Preparation and characterization of reduced graphene oxide-reinforced boron carbide ceramics by self-assembly polymerization and spark plasma sintering

A self-assembly polymerization process was used to prepare graphene oxide/boron carbide (GO/B₄C) composite powders, spark plasma sintering (SPS) was used to fabricate reduced graphene oxide/boron carbide (rGO/B₄C) composites at 1800 °C and 30 MPa with a soaking time of 5 min. The effects of rGO addition on mechanical properties of the composites, such as Vickers hardness, flexural strength and fracture toughness, were investigated. The results showed that GO/B₄C composite powders were successfully self-assembled and a network structure was formed at high GO contents. The flexural strength and fracture toughness of rGO/B₄C composites were 643.64 MPa and 5.56 MPa m^1/2, respectively, at 1 and 2.5 wt.% rGO content, corresponding to an increase of 99.11% and 71.6% when compared to B₄C ceramics. Uniformly dispersed rGO in rGO/B₄C composites played an important role in improving their strength and toughness. The toughening mechanisms of rGO/B₄C composites were explained by graphene pull-out, crack deflection and bridging.     

Graphene induced carbonization of polyimide films to prepared flexible carbon films with improving-thermal conductivity

Carbon films prepared by polyimide (PI) films treated under 1500°C exhibit favorable thermal conductivity. However, the bonds of carbon films will fracture and recombine which will cause shrinking and forming defects. The flexibility of the carbon films will be greatly reduced, and then affect the application of the carbon films in the field of thermal conduction. When the films prepared by the graphene oxide/polyimide (GO/PI) composite films and the reduced graphene oxide/polyimide (rGO/PI) composite films, respectively, rGO and GO can fill the defects, then increasing the flexibility of the carbon films and inducing the carbonation process. Because of the high thermal conductivity and the six-membered ring structure of rGO and GO, the carbonization temperature will decrease and save costs. When the composite films treated under 1500°C, the thermal conductivity increases with the content of rGO and GO. There are connections between PI and graphene. As the amount of rGO and GO increases, the strong interactions between the rGO or GO and PI lead to contact that enhances its thermal conductivity. However, the rGO and GO have different effects on the films flexibility and thermal conductivity and the differences will be described in the article.     

Reduced-graphene-oxide-reinforced boron carbide ceramics fabricated by spark plasma sintering from powder mixtures obtained by heterogeneous co-precipitation

Reduced graphene oxide (rGO) sheets were uniformly dispersed in boron carbide ceramics by a heterogeneous co-precipitation method. This approach was used to improve the fracture toughness of boron carbide ceramics and to address the problem of agglomeration of graphene in the boron carbide matrix. Cetyltrimethyl ammonium bromide was used as a heterogeneous co-precipitation reaction initiator to prepare a homogeneously dispersed graphene oxide/boron carbide (GO/B₄C) mixture. Reduced graphene oxide/boron carbide (rGO/B₄C) powder mixtures with good dispersion were obtained by high temperature heat treatment. Dense rGO/B₄C composite ceramics were fabricated by spark plasma sintering at 1800 °C and 50 MPa. The fracture toughness and flexural strength of the rGO/B₄C with an rGO content of 2 vol% composite increased by 42% (from 3.43 to 4.88 MPa·m^1/2) and 28% (from 372 to 476 MPa) compared with those of pure B₄C, respectively. The markedly improved fracture toughness and flexural strength of the boron carbide ceramics were attributed to the effect of crack bridging and crack deflection by graphene sheets, graphene interface sliding, and pulling out of graphene.     

