A novel strategy for making poly(vinyl alcohol)/reduced graphite oxide nanocomposites by solvothermal reduction

Poly(vinyl alcohol) (PVA)/reduced graphite oxide (rGO) nanocomposites were synthesized by solvothermal reduction of graphite oxide (GO) in the presence of PVA. The solvent, the mixed dimethyl sulfoxide (DMSO)-dimethylformamide (DMF), could act not only as a reducing agent but also as a good stabilizer, which achieved effectively reduction of GO in the PVA matrix and avoided the agglomeration of rGO during reduction. A 53.0% increase in tensile strength and 52.6% improvement of Young’s modulus were achieved by addition of 3 wt% of rGO. Furthermore, a significant improvement of thermal stability was observed for the PVA/rGO nanocomposites.     

Crystallization,mechanical performance and hydrolytic degradation of poly(butylene succinate)/graphene oxide nanocomposites obtained via in situ polymerization

Poly(butylene succinate) (PBS)/graphene oxide (GO) nanocomposites were fabricated via in situ polymerization with very low GO content (from 0.03 to 0.5 wt%). The microstructures of the nanocomposites were characterized with Raman spectroscopy, fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), sedimentation experiments and atomic force microscopy (AFM). The results showed that PBS chains have been successfully grafted onto GO sheets during in-situ polymerization, accompanied by the thermo-reduction from GO to graphene. The grafted GO displayed a great nucleating effect on PBS crystallization, resulting in largely improved crystallization temperature and decreased spherules size. A simultaneous enhancement in tensile strength and elongation was achieved for PBS/GO nanocomposites fiber. Meanwhile, increase in hydrolytic degradation rate was also observed for these nanohybrids. Our result indicates that using very low content GO is a simple way to achieve good dispersion yet with remarkable property enhancement for polymer/GO nanocomposites.     

In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites

Electrically conductive and thermally stable polyamide 6 (PA 6) nanocomposites were prepared through one-step in situ polymerization of ε-caprolactam monomer in the presence of electrically insulating and thermally unstable graphene oxide (GO) nanosheets. These nanocomposites show a low percolation threshold of ∼0.41 vol.% and high electrical conductivity of ∼0.028 S/m with only ∼1.64 vol.% of GO. Thermogravimetric analysis and X-ray photoelectron spectroscopy results of GO before and after thermal treatment at the polymerization temperature indicate that GO was reduced in situ during the polymerization process. X-ray diffraction patterns and scanning electron microscopy observation confirm the exfoliation of the reduced graphene oxide (RGO) in the PA 6 matrix. The low percolation threshold and high electrical conductivity are attributed to the large aspect ratio, high specific surface area and uniform dispersion of the RGO nanosheets in the matrix. In addition, although GO has a poor thermal stability, its PA 6 nanocomposite is thermally stable with a satisfactory thermal stability similar to those of neat PA 6 and PA 6/graphene nanocomposite. Such a one-step in situ polymerization and thermal reduction method shows significant potential for the mass production of electrically conductive polymer/RGO nanocomposites.     

Click coupled stitched graphene sheets and their polymer nanocomposites with enhanced photothermal and mechanical properties

The chemically stitched graphene oxide (GO) sheets were obtained using a click chemistry reaction between azide-functionalized GO and alkyne-functionalized GO. The click coupled GO (GO-click-GO) sheets showed the largely increased electrical conductivity and near infrared laser-induced photothermal properties compared to the GO sheets, which result from formation of triazole ring as a bridging linker between the GO sheets. The polyurethane (PU) nanocomposites incorporating the GO-click-GO sheets exhibited enhanced mechanical properties of breaking stress and modulus than the GO/PU nanocomposites. The modulus of GO-click-GO/PU nanocomposites was higher than that of the GO/PU nanocomposites at the same filler loading of 0.1 and 0.5 wt%. The GO-click-GO/PU nanocomposites also showed a significantly improved photothermal properties compared to the GO/PU nanocomposites at the same filler loading. The click coupled stitched GO sheets in this study can be used as the superior reinforcing fillers for mechanically and photothermally high performance polymer nanocomposites.     

