers and the epoxy matrix is responsible for the higher wear resistance under oscillating conditions. The wear tracks were inspected by microscopy to analyze the corresponding wear mechanisms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 854–863, 2006     

聚甲基丙烯酸甲酯/石墨薄片纳米复合及其导电性能研究

在聚合物绝缘材料基体中添加入足够数量的导电填料 ,聚合物便具有导电性或半导体性能 .石墨材料 ,由于资源丰富、价廉、性质稳定 ,被广泛用作导电聚合物复合材料的填料 .一般 ,填料含量越高 ,复合材料的导电性能越好 ,但是材料的力学性能也随之劣化 ,特别是材料脆性增加 .将石墨加工成纳米级粒子 ,再与聚合物纳米复合 ,有望用较少的石墨填充量使复合材料具有良好的电传导性能 ,从而保持材料的力学性能 .最近报道的利用膨胀石墨与聚合物实现纳米复合的研究引起了人们的兴趣 ,如所报道的尼龙 6 膨胀石墨[1] 、PS PMMA 膨胀石墨[2 ] 、PP …     

Low contents of graphite improving general properties of poly(vinylidene fluoride)

Studies on graphite flakes with a lateral size greater than 50 μm, having a large number of stacked collapse blocks, are neglected and replaced by graphene nanosheets or by powdered graphite, which can be obtained from graphite through chemical or physical exfoliation, as filler in polymer composites. Besides, the production of graphene nanosheets or the purification of powdered graphite uses a high concentration of strong and toxic acids that pollutes the environment. These processes are extremely time-consuming and generate an expensive product. Composites of poly(vinylidene fluoride) (PVDF) were prepared via extrusion with graphite flakes with up to 60 μm thick and 700 μm lateral size, in the range from 0.1 to 5% m/m. The quality of graphite flakes was analyzed by thermogravimetric analysis, x-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared spectroscopy, and scanning electron microscopy. The increase in the graphite content in the PVDF matrix improved thermal resistance while showed an increase in the degree of crystallinity up to 25% by XRD and 43% by differential scanning calorimetry, approximately. Although the graphite acted as a nucleating agent, the content of the PVDF beta phase did not change. In the composites with up to 2.0% of graphite, a significant increase in mechanical properties, 13% modulus, and 36% in the storage modulus, evaluated by thermodynamic-mechanical analysis and tensile tests. In the analyses of time-domain nuclear magnetic resonance and oscillatory rheology in parallel plates, it was noticed that the increase of mechanical properties is due to the reinforcing effect along with the lubricant protection of stacked graphene sheets, attenuating the stress and friction between the polymer chains. Therefore, even though graphite flakes are inexpensive, that filler without any treatment at low contents are capable of significantly improving the performance of PVDF. This work suggests that these composites could be employed in applications such as electrical insulator with less energy dissipation, and also in oil pipelines, specifically to replace PVDF-based terpolymers or mixtures thereof, and polyamide-11 in flexible risers as a barrier layer, improving their performance.     

Theoretical and experimental investigation of the stiffness of iron-filled epoxy polymers

The static elastic moduli of particulate-filled epoxy resins, consisting of two phases, one of which has isotropic-elastic and the other linear viscoelastic properties, were studied. The effects of parameters such as the filler volume fraction, the filler size and aspect ratio, and the filler distribution were evaluated. For this purpose, in the theoretical part a development of a simplified model based on mechanics of materials approach was used. In the experimental part a class of iron-filled epoxy composites with various filler content, filler size, and filler distribution was subjected to tests in order to obtain the elastic modulus. The experimental results were compared with the theoretical values derived from the developed model as well as with theoretical values obtained from other investigators.     

Electrical conductivity of poly(ethylene terephthalate)/expanded graphite nanocomposites prepared by in situ polymerization

Nanocomposites based on poly(ethylene terephthalate) (PET) and expanded graphite (EG) have been prepared by in situ polymerization. Morphology of the nanocomposites has been examined by electronic microscopy. The relationship between the preparation method, morphology, and electrical conductivity was studied. Electronic microscopy images reveal that the nanocomposites exhibit well dispersed graphene platelets. The incorporation of EG to the PET results in a sharp insulator‐to‐conductor transition with a percolation threshold (?_c) as low as 0.05 wt %. An electrical conductivity of 10^?3 S/cm was achieved for 0.4 wt % of EG. The low percolation threshold and relatively high electrical conductivity are attributed to the high aspect ratio, large surface area, and uniform dispersion of the EG sheets in PET matrix. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Epoxy nanocomposites with high thermal conductivity and low loss factor: Realize 3D thermal conductivity network at low content through core-shell structure and micro-nano technology