Effect of copper sulfate pentahydrate on the structure and properties of poly(vinyl alcohol)/graphene oxide composite films

Poly(vinyl alcohol) (PVA)/graphene oxide (GO)/copper sulfate pentahydrate (CuSO₄·5H₂O) composite films were prepared by the solution casting method, and the effect of CuSO₄·5H₂O on the structure and properties of the PVA/GO composites was investigated. Fourier transform infrared (FTIR) analysis proved the crosslinking interaction between CuSO₄·5H₂O and the ? OH group of PVA. The crystallinity of the composite films increased first and then decreased. For the composite films, the tensile strength, Young's modulus, and yield stress values improved with increasing CuSO₄·5H₂O, whereas the elongation at break decreased compared with that of the neat PVA/GO composite film. The thermogravimetric analysis (TGA) and derivative thermogravimetry (DTG) patterns of the PVA/GO/CuSO₄·5H₂O composite films showed that the thermal stability decreased; this was consistent with the TGA–FTIR analysis. A remarkable improvement in the oxygen‐barrier properties was achieved. The oxygen permeability coefficient was reduced by 60% compared to that of the neat PVA/GO composite film. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44135.     

Proanthocyanidin‐Induced Horizontal Arrangement in Poly(vinyl alcohol)/Graphene Composites with Enhanced Mechanical Properties

A green approach is employed to prepare mechanically enhanced composites by adding noncovalently proanthocyanidin (PC)‐modified graphene (PC‐rGO) into poly(vinyl alcohol) (PVA). Ascorbic acid (AA) is used as the reducing agent, and PC is used as a dispersant to synthesize low‐defect and fully dispersed graphene. After static treatment, the PC‐rGO sheets in the composite form a horizontally arranged structure. Compared with neat PVA, the Young's modulus of the graphene‐modified composites is significantly enhanced by approximately 79.3% with incorporation of 0.9 wt% PC‐rGO. The composites incorporated with GO or AA‐rGO (without PC) have randomly distributed GO structures and apparent rGO agglomeration, resulting in a weaker mechanical property. The dispersibility, degree of defects, distribution state of graphene, and interactions with the polymer matrix are directly related to the final mechanical performance. This new approach to mechanically enhance graphene‐embedded PVA composites provides the possibility for large‐scale production of graphene‐reinforced composite materials.     

聚偏氟乙烯/石墨烯复合材料的制备及性能研究

用溶液共混法制备出聚偏氟乙烯/氧化石墨烯复合材料(PVDF/GO),经高温热压将GO还原得到聚偏氟乙烯/还原氧化石墨烯复合材料(PVDF/rGO)。研究了填料种类及含量对复合材料电学性能、热稳定性和力学性能的影响。结果表明：随GO和rGO的添加,两种复合材料的介电常数(ε _r)均变大、介电损耗(tanδ)变化不大;低含量下GO和rGO均能提高PVDF的热稳定性,但rGO对PVDF性能的改善效果更好;随填料含量从0增加到8%(质量),100 Hz下PVDF/rGO复合材料的ε _r从3.60增加到38.30,PVDF/rGO[4%(质量)]复合材料失重率为5%的分解温度较纯PVDF提高了6.44℃。rGO增强了PVDF的刚性,PVDF/rGO复合材料的拉伸强度先增大后减小,杨氏模量逐渐增大,当rGO含量为4%(质量)时拉伸强度最大,拉伸强度和弹性模量分别较纯PVDF提高了35.30%、22.58%。但GO和rGO都降低了复合材料的击穿场强。     

Poly (vinyl alcohol)/graphene oxide nanocomposite films and hydrogels prepared by gamma ray

ABSTRACT

Poly (vinyl alcohol)/graphene oxide (PVA/GO) gamma irradiated nanocomposite films and hydrogels were prepared. In composite films, GO was initially irradiated by gamma ray in order to improve interactions between GO and PVA. The film containing 1?wt-% GO was very strong where tensile modulus and tensile yield strength were 45 and 115% higher than those of pure PVA. In the second set of experiments PVA/GO hydrogels were made by irradiating PVA/GO suspensions by gamma ray at various doses. It was an interesting finding that GO increased the gel portion of hydrogels through contribution of H-bonds between PVA and GO. The hydrogels prepared at 20?kGy had remarkable water swelling ratio that reached as high as 20 at water temperature of 80°C. The hydrogel metal ion adsorption capability was tested on Cu²⁺ ions. It was shown that the GO contributed significantly to the adsorption capacity of PVA hydrogels.     

