Non-covalently modified reduced graphene oxide/polyurethane nanocomposites with good mechanical and thermal properties

Non-covalently modified graphene nanosheets were prepared by reduction graphene oxide with hydrazine hydrate and simultaneous non-covalent functionalization via 1-allyl-methylimidazolium chloride (AmimCl) ionic liquid. Atomic force microscopy revealed that AmimCl ionic liquid modified graphene (IL-G) was well-dispersed in a single exfoliation with a thickness of around 0.96 nm in DMF. Subsequently, the prepared IL-G nanosheets were incorporated into polyurethane (PU) to fabricate IL-G/PU nanocomposites by solution blending. X-ray diffraction disclosed an exfoliated morphology of IL-G nanosheets dispersed in the PU matrix, while the fractured morphology of the IL-G/PU nanocomposites showed that IL-G nanosheets presented a wrinkled morphology when dispersed in the matrix. Both techniques revealed homogeneous dispersion and good compatibility of IL-G nanosheets with PU matrix, indicating the existence of interfacial interactions. At 0.608 wt% loadings of IL-G nanosheets, the tensile strength and storage modulus of the composites were increased by 68.5 and 81.1 %, respectively. High thermal properties were also achieved at a low loading of IL-G nanosheets. An approximately 40 °C improvement in temperature of 5 % weight loss and 34 % increase in thermal conductivity were obtained at just 0.608 wt% loading of IL-G nanosheets.     

High concentration exfoliation of graphene in ethyl alcohol using block copolymer surfactant and its influence on properties of epoxy nanocomposites

In this work, high concentration exfoliation (～0.2 mg/ml) of graphene in ethyl alcohol is achieved in presence of block copolymer of polyethylene oxide–polypropylene oxide–polyethylene oxide (PEO–PPO–PEO) using sonication followed by centrifugation. The obtained graphene solution is used to prepare epoxy nanocomposites. Flexural tests were conducted over epoxy nanocomposites. The 0.018 wt% of PEO–PPO–PEO block copolymer exfoliated graphene in epoxy matrix shows 21.7% and 15.8% enhancement in flexural modulus and flexural strength respectively as compared to pure epoxy. Transmission electron microscopy reveals well dispersion of graphene in epoxy matrix; and fractography of flexural fractured sample shows graphene dispersion restricts the crack propagation. The well-dispersed graphene in epoxy matrix increase the dielectric constant and thermal stability of epoxy nanocomposites. Further, the enhanced graphene dispersion in epoxy nanocomposites reduces the glass transition temperature (T_g). Thus, enhanced mechanical properties achieved by dispersion of block copolymer exfoliated graphene in epoxy nanocomposites make it suitable for several applications.     

Electrochemical stripping features of graphite and its products characterization

A stable dispersion in mixed solvent of water and N,N-dimethyl formamide (DMF) of graphene was synthesized by one-step electrochemical approach. Here we demonstrate about electrochemical stripping graphite to prepare graphene influence by different electrolytes. The physical and chemical properties of the stripping product had been characterized by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), UV-Vis spectrophotometer (UV-Vis), Scanning electron microscopy (SEM), Transmission Electron Microscope (TEM) . The characteristic results of XRD showed that it could improve the efficiency of graphite stripping when H₂SO₄ was used as electrolyte mother liquid and amount of HNO₃ was doped in electrolyte; XPS and FTIR results indicate that the electrochemical stripping products preserve the intrinsic structure of graphene. The results of SEM and TEM shown that the surface morphology of the as-prepared graphene was folded lamellar structure and have good transparency;its thickness varies from 0.8 nm to a few nanometers.     

Effects of graphene nanoplatelets and graphene nanosheets on fracture toughness of epoxy nanocomposites

The effects of graphene nanoplatelets (GPLs) and graphene nanosheets (GNSs) on fracture toughness and tensile properties of epoxy resin have been studied. A new technique for synthesis of GPLs based on changing magnetic field is developed. The transmission‐electron microscopy and the Raman spectroscopy were employed to characterize the size and chemical structure of the synthesized graphene platelets. The critical stress intensity factor and tensile properties of epoxy matrix filled with GPL and GNS particles were measured. Influence of filler content, filler size and dispersion state was examined. It was found that the GPLs have greater impact on both fracture toughness and tensile strength of nanocomposites compared with the GNSs. For instance, fracture toughness increased by 39% using 0.5 wt% GPLs and 16% for 0.5 wt% GNSs.     