Graphene/thermoplastic polyurethane nanocomposites: Surface modification of graphene through oxidation,polyvinyl pyrrolidone coating and reduction

Herein, oxidation, polyvinyl pyrrolidone (PVP) coating and reduction are used to modify the surface of graphene in thermoplastic polyurethane (TPU)/graphene nanocomposites. It is demonstrated that graphene could be easily dispersed in TPU with PVP absorbed on reduced graphene oxide (RGO) as stabilizer during reduction. In the stress–strain curves for these composites containing GO, PVP coated GO (GO/PVP) and reduced GO/PVP (RGO/PVP) as filler, PVP coating and reduction can largely enhance the stress in low modulus region. It is thought to largely related with enhanced interfacial interaction between filler and matrix and healing of graphene structure during reduction. Consequently, the modulus of TPU/GO/PVP and TPU/RGO/PVP is significantly increased. Meanwhile, an electrical percolation threshold of 0.35 wt.% is obtained for TPU/RGO/PVP. Comparing with the results in literature, the filler surface modification used in this study has created nanocomposites with a good balance between electrical conductivity and mechanical properties.     

Effect of graphene oxide on the physical,mechanical and thermo-mechanical properties of neoprene and chlorosulfonated polyethylene vulcanizates

The present research work demonstrated the effect of graphene oxide (GO) on the physical, mechanical, thermo-mechanical etc., properties of neoprene (CR) and chlorosulfonated polyethylene (CSPE) vulcanizates. CR and CSPE based nanocomposites were prepared by both solution intercalation and melt intercalation methods. The changes obtained in the morphology, cure characteristics, mechanical, thermal, thermo-mechanical properties of the rubber nanocomposites have been widely investigated. X-ray diffraction analysis (XRD) and transmission electron microscopic (TEM) analysis of the samples revealed partial exfoliated structure of GO containing rubber composites. Mechanical, thermal, cure and thermo-mechanical properties of the elastomeric nanocomposites were improved compared to the neat rubbers.     

Effects of functional groups on the graphene sheet for improving the thermomechanical properties of polyurethane nanocomposites

Dispersibility of graphene sheets in polymer matrices and interfacial interaction are challenging for producing graphene-based high performance polymer nanocomposites. In this study, three kinds nanofillers; pristine graphene nanoplatelets (GNPs), graphene oxide (GO), and functionalized graphene sheet (FGS) were used to prepare polyurethane (PU) composite by in-situ polymerization. To evaluate the efficacy of functional groups on the graphene sheets, PU reinforced with GNPs, GO, and FGS were compared through tensile testing and dynamic mechanical thermal analysis. The Young's moduli of 2 wt% GO and FGS based PU nanocomposites were found significantly higher than that of same amount of GNPs loading as an evidence of the effect of functional groups on graphene sheets for the mechanical reinforcement. The strong interaction of FGS with PU was responsible to exhibit notably high modulus (25.8 MPa) of 2 wt% FGS/PU composite than the same amount of GNPs and GO loading even at elevated temperature (100 °C).     

Influence of multi-walled carbon nanotubes on electrochemical performance of transparent graphene electrodes

In this work, carbon-carbon nanocomposites as transparent electrodes were prepared by a chemical reduction of graphite oxide (GO) and multi-walled carbon nanotubes (MWNTs). The electric, optical, and electrochemical properties of graphene-MWNT nanocomposites (G-MCs) were investigated as a function of the MWNT content. It was found that chemically bonded G-MCs were successfully formed with a reduction of the functional groups of the GO and acid-treated MWNTs, resulting in the conjugation of 1D MWNTs onto a 2D graphene surface. The electrical conductivity of the graphene was significantly enhanced by introducing the MWNTs. In addition, the G-MCs showed improved current density and high efficiency compared with graphene alone. This indicated that the improved electrochemical performance of the G-MCs can be attributed to the increase in the activity and electrical conductivity enhanced by π-π interaction between graphene and MWNTs.     