Effect of oxygen functional groups of reduced graphene oxide on the mechanical and thermal properties of polypropylene nanocomposites

Reduced graphene oxide (rGO) with various surface structures was prepared by reducing graphene oxide (GO) with hydrazine hydrate (N₂H₄), sodium borohydride (NaBH₄) and l ‐ascorbic acid, respectively. The resulting rGO were used to fabricate rGO/polypropylene (PP) nanocomposites by a melt‐blending method. The surface structure of rGO as well as multifunctional properties of rGO/PP nanocomposites were thoroughly investigated. It was shown that rGO with highest C/O ratio could be obtained by reducing GO with N₂H₄. The crystallization behaviors, tensile strength, thermal conductivity and thermal stability of rGO/PP nanocomposites were significantly improved with the increase of C/O ratio of rGO. For example, with only 1 phr (parts per hundred PP) rGO reduced by N₂H₄, the degree of crystallinity, tensile strength, maximum heat decomposition temperature and thermal conductivity of PP nanocomposite were increased by 6.2%, 20.5%, 48.0 °C and 54.5%, respectively, compared with those of pure PP. Moreover, the thermal degradation kinetics indicated that the decomposition activation energy of rGO/PP nanocomposites could be enhanced by adding rGO with higher C/O ratio. © 2018 Society of Chemical Industry     

Radiation synthesis of graphene oxide/composite hydrogels and their ability for potential dye adsorption from wastewater

A high yield of graphene oxide (GO) was chemically synthesized from graphite powder utilizing adjusted Hummer's method. The contents of acidic functional groups in GO were determined using potentiometric titration. Composite hydrogels dependent on graphene oxide/poly(2-acrylamido-2-methylpropanesulfonic acid)/polyvinyl alcohol (GO/PAMPS/PVA) were synthesized utilizing a ⁶⁰Co gamma irradiation source at different doses. The synthesized graphene oxide and composite hydrogels were portrayed via X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared analysis. The morphology of composite hydrogels was characterized by scanning electron microscope. The gel % and swelling % for the prepared hydrogel demonstrated that the swelling % of hydrogel increased with raising AMPS content. Whereas the increment of GO and increasing the irradiation dose lead to a reduction in the swelling %. The influences of pH, GO percentage, initial dye concentration, the adsorbent dosage, contact time, and temperature on the adsorption of basic blue 3 dye were evaluated and the adsorption capacity was 194.6 mg/g at optimum conditions; pH = 6, GO/PAMPS/PVA composite hydrogels with 5 wt% of GO, initial dye concentration = 200 mg/L, adsorbent dose = 0.1 g, solution volume = 50 mL after 360 min at room temperature (25°C). The adsorption of dye onto the GO/PAMPS/PVA composite hydrogels follows Pseudo-second-order adsorption kinetics, fits the Freundlich adsorption isotherm model.     

Hydrothermal synthesis of Ag2CO3-TiO2 loaded reduced graphene oxide nanocomposites with highly efficient photocatalytic activity

Abstract

In this work, a growth of Ag₂CO₃-TiO₂ NPs over GO sheets and reduction of GO were simultaneously achieved by the hydrothermal process at 130 °C for 4?h. The photocatalytic activity of the as-prepared Ag₂CO₃-TiO₂ NPs decorated reduced graphene oxide (Ag₂CO₃-TiO₂/rGO) composite was studied by the degradation of methylene blue (MB) solution under visible light irradiation. A remarkable enhancement in the photocatalytic activity of the TiO₂ was achieved after sensitizing with Ag₂CO₃ and loading in rGO sheets which is attributed to the reduced charge recombination, enhanced dye adsorption, and the improvement in the light harvesting capacity of the composite.     