碳纳米管和石墨烯纳米片复合增强AZ91镁基复合材料组织与力学性能

目的 解决纳米碳材料在镁基体中分散难的瓶颈问题,制备出力学性能优异的镁合金复合材料。方法 采用超声工艺将质量分数为3.0%的碳纳米管插入到质量分数为0.5%的石墨烯纳米片的片层之间,添加到AZ91镁合金基体中,借助粉末冶金技术+热挤压工艺制备了0.5%GNS+3.0%CNTs复合增强的镁基复合材料。采用光学显微镜和透射电子显微镜观察和分析了复合材料的显微组织和界面结合。测试了复合材料的力学性能,并利用扫描电子显微镜观察了复合材料的拉伸断口形貌。结果 复合材料的屈服强度、伸长率和显微硬度分别为（274±5.0）MPa,（8.4±0.2）%,HV（90.5±1.8）,与基体合金相比,分别提高了63.1%,20.0%,20.1%。结论 GNS+CNTs的加入有效细化了基体合金的晶粒组织,且与镁基体形成了较好的界面结合,促使细晶强化、应力转移强化等各种强化机制的共同作用,使复合材料力学性能显著提高。     

Production of graphene nanosheets by supercritical CO2 process coupled with micro-jet exfoliation

A facile and cost-effective method which combines supercritical CO₂ and micro-jet exfoliation has been developed for producing graphene nanosheets with high-quality. CO₂ molecules can intercalate into the interlayer of graphite because of their high diffusivity and small molecule size in supercritical operation. The tensile stress induced by graphite interfacial reflection of compressive waves exert on the graphite flakes, which lead to further exfoliation of graphite. Scanning electron microscope (SEM), transmission electron microscope (TEM), atomic force microscopy (AFM), Raman spectrum and X-ray diffraction (XRD) are used to identify morphology and quality of the exfoliated graphene nanosheets, which reveal that the graphite was successfully exfoliated into graphene and more than 88% of graphene nanosheets are less than three layers. The yield of graphene nanosheets is about 28 wt% under optimum conditions, which can be greatly improved by repeated exfoliation of the graphene sediment. The pure graphene film has a high conductivity of 2.1 × 10⁵ S/m.     

Significant improvement in static and dynamic mechanical properties of graphene oxide–carbon nanotube acrylonitrile butadiene styrene hybrid composites

Herein, hybridization of graphene nanosheets and carbon nanotubes (CNTs) has been made to solve the problem of restacking of graphene nanosheets and agglomeration of CNTs. The multiwalled carbon nanotubes (MWCNTs), reduced graphene oxide (RGO) and graphene oxide–carbon nanotubes (GCNTs) reinforced acrylonitrile butadiene styrene (ABS) composites have been prepared using micro-twin-screw extruder. The effect of these reinforcements on static and dynamic mechanical properties of composites is studied. The ultimate tensile strength and elastic modulus for 7 wt.% GCNT–ABS composites show enhancement of 26.1 and 71.3% over pure ABS matrix, respectively. Various parameters such as coefficient “C” factor (the ratio of storage modulus of the composite to polymer in glassy and rubbery regions), degree of entanglement, crosslink density and adhesion factor have been calculated to analyze the interaction between fillers and polymer matrix. The 3-D hybrid structure of GCNTs overcomes the associated problem of CNTs agglomeration and graphene restacking. GCNT hybrid composites show higher dispersion as well as effectiveness for increased filler amount as compared to RGO and MWCNTs based composites. GCNTs prove its superiority over MWCNTs and RGO by showing a synergistic effect in the glass transition temperature and storage modulus. Raman spectroscopy and scanning electron microscopy are used to confirm the interaction and distribution of the filler and matrix, respectively.     

Synthesis of conductive PPy/graphene/rare-earth ions composites and its application in the electrode materials

PPy/graphene/rare-earth ions composites were prepared by in-situ polymerization. The structure and morphology of the composites are characterized by transmission electron microscope and scanning electron microscope, the results revealed that the graphene nanosheets were distributed homogeneously within the PPy matrix. Cyclic voltammetry was used to study the electrochemical properties of composites in K₃Fe(CN)₆ (pH 7.4) at a scan rate of 10 mV s^?1 with a applied voltage range of ?0.2 to 0.6 V, indicating that composite has excellent cycling performance. These results demonstrate the viability of the use of this composites as electrode material for the capacitors.     