Influence of reduced graphene oxide on mechanical behaviors of sodium carboxymethyl cellulose

Sodium carboxymethyl cellulose/reduced graphene oxide (NaCMC/rGO) nanocomposite films were prepared by a simple solution mixing-evaporation method. The NaCMC/rGO nanocomposite films were characterized and compared with sodium carboxymethyl cellulose/graphene oxide (NaCMC/GO) nanocomposite films. The stability of the rGO dispersion, and the structural and mechanical properties of the composite films were investigated by UV–Vis spectrophotometry, X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and using a universal testing machine (UTM). The results revealed that CMC and rGO were able to form a homogenous mixture. Compared with pure CMC, the tensile strength and Young's modulus of the CMC/rGO nanocomposite films were considerably enhanced (by 72.52% and 131.79%, respectively) upon incorporation of 2 wt% rGO.     

Simple facile route for the preparation of graphite oxide and graphene

A simple method is reported for the preparation of graphite oxide (GO) and graphene using KCIO3/NaNO3/H2SO4 and Na2S as oxidizing agent as oxidizing and reducing agents respectively. The formation of GO and graphene have also been confirmed by X-ray diffraction studies, UV-visible, spectroscopy, FTIR and Raman spectroscopy. The morphology, surface charge characteristic and thermal stability behaviour have been studied by SEM/TEM, Zeta potential measurements, thermogravimetric analysis.     

Water dispersible graphene noncovalently functionalized with tryptophan and its poly(vinyl alcohol) nanocomposite

Graphene sheets functionalized noncovalently with aromatic amino acid, tryptophan (Tryp), were prepared by reducing graphene oxide through hydrazine hydrate. Tryp-functionalized graphene is water dispersible and can be stabilized for several months. Atomic force microscopy (AFM), X-ray diffraction (XRD), UV–vis absorption and Raman spectroscopy were used to investigate the nanostructures and the properties of graphene. Application of the graphene dispersion to poly(vinyl alcohol) (PVA) with the help of tryptophan to prepare nanocomposite was also carried out. And the PVA/graphene nanocomposite was characterized by thermogravimetric analysis (TGA) and tensile testing. A 23% improvement in tensile strength and moderate increases in Young’s modulus and thermal stability for PVA were achieved by adding only 0.2 wt% graphene sheets.     

Morphology, mechanical and thermal properties of graphene-reinforced poly(butylene succinate) nanocomposites

Graphene nanosheets (GNSs) reinforced poly(butylene succinate) (PBS) nanocomposites are facilely obtained by a solution-based processing method. Graphene nanosheets, which are derived from chemically reduced graphite oxide (GO), are characterized by AFM, TEM, XRD and Raman spectra. The state of dispersion of the GNSs in the PBS matrix is examined by SEM observations that reveals homogeneous distribution of GNSs in PBS matrix. A 21% increase in tensile strength and a 24% improvement of storage modulus are achieved by addition of 2.0 wt% of GNS. The electrical conductivity and thermal stability of the graphene-based nanocomposite are also improved. DSC measurement indicates that the presence of graphene sheets does not have a remarkable impact on the crystallinity of the nanocomposites. Therefore, the high performances of the nanocomposites are mainly attributed to the uniform dispersion of GNSs in the polymer matrix and strong interfacial interactions between both components.     

Transparent and high gas barrier films based on poly(vinyl alcohol)/graphene oxide composites

Composites of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were synthesized by a modified Hummers method and a solution-mixing method. GO was fully exfoliated in the PVA/GO composites. GO did not affect the crystallization of PVA during solvent evaporation. GO is itself an excellent gas barrier without any chemical reduction. The oxygen permeability of the PVA/GO (0.3 wt.%) composite coated film was 17 times lower than that of the pure poly(ethylene terephthalate) (PET) film, with 92% light transmittance at 550 nm. Composites of PVA and reduced graphene oxide (RGO) were synthesized by performing chemical reduction using hydrazine monohydrate. The oxygen permeability of the PVA/RGO (0.3 wt.%) composite coated film was 86 times lower than that of the pure PET film, with 73% light transmittance at 550 nm. The reduction of oxygen permeability was mainly attributed to the reduced oxygen solubility in the PVA/GO composite film, while it was attributed to both the reduced oxygen diffusivity and solubility in the PVA/RGO composite film.     