Preparation and properties of acrylonitrile–butadiene rubber–graphene nanocomposites

The graphene oxide (GO) was prepared by sonication‐induced exfoliation from graphite oxide, which was produced by oxidation from graphite flakes with a modified Hummer's method. The GO was then treated by hydrazine to obtain reduced graphene oxide (rGO). On the basis of the characterization results, the GO was successfully reduced to rGO. Acrylonitrile–butadiene rubber (NBR)–GO and NBR–rGO composites were prepared via a solution‐mixing method, and their various physical properties were investigated. The NBR–rGO nanocomposite demonstrated a higher curing efficiency and a change in torque compared to the gum and NBR–GO compounds. This agreed well with the crosslinking density measured by swelling. The results manifested in the high hardness (Shore A) and high tensile modulus of the NBR–rGO compounds. For instance, the tensile modulus at a 0.1‐phr rGO loading greatly increased above 83, 114, and 116% at strain levels of 50, 100, and 200%, respectively, compared to the 0.1‐phr GO loaded sample. The observed enhancement was highly attributed to a homogeneous dispersion of rGO within the NBR matrix; this was confirmed by scanning electron microscopy and transmission electron microscopy analysis. However, in view of the high ultimate tensile strength, the NBR–GO compounds exhibited an advantage; this was presumably due to strong hydrogen bonding or polar–polar interactions between the NBR and GO sheets. This interfacial interaction between GO and NBR was supported by the marginal increase in the glass‐transition temperatures of the NBR compounds containing fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42457.     

Functionalized graphene‐reinforced rubber composite: Mechanical and tribological behavior study

A functionalized graphene, fluorinated graphene nanosheets (FGS), and SiO₂ nanoparticles as reinforcing fillers were employed to improve the mechanical properties of the solution styrene butadiene and butadiene rubber composites (SSBR‐BR). The results showed that the mechanical properties of SSBR‐BR composite filled with FGS were substantially improved than those of the unfilled and equivalent filler loaded graphene oxide (GO) and reduced graphene oxide (rGO) filled SSBR‐BR composites. It can be ascribed to the fact that the hydrophobic surface of FGS can be endowed the good dispersion in rubber matrix and stronger interfacial interaction between rubber and fillers. The tribological properties of these composites are also investigated. The results reveal that incorporation of GO, rGO, and FGS in SSBR‐BR composites can decrease antiwear properties because the existence of layered graphene promotes to tear and peel off. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44970.     

Facile synthesis of reduced graphene oxide/MWNTs nanocomposite supercapacitor materials tested as electrophoretically deposited films on glassy carbon electrodes

This paper reports on a facile synthesis method for reduced graphene oxide (rGO)/multi-walled carbon nanotubes (MWNTs) nanocomposites. The initial step involves the use of graphene oxide to disperse the MWNTs, with subsequent reduction of the resultant graphene oxide/MWNTs composites using l-ascorbic acid (LAA) as a mild reductant. Reduction by LAA preserves the interaction between the rGO sheets and MWNTs. The dispersion-containing rGO/MWNTs composites was characterized and electrophoretically deposited anodically onto glassy carbon electrodes to form high surface area films for capacitance testing. Pseudo capacitance peaks were observed in the rGO/MWNTs composite electrodes, resulting in superior performance with capacitance values up to 134.3 F g^?1 recorded. This capacitance value is higher than those observed for LAA-reduced GO (LAA-rGO) (63.5 F g^?1), electrochemically reduced GO (EC-rGO) (27.6 F g^?1), or electrochemically reduced GO/MWNTs (EC-rGO/MWNTs) (98.4 F g^?1)-based electrodes.     