Preparation of MnO<Subscript>2</Subscript>/graphene composite as electrode material for supercapacitors

MnO₂/graphene composite was synthesized by a facile and effective polymer-assisted chemical reduction method. The nanosized MnO₂ particles were homogeneously distributed on graphene nanosheets, which have been confirmed by scanning electron microscopy and transmission electron microscopy analysis. The capacitive properties of the MnO₂/graphene composite have been investigated by cyclic voltammetry(CV). MnO₂/graphene composite exhibited a high specific capacitance of 324 F g⁻¹ in 1 M Na₂SO₄ electrolyte. In addition, the MnO₂/graphene composite electrode shows excellent long-term cycle stability (only 3.2% decrease of the specific capacitance is observed after 1,000 CV cycles).     

Preparation and characterization of in situ polymerized cyclic butylene terephthalate/graphene nanocomposites

Graphene-reinforced cyclic butylene terephthalate (CBT) matrix nanocomposites were prepared and characterized by mechanical and thermal methods. These nanocomposites containing different amounts of graphene (up to 5 wt%) were prepared by melt mixing with CBT that was polymerized in situ during a subsequent hot pressing. The nanocomposites and the neat polymerized CBT (pCBT) as reference material were subjected to differential scanning calorimetry, dynamical mechanical analysis, thermogravimetrical analysis, and heat conductivity measurements. The dispersion of the grapheme nanoplatelets was characterized by transmission electron microscopy. It was established that the partly exfoliated graphene worked as nucleating agent for crystallization, acted as very efficient reinforcing agent (the storage modulus at room temperature was increased by 39 and 89 % by incorporating 1- and 5-wt% graphene, respectively). Graphene incorporation markedly enhanced the heat conductivity but did not influence the TGA behavior, except the ash content, due to the not proper exfoliation except the ash content.     

Few-layer graphene films prepared from commercial copper foil tape

We present a facile, versatile and cost-effective method for the synthesis of mono- and bilayer graphene films on copper substrate using as carbon feedstock the pyrolysis products of the conductive adhesive polymer of a commercial copper tape commonly used in electron microscopy. A copper tape with adhesive on both sides is subjected to a heat treatment during 15 min at temperatures of 900, 1000, and 1050 °C under the flow of an Ar + 3%H₂ gas mixture. With this treatment, the tape adhesive polymer is pyrolized and the interaction of its decomposition products with the copper substrate gives rise to a graphene film of good structural quality mixed with amorphous carbon residues of the pyrolysis. For a temperature of 1050 °C (few degrees below the melting point of Cu), mono- and bilayer coexisting domains of graphene are obtained with almost 100% area coverage of the Cu substrate. For lower heat treatment temperatures, area coverage is reduced to 60–70% and the graphene film becomes predominantly bilayer. The treatment at the lowest temperature of 900 °C results in isolated hexagonal domains of graphene intermixed with a large amount of amorphous carbon residues and large uncovered areas of oxidized copper substrate. These results indicate that the number of active species for the formation of graphene films increases with increasing temperature, nevertheless limited by the copper melting point. Characterization of the obtained samples was performed with scanning electron microscopy, Raman scattering, and high-resolution transmission electron microscopy.     

The reinforcing effect of graphene nanosheets on the cryogenic mechanical properties of epoxy resins

The reinforcing effect of graphene in enhancing the cryogenic tensile and impact properties of epoxy composites is examined at a weight fraction of 0.05–0.50%. The micro-structure and cryogenic mechanical properties of the graphene/epoxy composites are investigated using scanning electron microscopy, transmission electron microscopy, small-angle X-ray scattering and mechanical testing techniques. The results show that the graphene dispersion in the epoxy matrix is good at low contents while its aggregation takes place and becomes severer as its content increases. And the cryogenic tensile and impact strength at liquid nitrogen temperature (77 K) of the composites are effectively improved by the graphene addition at proper contents. The cryogenic Young’s modulus increases almost linearly with increasing the graphene content. Moreover, the results for the mechanical properties at room temperature (298 K) of the graphene/epoxy composites are also presented for the purpose of comparison.     