Dielectric polymers with high thermal conductivity are very promising in the fields of aerospace and electronic device packaging. However, composites with excellent dielectric properties usually have low thermal conductivity. It is usually to fill the polymer with thermal conductivity particles to improve the thermal conductivity, but the high content of filler often reduces the mechanical properties of the polymer. In this paper, the traditional insulating polymer epoxy resin was used as the matrix, by covering the surface of silicon carbide with graphene to form a core-shell structure and co-filled with nano diamonds to achieve the preparation of high-performance epoxy resin at low content. The results showed that at the filling content of 30 wt%, the thermal conductivity of epoxy nanocomposites showed a dramatic thermal conductivity enhancement of 1263%, the energy storage modulus increased by 1.1 GPa, and the dielectric loss remained unchanged at 50 Hz. The advantages of the composite are the structural design and surface modification of the filler, which not only take advantage of its inherent advantages, but also improve the interface area with the epoxy matrix. The composite materials with excellent properties are expected to provide theoretical guidance for the application of high thermal conductivity dielectric materials.     

Epoxy‐based composite adhesives: Effect of hybrid fillers on thermal conductivity,rheology, and lap shear strength

Thermal management is an important parameter in an electronic packaging application. In this work, three different types of fillers such as natural graphite powder (Gr) of 50‐μm particle size, boron nitride powder (h‐BN) of 1‐μm size, and silver flakes (Ag) of 10‐μm particle size were used for thermal conductivity enhancement of neat epoxy resin. The thermal properties, rheology, and lap shear strength of the neat epoxy and its composite were investigated. The analysis showed that the loading of different wt% of Gr‐based fillers can effectively increase the thermal conductivity of the epoxy resin. It has also been observed that the thermal conductivity of the hybrid filler (Gr/h‐BN/Ag) reinforced epoxy adhesive composite increased six times greater than that of neat epoxy resin composite. Further, the viscosity of hybrid filler reinforced epoxy resin was found to be increased as compared with its virgin counterpart. The adhesive composite with optimized filler content was then subsequently subjected to determine single lap shear strength. The degree of filler dispersion and alignment in the matrix were determined by scanning electron microscopy (SEM) analysis.     

Dispersion of graphene oxide and its flame retardancy effect on epoxy nanocomposites

Graphene oxide was prepared by ultrasonication of completely oxidized graphite and used to improve the flame retardancy of epoxy.The epoxy/graphene oxide nanocomposite was studied in terms of exfoliation/dispersion,thermal stability and flame retardancy.X-ray diffraction and transmission electron microscopy confirmed the exfoliation of the graphene oxide nanosheets in epoxy matrix.Cone calorimeter measurements showed that the time to ignition of the epoxy/graphene oxide nanocomposite was longer than that of neat epoxy.The heat release rate curve of the nanocomposite was broadened compared to that of neat epoxy and the peak heat release rate decreased as well.     

Reinforcing epoxy resin through covalent integration of functionalized graphene nanosheets

A chemically converted graphene/epoxy (EP) resin nanocomposite has been developed through the use of the functionalized graphene nanosheets (FGNs). The FGNs were prepared via the reaction of amines with alkylcarboxyl groups attached to the graphite oxides in the course of a dicarboxylic acid acyl peroxide treatment. FGNs/EP composites were prepared by dissolving the FGNs in organic solvent followed by mixing with EP and curing agent. In this composite, the FGNs were able to create molecular entanglement with EP matrix by taking advantage of the reactions between amine groups of FGNs and EP groups of EP, thus the FGNs could be covalently integrated into the EP matrix and became part of the cross‐linked network structure rather than just a separated component. Great enhancement in the mechanical properties of the epoxy composite, such as the ultimate tensile strength and toughness, had been achieved with small loading (0.1 wt%) of FGNs by 17.0% and 262.2%, respectively. However, the FGNs reinforced EP composites showed a slight decrease in glass transition temperature (Tg). Copyright © 2014 John Wiley & Sons, Ltd.     

