Preparation and characterization of long-chain alkyl silane-functionalized graphene film

Functionalized graphene (FG) was prepared in one step by treating graphene oxide (GO) successively with hexadecyltrimethoxysilane and triethylamine. The FG sheets were subsequently assembled into a thin film by vacuum extraction filtering. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, X-ray diffraction, and Raman spectroscopy were employed to confirm the reduction and silane functionalization of GO to be simultaneously completed during the treatment. The presence of the long hexadecyl chain made the FG hydrophobic. The graphene film showed a high surface roughness, which consisted of many randomly stacked flakes, exhibiting a contact angle of up to 128.1°.     

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).     

γ-Aminopropyl triethoxysilane functionalized graphene oxide for composites with high dielectric constant and low dielectric loss

A facile and efficient approach was developed to simultaneously functionalize and tune the reduction state of graphene oxide (GO) with γ-aminopropyl triethoxysilane (APTES) aided by NH₃ solution. X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy indicated that many surface groups of GO sheets were removed, and APTES were successfully functionalized onto GO sheets. The APTES-functionalized GO sheets (GO-APTES) were dispersed in water and further incorporated into nitrile butadiene rubber (NBR) by latex co-coagulation to form GO-APTES/NBR composites. These composites featured high degrees of exfoliation and intercalation of GO-APTES sheets throughout the NBR matrix. More significantly, the GO-APTES/NBR composites exhibited a relatively high dielectric constant (∼30.8) and a small loss factor (<0.04) at 1.0 kHz, combining with a good insulating property. The unique dielectric responses of GO-APTES/NBR composites open up the potential applications of these materials in resistive and capacitive field grading materials.     

Facile synthesis and application of Ag-chemically converted graphene nanocomposite

An in situ chemical synthesis approach has been employed to prepare an Ag-chemically converted graphene (CCG) nanocomposite. The reduction of graphene oxide sheets was accompanied by generation of Ag nanoparticles. The structure and composition of the nanocomposites were confirmed by means of transmission electron microscopy (TEM), atomic force microscopy (AFM) and X-ray diffraction. TEM and AFM results suggest a homogeneous distribution of Ag nanoparticles (5–10 nm in size) on CCG sheets. The intensities of the Raman signals of CCG in such nanocomposites are greatly increased by the attached silver nanoparticles, i.e., there is surface-enhanced Raman scattering activity. In addition, it was found that the antibacterial activity of free Ag nanoparticles is retained in the nanocomposites, which suggests they can be used as graphene-based biomaterials.      

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.     

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.     

Highly aligned,ultralarge-size reduced graphene oxide/polyurethane nanocomposites: Mechanical properties and moisture permeability

Polyurethane (PU) nanocomposite films containing highly-aligned graphene sheets are produced. Aqueous dispersion of ultralarge-size graphene oxide (GO) is in situ reduced in waterborne polyurethane, resulting in fine dispersion and high degree of orientation of graphene sheets, especially at high graphene contents. The PU/reduced GO nanocomposites present remarkable 21- and 9-fold increases in tensile modulus and strength, respectively, with 3 wt.% graphene content. The agreement between the experiments and theoretical predictions for tensile modulus proves that the graphene sheets are indeed dispersed individually on the molecular scale and oriented in the polymer matrix to form a layered structure. The moisture permeability of the nanocomposites presents a systematic decrease with increasing graphene content, clearly indicating the impermeable graphene sheets acting as moisture barrier. The synergy arising from the very high aspect ratio and horizontal alignment of the graphene sheets is responsible for this finding.     

The preparation of high performance and conductive poly (vinyl alcohol)/graphene nanocomposite via reducing graphite oxide with sodium hydrosulfite

Sodium hydrosulfite is used to reduce graphite oxide in current study. The preparation of poly (vinyl alcohol) (PVA)/graphene nanocomposites is realized using two simple steps: the synthesis of PVA/graphite oxide (GO) nanocomposites film and immersion of such a film in the reducing agent aqueous solution. This method prohibits the agglomeration of GO during direct reduction in PVA/GO aqueous solution, and opens a new way to scale up the production of graphene nanocomposites using a simple reducing agent. A 40% increase in tensile strength and 70% improvement in elongation at break have been obtained with only the addition of 0.7 wt.% of reduced graphite oxide. Furthermore, a good level of conductivity and a variation in the surface property of the prepared films have been observed for the composites containing graphene.     