Electrochemical performance of a graphene-polypyrrole nanocomposite as a supercapacitor electrode

A unique nanoarchitecture has been established involving polypyrrole (PPy) and graphene nanosheets by in situ polymerization. The structural aspect of the nanocomposite has been determined by Raman spectroscopy. Atomic force microscopy reveals that the thickness of the synthesized graphene is ～ 2 nm. The dispersion of the nanometer-sized PPy has been demonstrated through transmission electron microscopy and the electrochemical performance of the nanocomposite has been illustrated by cyclic voltammetry measurements. Graphene nanosheet serves as a support material for the electrochemical utilization of PPy and also provides the path for electron transfer. The specific capacitance value of the nanocomposite has been determined to be 267 F g(-1) at a scan rate of 100 mV s(-1) compared to 137 mV s(-1) for PPy, suggesting the possible use of the nanocomposite as a supercapacitor electrode. After 500 cycles, only 10% decrease in specific capacitance as compared to initial value justifies the improved electrochemical cyclic stability of the nanocomposite.     

Graphene/MnO2 hybrid nanosheets as high performance electrode materials for supercapacitors

Graphene/MnO₂ hybrid nanosheets were prepared by incorporating graphene and MnO₂ nanosheets in ethylene glycol. Scanning electron microscopy and transmission electron microscopy analyses confirmed nanosheet morphology of the hybrid materials. Graphene/MnO₂ hybrid nanosheets with different ratios were investigated as electrode materials for supercapacitors by cyclic voltammetry (CV) and galvanostatic charge–discharge in 1 M Na₂SO₄ electrolyte. We found that the graphene/MnO₂ hybrid nanosheets with a weight ratio of 1:4 (graphene:MnO₂) delivered the highest specific capacitance of 320 F g⁻¹. Graphene/MnO₂ hybrid nanosheets also exhibited good capacitance retention on 2000 cycles.     

In situ thermal preparation of polyimide nanocomposite films containing functionalized graphene sheets

Graphene oxides (GO) were exfoliated in N,N-dimethylformamide by simple sonication treatment of the as-prepared high quality graphite oxides. By high-speed mixing of the pristine poly(amic acid) (PAA) solution with graphene oxide suspension, PAA solutions containing uniformly dispersed GO can be obtained. Polyimide (PI) nanocomposite films with different loadings of functionalized graphene sheets (FGS) can be prepared by in situ partial reduction and imidization of the as-prepared GO/PAA composites. Transmission electron microscopy observations showed that the FGS were well exfoliated and uniformly dispersed in the PI matrix. It is interesting to find that the FGS were highly aligned along the surface direction for the nanocomposite film with 2 wt % FGS. Tensile tests indicated that the mechanical properties of polyimide were significantly enhanced by the incorporation of FGS, due to the fine dispersion of high specific surface area of functionalized graphene nanosheets and the good adhesion and interlocking between the FGS and the matrix.     

The Effect of Shear Mixing Speed and Time on the Mechanical Properties of GNP/Epoxy Composites

The aim of this study was to examine the effect of shear mixing speed and time on the mechanical properties of graphene nanoplatelet (GNP) composites. Shear mixing is cited in the literature as one method of making a good dispersion of nanofillers in a polymer that breaks down agglomerates into smaller particles and in the case of GNP can exfoliate layers of graphene. In this paper 0.1 to 5 wt% GNP was mixed with epoxy at different speeds and for different lengths of time. The composites were then cured and the tensile strength and Young’s modulus was measured. Optical microscopy was performed to examine the dispersion of the GNP in the epoxy. The results show that the shear mixing speed and time affect the size of agglomerates, which has an impact on the mechanical properties of the composite. At 3000 rpm and 2 h of mixing the average size of agglomerate was 26.3 μm (30 % reduction compared to that of 1000 rpm and 1 h duration), the tensile strength of epoxy was not affected by the addition of GNP, while a 12 % increase was recorded for the Young’s modulus. It is also found that functionalisation of the surface of the GNP improves the bond formed between the GNP and the resin that enhances its mechanical properties with no effect on the size of the agglomerates. Acetone was used to improve the GNP dispersion and found that shear mixing 5 wt% of GNP with acetone increases the Young’s modulus up to 3.02 from 2.6 GPa for the neat epoxy, an almost 14 % rise.     