Enhanced mechanical properties of glass fibre epoxy composites by 2D exfoliated graphene oxide filler

Graphene oxide (GO) received a significant attention in the scientific community due to their excellent mechanical properties identifying themselves as an alternative and combinatory to various other metals and composites. Though GO possess excellent strength, it was observed from the literature that graphene oxide consisting of hydroxyl group elements ensue in poor bonding. Thus reduced functional group density (rFGD) graphene is preferred which has an advantage of good bonding, alongside very small quantity as a filler is required to achieve the enhancement equivalent to graphene oxide which forms the novelty of the current work. In current case, 3, 6 and 9 wt% of rFGD is dispersed into E-glass fibre reinforced composite by traditional hand layup technique. The obtained results revealed that, the tensile, flexural and impact strength have shown superior enhancement with 3 and 6 wt% of rGO than neat E-glass epoxy (0 wt% rGO), whereas an asymptotic decrement is noticed at 9 wt% when tested with ASTM standards except for impact strength. The microstructural studies also indicated the proper adhesion and alignment of fibres without any agglomerations corroborate the enhancement of properties. These overall finding supports the suitability of the developed laminates for potential use in structural applications in aerospace industry.     

Conversion of pencil graphite to graphene/polypyrrole nanofiber composite electrodes and its doping effect on the supercapacitive properties

Graphene platelets were synthesized from pencil flake graphite and commercial graphite by chemical method. The chemical method involved modified Hummer's method to synthesize graphene oxide (GO) and the use of hydrazine monohydrate to reduce GO to reduced graphene oxide (rGO). rGO were further reduced using rapid microwave treatment in presence of little amount of hydrazine monohydrate to graphene platelets. Chemically modified graphene/polypyrrole (PPy) nanofiber composites were prepared by in situ anodic electropolymerization of pyrrole monomer in the presence of graphene on stainless steel substrate. The morphology, composition, and electronic structure of the composites together with PPy fibers, graphene oxide (GO), rGO, and graphene were characterized using X‐ray diffraction (XRD), laser‐Raman, and scanning electron microscopic (SEM) methods. From SEM, it was observed that chemically modified graphene formed as a uniform nanocomposite with the PPy fibers absorbed on the graphene surface and/or filled between the graphene sheets. Such uniform structure together with the observed high conductivities afforded high specific capacitance and good cycling stability during the charge–discharge process when used as supercapacitor electrodes. A specific capacitance of supercapacitor was as high as 304 F g^?1 at a current density of 2 mA cm^?1 was achieved over a PPy‐doped graphene composite. POLYM. ENG. SCI., 55:2118–2126, 2015. © 2014 Society of Plastics Engineers     

Preparation and characterization of graphene oxide/poly(vinyl alcohol) composite nanofibers via electrospinning

Graphene oxide (GO) was well dispersed in poly(vinyl alcohol) (PVA) diluted aqueous solution, and then the mixture was electrospun into GO/PVA composite nanofibers. Electron microscopy and Raman spectroscopy on the as‐prepared and calcined samples confirm the uniform distribution of GO sheets in the nanofibers. The thermal and mechanical properties of the nanofibers vary considerably with different GO filler contents. The decomposition temperatures of the GO/PVA composite nanofiber dropped by 38–50°C compared with pure PVA. A very small loading of 0.02 wt % GO increases the tensile strength of the nanofibers by 42 times. A porous 3D structure was realized by postcalcining nanofibers in H₂. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

In Situ Processing of Graphene/Leucite Nanocomposite Through Graphene Oxide/Geopolymer

Graphene/leucite nanocomposites (rGO/leucite) were prepared through in situ reduction of graphene oxide/geopolymer (rGO/KGP) composites. The effects of rGO on the microstructure and mechanical properties with respect to the geopolymer matrix after the high‐temperature treatment were investigated systematically. The results show that GO is first partially reduced in the geopolymeric solution and then completely under the post high‐temperature treatment. The rGO sheets undergo no interfacial reactions with the matrix even after thermal treatment. The rGO/geopolymer composites fully transform to rGO/leucite composites after being treated at 1000°C for 30 min in an argon atmosphere. Significant improvements in mechanical properties were achieved through rGO reinforcement giving flexural strength, elastic modulus, and fracture toughness of 91.1 MPa, 60.5 GPa, and 2.04 MPa·m^1/2, increased by 120%, 8%, and 1.5%, respectively, compared with the leucite matrix alone.     