石墨烯和氧化石墨烯水基润滑添加剂在镁合金冷轧中的摩擦学行为EI北大核心CSCD

选用石墨烯和氧化石墨烯作为水基润滑添加剂,对比研究两种纳米材料对AZ31镁合金在冷轧过程中的摩擦学性能的影响。采用场发射扫描电镜(FESEM)和拉曼光谱仪(Raman)对石墨烯和氧化石墨烯水基润滑液润滑条件下轧后板材表面形貌和成分进行了分析,探讨了石墨烯和氧化石墨烯作为水基润滑添加剂的润滑机理。结果表明,石墨烯和氧化石墨烯在水中最优含量为0.5%(质量分数),摩擦因数分别为0.132和0.038,磨损体积分别为23.1 mm^3和2.59 mm^3。同时氧化石墨烯水基润滑液优良的润滑性能降低了镁合金轧制过程中的轧制力,改善了轧后板材表面质量。相同测试条件下,氧化石墨烯水基润滑液的润滑性能优于石墨烯水基润滑液,主要原因是其在水中良好的分散性和在镁合金表面优异的润湿性。     

Rapid and effective functionalization of graphene oxide by ionic liquid

Functionalized graphene oxide (DDIB-GO) sheets, which can be homogeneously distributed into ortho-dichlorobenene, were obtained via rapid and effective covalent functionalization with imidazolium ionic liquids (1,3-didodecylimidazolium bromine) through ion exchange. The resulting DDIB-GO sheets were characterized by Fourier transform infrared spectroscopy (FTIR), UV Vis NIR spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), Atomic force microscopy (AFM). Furthermore, FTIR, XPS and TGA show that the 1,3-didodecylimidazolium have been covalently attached to the GO sheets. UV Vis NIR, TEM, and AFM demonstrate that after functionalization, the size and shape of DDIB-GO sheets had little change compared with GO sheets and it was mostly dispersed in single layer. And good electronic conductivity of the film prepared from DDIB-GO in ODCB was obtained after high temperature annealing.     

化学还原氧化石墨烯制备高性能石墨烯自组装水凝胶

提出了一种以抗坏血酸钠为还原剂,通过化学还原氧化石墨烯制备高性能石墨烯自组装水凝胶的方法.用扫描电镜,流变及电导率测试,光电子能谱,X-射线晶体衍射和拉曼光谱等手段对该石墨烯水凝胶的结构与性能进行了表征.结果表明:化学还原氧化石墨烯对形成石墨烯水凝胶具有决定性作用.该石墨烯水凝胶具有优异的导电性(1 S·m-1),机械强度和电化学性能.在1 mol·L-1的硫酸电解质溶液中,通过1.2A·g-1恒电流允放电测试,石墨烯水凝胶电极的比电容高达240F·g-1.

Abstract：

Three-dimensional self-assembled graphene hydrogels (SGHs)have been fabricated by chemical reduction of graphene oxide (GO)with sodium ascorbate. The SGHs were characterized by scanning electron microscopy,rheological tests,electrical conductivity measurements,X-ray photoelectron spectroscopy,X-ray diffraction,and Raman spectroscopy. Results indicate that the reduction of GO promotes the assembly of graphene sheets. The SGHs are electrically conductive(1s·m-1)and mechanically strong and exhibit excellent electrochemical performance.In 1 mol·L-1 aqueous solution of H2SO4,the specific capacitance of SGHs was measured to be about 240F·g-1 at a discharge current density of 1.2·-1.     

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.     

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.     

Enhanced thermal resistance of phenolic resin composites at low loading of graphene oxide

By incorporating graphene oxide (GO) into phenolic resin (PR), GO/PR composites were prepared, and the effects of the content and reduction degree of GO on thermal resistance of GO/PR composites were studied. The peak degradation temperature of the PR was increased by about 14 °C with GO which was heat treated. The char yield of GO/PR composite at a GO weight fraction of 0.5% was about 11% greater than that of PR. The interactions such as covalent bonds and π–π stacking between GO and PR were regarded as the main reason for the enhancement. Located at the GO–PR interface, GO effectively anchored and structured PR molecular near the surfaces of GO sheets, and thus facilitated the formation of char. The superiority of GO/PR composites over PR in terms of thermal properties enhancement should also be related to the promoting graphitization by the addition of GO.     

Morphology and properties of segregated-network chemically converted graphene-poly(vinyl chloride) composite

The poly(vinyl chloride)-chemically converted graphene (PVC-CCG) composite prepared using colloidal blending, filtration and drying, and followed by compression molding at 175 degrees C, exhibited an electrical percolation threshold as low as 0.4 wt% and an electrical conductivity as high as 46.5 S/m corresponding to 4.0 wt% of CCG. The high electrical conductivity of the PVC-CCG composite was the result of minimizing the amount of surfactant using various methods. For example, the PVC latex was prepared using miniemulsion polymerization, and the CCG was synthesized via hydrazine reduction of graphene oxide at ambient temperature in order to diminish the irreversible agglomeration of CCG sheets during reduction. The morphology of the PVC-CCG composite, characterized using scanning electron microscopy in charge contrast mode, revealed that the CCG sheets created a segregated network in the PVC matrix.     