Thickness effect on properties of titanium film deposited by d.c. magnetron sputtering and electron beam evaporation techniques

This paper reports effect of thickness on the properties of titanium (Ti) film deposited on Si/SiO₂ (100) substrate using two different methods: d.c. magnetron sputtering and electron beam (e-beam) evaporation technique. The structural and morphological characterization of Ti film were performed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). XRD pattern revealed that the films deposited using d.c. magnetron sputtering have HCP symmetry with preferred orientation along (002) plane, while those deposited with e-beam evaporation possessed fcc symmetry with preferred orientation along (200) plane. The presence of metallic Ti was also confirmed by XPS analysis. FESEM images depicted that the finite sized grains were uniformly distributed on the surface and AFM micrographs revealed roughness of the film. The electrical resistivity measured using four-point probe showed that the film deposited using d.c. magnetron sputtering has lower resistivity of ～13 μΩcm than the film deposited using e-beam evaporation technique, i.e. ～60 μΩcm. The hardness of Ti films deposited using d.c. magnetron sputtering has lower value (～7·9 GPa) than the film deposited using e-beam technique (～9·4 GPa).     

Electrodeposition of platinum nanoparticles on polypyrrole-functionalized graphene

In this study, the new electrocatalyst of platinum support on polypyrrole-functionalized graphene (GNS–PPy/PtNPs) is reported. The polypyrrole-functionalized graphene (GNS–PPy) is constructed first with graphene nanosheets (GNS) and polypyrrole (PPy) particles by constant potential deposition. And then PtNPs are deposited on the surface of GNS–PPy by cyclic voltammetry. The as-prepared GNS–PPy/PtNPs is characterized by scanning electron microscopy, energy-dispersive spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy. The prepared GNS–PPy/PtNPs catalyst is employed for methanol oxidation reactions. Compared with GNS/PtNPs and PPy/PtNPs, the GNS–PPy/PtNPs has higher catalytic activity (508 mA/mg), better stability, and stronger poisoning-tolerance (I _f/I _b = 4.18) due to high dispersion of PtNPs on large surface of GNS–PPy as well as synergic effect among the GNS, PPy particles, and PtNPs. The experimental results indicate that GNS–PPy/PtNPs may be an ideal candidate catalyst for direct methanol fuel cell.     

Preparation and properties of polystyrene nanocomposites with graphite oxide and graphene as flame retardants

In this study, graphite oxides (GOs) with different oxidation degrees and graphene nanosheets were prepared by a modified Hummers method and thermal exfoliation of the prepared GO, respectively. Polystyrene (PS)/GO and PS/graphene nanocomposites were prepared via melt blending. X-ray diffraction results showed that GOs and graphene were exfoliated in the PS composites. It could be observed from the scanning electron microscope images that GOs and graphene were well dispersed throughout the matrix without obvious aggregates. Dynamic mechanical thermal analysis suggested that the storage modulus for the PS/GO1 and PS/graphene nanocomposites was efficiently improved due to the low oxygen content of GO1 and the elimination of the oxygen groups from GO. The flammability of nanocomposites was evaluated by thermal gravimetric analysis and cone calorimetry. The results suggested that both the thermal stability and the reduction in peak heat release rate (PHRR) decreased with the increasing of the oxygen groups in GOs or graphene. The optimal flammability was obtained with the graphene (5 wt%), in which case the reduction in the PHRR is almost 50 % as compared to PS.     

石墨烯增强铜基复合材料的研究进展

石墨烯具有超高的比表面积和优异的力学性能, 是铜基复合材料理想的增强体。传统的粉末冶金工艺很难解决石墨烯在铜基体中的分散问题, 以及石墨烯与铜基体结合性差的难题。随着近些年研究者对石墨烯-铜界面问题深入的探索, 一些新的制备工艺不断出现。本文系统地介绍和对比了近几年石墨烯增强铜基复合材料的制备工艺, 概述了关于石墨烯/铜复合材料力学性能的研究进展, 总结了石墨烯增强铜基复合材料力学性能的机理, 并对未来石墨烯增强铜基复合材料的研究重点进行了展望。