Simultaneous reduction and surface functionalization of graphene oxide and the application for rubber composites

The simultaneous reduction and functionalization of graphene oxide (GO) was realized through a chemical grafting reaction with a functionalization agent N,N-bis(3-aminopropyl)methylamine (APMEL). The reduced and functionalized reduced GO (rGO-APMEL) sheets can be well dispersed in water without any added surfactant and the formed stable rGO aqueous dispersion can be kept for a long time, which can be used for the preparation of rubber–graphene (GE) composites by latex mixing. The electrostatic interaction between rGO–APMEL (positively charged) and natural rubber latex particles (negatively charged) leads to the formation of NR/rGO–APMEL composites with strong interaction. Compared with blank NR, the tensile strength and modulus for NR/rGO–APMEL increase with the rGO–APMEL loading. Especially, when the filler content is 5 phr, the tensile strength of NR/rGO–APMEL-5 increases by 32.7%, as a control the tensile strength of NR/GO-5 and NR/rGO-5 decrease by 20.1 and 15.6%, respectively. The entanglement-bound rubber tube model was used to analyze the reinforcing effect of GE on NR/rGO–APMEL nanocomposites at a molecular level. This study may provide us a novel approach to prepare well dispersed and exfoliated rGO–polymer nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47375.     

Ionic liquid‐modified graphene/poly(vinyl alcohol) composite with enhanced properties

How to preserve the structure integrity of graphene while enhance its dispersion and compatibility in matrix attracts the attention of researchers in graphene/polymer nanocomposite field. In this paper, methacryloxyethyltrimethyl ammonium chloride (DMC), a kind of ionic liquids, was first used to non‐covalently functionalize graphene in the process of graphene oxide (GO) reduction. The as‐modified graphene (DMC‐rGO) was further incorporated into poly(vinyl alcohol) (PVA) matrix by solution casting technique to fabricate DMC‐rGO/PVA composites. The structure and properties of the obtained DMC‐rGO were investigated by X‐ray diffraction analysis (XRD), X‐ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscope (TEM), Atomic force microscopy (AFM), and Raman test. The results showed that graphene could be successfully modified by DMC through ionic–π interaction and the structure integrity of the graphene could be reserved by this non‐covalently approach. Furthermore, after co‐reduction process, some hydroxyl groups were introduced into DMC‐rGO. In virtue of these intrinsic properties of DMC‐rGO, the fabricated DMC‐rGO/PVA composites exhibit considerable enhancements in mechanical properties and remarkable improvements in thermal stability, as well as the enhancement in electrical conductivity at low DMC‐rGO loading. This simple modification approach gives a new opportunity to improve the performances of graphene/polymer composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45006.     

Microfluidic synthesis of ultrasmall Co nanoparticles over reduced graphene oxide and their catalytic properties

We prepared a one-stage microfluidic-based method for continuous synthesis of cobalt (Co) nanoparticles over reduced graphene oxide (rGO) to produce Co/rGO composites. These were generated by the coreduction of Co²⁺ ions and GO with NaBH₄ which was confined within discrete aqueous plugs segmented by octane as continuous phase. Owing to the excellent transfer properties from recirculation in these plugs, ultrasmall Co nanoparticles were distributed homogeneously on the GO sheets without using any surfactants. As compared to batch methods, the average size of Co nanoparticles and the relative standard deviation decreased from 4.0 ± 1.42 nm and 35.9% to 2.0 ± 0.45 nm and 22.6%, respectively. The as-prepared Co/rGO composites exhibited superior activity towards the catalytic reduction of p-nitrophenol to p-aminophenol with NaBH₄ compared with Co nanoparticles and rGO; this enhanced activity could be attributed to the synergistic effect between Co nanoparticles and rGO.