An electrochemical route to graphene oxide

Large-scale graphene oxide (GO) with adjustable resistivity was synthesized from graphite via an electrochemical method using KCl solution as an effective electrolyte. During the exfoliation process, electrostatic force intercalates chloride ions between the expanded graphite layers on the anode. These chloride ions form small gas bubbles between the graphite layers in the electrochemical reaction. It is believed that the gas bubbles expand the gap between graphite sheets and produce a separating force between adjacent graphene layers. This separating force overcomes the Van der Waals force between adjacent sheets and exfoliates graphene layers from the starting graphite. Because the graphene is electrochemically oxidized by chorine during the exfoliation, the exfoliated GO sheets are hydrophilic and easily dispersed in the electrolyte solution. The GO solution prepared by the electrochemical exfoliation can be simply sprayed or spin-coated onto any substrate for device applications. The measured average thicknesses of a monolayer, bilayer, and trilayer exfoliated GO on SiO2 substrate were 1.9, 2.8, and 3.9 nm, respectively. It was observed that the measured resistance of the exfoliated GO sheets increases due to electrochemical oxidation in the solution. This electrochemical approach offers a low-cost and efficient route to the fabrication of graphene based devices.     

Noncovalently functionalized multiwalled carbon nanotubes by chitosan-grafted reduced graphene oxide and their synergistic reinforcing effects in chitosan films

Water-soluble chitosan-grafted reduced graphene oxide (CS-rGO) sheets are successfully synthesized via amidation reaction and chemical reduction. CS-rGO possesses not only remarkable graphitic property but also favorable water solubility, which is found to be able to effectively disperse multiwalled carbon nanotubes (MWCNTs) in acidic solutions via noncovalent interaction. The efficiency of CS-rGO in dispersing MWCNTs is tested to be higher than that of plain graphene oxide (GO) and a commercial surfactant, sodium dodecyl sulfate (SDS). With incorporation of 1 wt % CS-rGO dispersed MWCNTs (CS-rGO-MWCNTs), the tensile modulus, strength and toughness of the chitosan (CS) nanocomposites can be increased by 49, 114, and 193%, respectively. The reinforcing and toughening effects of CS-rGO-MWCNTs are much more prominent than those of single-component fillers, such as MWCNTs, GO, and CS-rGO. Noncovalent π-π interactions between graphene sheets and nanotubes and hydrogen bonds between grafted CS and the CS matrix are responsible for generating effective load transfer between CS-rGO-MWCNTs and the CS matrix, causing the simultaneously increased strength and toughness of the nanocomposites.     

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.     

Highly wrinkled cross-linked graphene oxide membranes for biological and charge-storage applications

Inspired by the amphiphilicity of graphene oxide (GO), the surface of water is used as a template for the assembly of a GO film. Methacrylate-functionalized GO sheets can be cross-linked instantaneously at the water-air interface to form a highly wrinkled membrane spreading over an extended area. The multiple covalent linkages amongst the GO sheets enhances the in-plane stiffness of the film compared to noncovalently bonded GO films. The highly convoluted GO membrane can be used in two applications: the promoting of spontaneous stem-cell differentiation towards bone cell lineage without any chemical inducers, and for supercapacitor electrodes. Due to reduced van der Waals restacking, capacitance values up to 211 F g(-1) can be obtained. The scalable and inexpensive nature of this assembly route enables the engineering of membranes for applications in regenerative medicine and energy-storage devices where secondary structures like nanotopography and porosity are important performance enhancers.     

High-resolution separation of graphene oxide by capillary electrophoresis

Separation and purification of graphene oxide (GO) prepared from chemical oxidation of flake graphite and ultrasonication by capillary electrophoresis (CE) was demonstrated. CE showed the ability to provide high-resolution separations of GO fractionations with baseline separation. The GO fractionations after CE were collected for Raman spectroscopy, atomic force microscopy, and transmission electron microscopy characterizations. GO nanoparticles (unexfoliated GO) or stacked GO sheets migrated toward the anode, while the thin-layer GO sheets migrated toward the cathode. Therefore, CE has to be performed twice with a reversed electric field to achieve a full separation of GO. This separation method was suggested to be based on the surface charge of the GO sheets, and a separation model was proposed. This study might be valuable for fabrication of GO or graphene micro- or nanodevices with controlled thickness.