Synergistic effect of hybrid graphene and boron nitride on the cure kinetics and thermal conductivity of epoxy adhesives

In the present study, the synergistic effect of hybrid boron nitride (BN) with graphene on the thermal conductivity of epoxy adhesives has been reported. Graphene was prepared by chemical reduction of graphite oxide (GO) in a mixture of concentrated H₂SO₄/H₃PO₄ acid. The particle size distribution of GO was found to be ~10 μm and a low contact angle of 54° with water indicated a hydrophilic surface. The structure of prepared graphene was characterized by Fourier transform infrared (FTIR), X‐ray diffraction (XRD), Raman spectroscopy and atomic force microscopy (AFM). The thermal conductivity of adhesives was measured using guarded hot plate technique. Test results indicated an improvement in the thermal conductivity up to 1.65 W/mK, which was about ninefold increase over pristine epoxy. Mechanical properties of different epoxy formulations were also measured employing lap shear test. The surface characterization of different epoxy adhesive systems was characterized through XRD, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies. Fourier transform infrared also served to determine the nature of interactions between filler particles and epoxy resin. Non‐isothermal differential scanning calorimetric (DSC) technique was used to investigate the effects of graphene and BN particles on the cure kinetics and cross‐linking reaction of epoxy cured with amine curing agent. The Kissinger equation, the model‐free isoconversional Flynn–Wall–Ozawa method and the Ozawa model were used to analyze the kinetic parameter. Copyright © 2017 John Wiley & Sons, Ltd.     

Experimental Investigations of AlMg3 Components with Polyurethane and Graphene Oxide Nanosheets Composite Coatings,after Accelerated UV-Aging

The use of graphene (Gr) and its derivates graphene oxide (GO) showed that these materials are good candidates to enhance the properties of polyurethane (PU) coatings, especially the anticorrosion ones since graphene absorbs most of the light and provides hydrophobicity for repelling water. An important aspect of these multifunctional materials is that all these improvements can be realized even at very low filler loadings in the polymer matrix. In this work, an ultrasound cavitation technique was used for the proper dispersion of GO nanosheets (GON) in polyurethane (PU) resin to obtain a composite coating to protect the AlMg3 substrate. The addition of GON considerably improved the physical properties of coatings, as demonstrated by electrochemical impedance spectroscopy (EIS) analysis, promising improved anticorrosion performance after accelerated UV-ageing. Computational methods and Differential Scanning Calorimetry (DSC) measurements showed that GON facilitates the formation of additional bonds and stabilizes the PU structures during the ultraviolet (UV) exposure and aggressive attack of corrosive species. Limiting oxygen index (LOI) data reveal a slow burning behaviour of PU-GON coatings during UV exposure, which is better than PU alone.     

Analysis of correlation between percolation concentration and elongation at break in filled electroconductive epoxy-based adhesives

Electrical conductivity and elongation at break of epoxy filled with electroconductive carbon black, graphite or with silver-coated basalt particles or fibres were investigated in this paper. Percolation concentrations were determined to be 14 vol% for epoxy/carbon black composites, 22 vol% for epoxy/graphite composites, 28-29 vol% for both epoxy/silver-coated basalt particles and fibres. The steepest increase in electrical conductivity and the most pronounced decrease in elongation at break occurs at similar filler concentration range for all investigated systems. A good correlation between phenomenological model, introduced in [J. Mater. Sci. Lett. 18 (1998) 1457] and experimental data for all investigated systems was observed.     

尼龙6/石墨纳米导电复合材料的制备与性能

通过原位插层聚合制备了尼龙 6 /石墨纳米导电复合材料 ,其室温导电渗滤阈值为 =0 75vol% ,远远低于常规导电粒子填充的聚合物复合材料 .当石墨体积分数为 2 0vol%时 ,室温电导率可达 10 -4 S/cm .透射电镜研究表明 :由于石墨经高温膨胀后其片层被剥离导致了片状石墨粒子具有巨大的径厚比 ,经原位插层聚合其片层厚度进一步被剥离为几十个纳米 ,同时原位插层聚合使得石墨粒子能够均匀分散在尼龙 6基体中 ,因而导致了该导电复合材料的低渗滤阈值和高导电性能 .     

Self assembled graphene/carbon nanotube/polystyrene hybrid nanocomposite by in situ microemulsion polymerization

Self-assembled graphene/carbon nanotube (CNT)/polystyrene hybrid nanocomposites were prepared by water-based in situ microemulsion polymerization. The resulting nanocomposites were used as filler in a host polystyrene matrix to form composite films. An admixture of the two types of carbon fillers provided better improvement in the thermal and mechanical properties compared to the neat polymer. The sheet resistance decreased progressively due to the formation of an extended conjugation network with the CNT bridging the gap between the graphene sheets coated with polymer nanoparticles. The details of the analysis are presented.