Green synthesis of nanosilver‐decorated graphene oxide sheets

A green facile method has been successfully used for the synthesis of graphene oxide sheets decorated with silver nanoparticles (rGO/AgNPs), employing graphite oxide as a precursor of graphene oxide (GO), AgNO₃ as a precursor of Ag nanoparticles (AgNPs), and geranium (Pelargonium graveolens) extract as reducing agent. Synthesis was accomplished using the weight ratios 1:1 and 1:3 GO/Ag, respectively. The synthesised nanocomposites were characterised by scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X‐ray diffraction, UV‐visible spectroscopy, Raman spectroscopy, energy dispersive X‐ray spectroscopy and thermogravimetric analysis. The results show a more uniform and homogeneous distribution of AgNPs on the surface of the GO sheets with the weight ratio 1:1 in comparison with the ratio 1:3. This eco‐friendly method provides a rGO/AgNPs nanocomposite with promising applications, such as surface enhanced Raman scattering, catalysis, biomedical material and antibacterial agent.Inspec keywords: silver, nanoparticles, graphene, nanocomposites, scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X‐ray diffraction, ultraviolet spectra, visible spectra, X‐ray chemical analysis, surface enhanced Raman scattering, catalysis, nanofabricationOther keywords: antibacterial agent, biomedical material, catalysis, surface enhanced Raman scattering, rGO‐AgNP nanocomposite, eco‐friendly method, homogeneous distribution, thermogravimetric analysis, energy dispersive X‐ray spectroscopy, Raman spectroscopy, UV‐visible spectroscopy, X‐ray diffraction, atomic force microscopy, transmission electron microscopy, scanning electron microscopy, nanocomposites, reducing agent, geranium, graphene oxide sheets, graphite oxide, silver nanoparticles, green facile method     

Characterization and properties of in situ emulsion polymerized poly(methyl methacrylate)/graphene nanocomposites

Poly(methyl methacrylate) (PMMA)/graphene nanocomposites were prepared by in situ emulsion polymerization. Raman and Fourier transform infrared spectra showed that PMMA polymer contained partially reduced graphite oxide. Dynamic mechanical analysis and differential scanning calorimetry analysis showed that graphene in the PMMA matrix acted as reinforcing filler; it enhanced the storage moduli and glass transition temperatures of the nanocomposites. Thermogravimetric analysis showed that the thermal stability of the nanocomposites increased by ca. 35 °C. The electrical conductivity of nanocomposite with 3 wt.% graphite oxide was 1.5 S m⁻¹ at room temperature.     

Reinforcing polyamide 1212 with graphene oxide via a two-step melt compounding process

In this study, graphene oxide (GO) was synthesized from graphite powders via Hummers’ method. Polyamide 1212 (PA1212)/GO composites were prepared via a two-step melt compounding process. First, GO concentrates were prepared via solution coagulation. In this method, a GO solution was mixed with an ethanol-soluble polyamide solution. The resulting product was melt-compounded with a PA1212 matrix. This method enabled GO nanosheets to be well-dispersed in a PA1212 matrix. GO, which functioned as a nucleation template, exhibited heterogeneous nucleation effect in the PA1212 matrix because of its large specific surface area. The mechanical properties of the oriented PA1212/GO composites improved efficiently compared with those of pure PA1212. Crystal orientation degree and crystallinity in the composites increased slightly when GO was added after drawing. The composites’ reinforcing effect was mainly attributed to GO nanosheet alignment. These nanonsheets functioned as the nuclei to reinforce the entire oriented crystals.     

The mechanics of graphene nanocomposites: A review

The preparation and characterisation of the different forms of graphene are reviewed first of all. The different techniques that have been employed to prepare graphene such as mechanical and solution exfoliation, and chemical vapour deposition are discussed briefly. Methods of production of graphene oxide by the chemical oxidation of graphite are then described. The structure and mechanical properties of both graphene and graphene oxide are reviewed and it is shown that although graphene possesses superior mechanical properties, they both have high levels of stiffness and strength. It is demonstrated how Raman spectroscopy can be used to characterise the different forms of graphene and also follow the deformation of exfoliated graphene, with different numbers of layers, in model composite systems. It is shown that continuum mechanics can be employed to analyse the behaviour of these model composites and used to predict the minimum flake dimensions and optimum number of layers for good reinforcement. The preparation of bulk nanocomposites based upon graphene and graphene oxide is described finally and the properties of these materials reviewed. It is shown that good reinforcement is only found at relatively low levels of graphene loading and that, due to difficulties with obtaining good dispersions, challenges still remain in obtaining good mechanical properties for high volume fractions of reinforcement.     

Preparation and properties of novel epoxy/graphene oxide nanosheets (GON) composites functionalized with flame retardant containing phosphorus and silicon

2-(Diphenylphosphino)ethyltriethoxy silane (DPPES) was grafted onto the surface of graphene oxide nanosheets (GON) via a condensation reaction. X-ray photoelectron spectroscopy, X-ray diffractometry, Fourier transform infrared spectroscopy and Raman spectroscopy verify that DPPES did not only covalently bond to GON as a functionalization moiety, but partly restored its conjugated structure as a reducing agent. DPPES on graphene sheets oxide was observed by transmission electron microscopy, and contributed to the favorable dispersion of DPPES-GON in nonpolar toluene. Additionally, the flame retardancy and thermal stability of epoxy/DPPES-GON nanocomposites that contain various weight fractions of DPPES-GON were studied using the limiting oxygen index test, UL-94 test and by thermogravimetric analysis in nitrogen. The composites containing 10 wt% DPPES-GON can pass V-0 rating in UL-94 test. Adding 10 wt% DPPES-GON in epoxy greatly increased the char yield and LOI by 42% and 80%, respectively. Epoxy/DPPES-GON nanocomposites with phosphorus, silicon and graphene layer structures were found to exhibit much greater flame retardancy than neat epoxy. The synergistic effects among silicon, phosphorus and GON can improve the flame retardancy of epoxy resin.     

Nylon-6/Graphene composites modified through polymeric modification of graphene

The covalent functionalization of graphene oxide (GO) with poly(vinyl alcohol) (PVA) via ester linkages (GO-es-PVA) as well as the characterization of modified graphene based Nylon-6 (PA6) composite prepared by solution mixing techniques was examined. The anchoring of PVA chains on GO sheets was confirmed by XPS and FTIR measurements. The resulting functionalized sample became soluble in formic acid, allowing solution-phase processing for preparation of PA6/GO composites. Answering to the efficient polymer-chain grafting, a homogeneously dispersion of GO sheets in PA6 matrix and a dramatic improvement of interface adhesion between nanosheets and matrix were observed in PA6/GO-es-PVA composites by SEM and TEM. The depressed crystallization of PA6 chains in PA6/GO-es-PVA composites was investigated by their DSC and XRD results.     

石墨烯/环氧树脂复合材料的介电性能研究

通过Staudenmaier法制备了完全氧化的氧化石墨(GO),并通过高温热膨胀制备了单层石墨烯(graphene)。用FT-IR和TG对GO的氧化程度、含氧官能团进行了表征,用SEM和TEM对天然石墨(NG)、GO和graphene的微观结构进行了分析。利用超声共混法制备了graphene/环氧树脂介电纳米复合材料,介电性能的测试表明,graphene的加入使环氧树脂介电常数大幅提高,当graphene添加量为0.25%(质量分数)时,材料介电常数达到25,是纯环氧树脂的4倍,介电损耗0.11。这为石墨烯在介电储能方面的应用和低成本介电复合材料的制备提供了新思路。