Multiscale patterning of graphene oxide and reduced graphene oxide for flexible supercapacitors

A simple and facile method for multiscale, in-plane patterning of graphene oxide and reduced graphene oxide (GO–rGO) was developed by region-specific reduction of graphene oxide (GO) under a mild irradiation. The UV-induced reduction of graphene oxide was monitored by various spectroscopic techniques, including optical absorption, X-ray photoelectron spectroscopy (XPS), Raman, and X-ray diffraction (XRD), while the resultant GO–rGO patterned film morphology was studied on optical microscope, scanning electron microscope (SEM), and atomic force microscope (AFM). Flexible symmetric and in-plane supercapacitors were fabricated from the GO–rGO patterned polyethylene terephthalate (PET) electrodes to show capacitances up to 141.2 F/g.     

Preparation of well‐dispersed reduced graphene oxide and its mechanical reinforcement in polyvinyl alcohol fibre

The current work reports the preparation and characterization of polyvinyl alcohol (PVA) composite fibres reinforced with graphene reduced from graphene oxide (GO) by using oligomeric proanthocyanidin (OPC) as a reductant. After reduction, most of the oxygen‐containing groups were removed from the GO and reduced graphene oxide (rGO) was prepared. As a result of combined OPC as a dispersant, rGO could be well dispersed in a dimethyl sulfoxide/H₂O mixed solvent and in PVA matrix, and the PVA/rGO dispersion was wet spun followed by hot drawing to prepare continuous PVA/rGO composite fibres. The PVA/rGO composite fibres exhibited a significant enhancement of mechanical properties at low rGO loadings; in particular the tensile strength and Young's modulus of the 2.0 wt% rGO and PVA composite fibre increased to 244% and 294% respectively relative to neat PVA fibre. Moreover, the storage modulus (?10 °C) and T_g increased to 300% and 7.2 °C, respectively. © 2016 Society of Chemical 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     

Enhanced field emission properties of a reduced graphene oxide/carbon nanotube hybrid film

A facile vacuum filtration method for the preparation of hybrid films to achieve superior field emission properties from carbon nanotubes (CNTs) using reduced graphene oxide (rGO) as a bi-functional filler has been proposed. In the hybrid films, CNTs serve as electron emitters, while rGO helps to control the density of the CNT-emitters and reduce electrical resistance of the films. Via controlling volumes of CNTs and rGO dispersions, electron field emission properties of the hybrid films can be easily tailored. Higher weight ratio of rGO:CNT results in better electrical properties and the best field emission property is achieved when a rGO:CNT weight ratio of 1:3 is employed. The hybrid film reveals a significant improvement in field emission properties, as compared with the CNT film without adding rGO. Decreases in sheet resistance, turn-on field, and threshold field are attributed to the formation of extended conjugated network between CNTs and rGO in association with the reduction of screening effect through the optimization of density of CNT-emitters. The concept that rGO can be employed to control the density of CNT emitters will be of special interest for field emission enhancement.     

A facile one step electrostatically driven electrocodeposition of polyviologen–reduced graphene oxide nanocomposite films for enhanced electrochromic performance

Polyviologen (PV)–reduced graphene oxide (rGO) nanocomposite films were fabricated by simple, one-step reductive electropolymerization of cyanopyridinium based precursor monomer (CNP) in an aqueous dispersion of graphene oxide (GO). Since the polymer formation and reduction of graphene oxide occurs within the same potential window, electrocodeposition method was preferred for obtaining nanostructured PV–rGO films. Cyclic voltammetry experiments of PV–rGO displayed two well resolved, reversible one-electron redox processes typical of viologen. Being a redox polymer, incorporation of rGO further enhances the electroactivity of the PV in the composite films. Vibrational spectral analysis with surface characterization revealed structural changes after composite formation along with subsequent reduction of GO within the polymer matrix. The PV–rGO nanostructured film exhibits a high-contrast electrochromism with low driving voltage induced striking color changes from transparent (0 V) to purple (−0.6 V), high coloration efficiency, fast response times and better cycling stability compared to a pristine PV film. This improved performance can be attributed to the high stability of the electrochrome in the composite assembly induced by electrostatically driven non-covalent interactions between redox PV²⁺ and negatively charged rGO, improved electrical conductivity and enlarged surface area accessed through reinforced nanostructured graphene sheets for tethering PV molecules.     

The electrical performance and conductive network of reduced graphene oxide-coated ultra-high-molecular-weight polyethylene fibers through electrostatic interaction and covalent bonding

In this work, methods for reactive coating with graphene (method A and B) are performed to demonstrate feasible ways to functionalize ultra-high-molecular weight polyethylene (UHMWPE) fibers. First, fiber surfaces were polarized by polydopamine (PDA) with amino and hydroxyl groups. In method A, a benchmark method, polarized fibers were dipped into graphene oxide (GO) suspensions for multiple (e.g., eight) cycles to absorb GO, which was then reduced into graphene on fiber surface. In method B, dipping operations were repeated for the same number of cycles, but treatment using 3-aminopropyltriethoxysilane (APS) was applied to induce reactions between the hydroxyl groups and APS, followed by the same reduction treatment. Compared with method A, method B generated fibers with improved and durable surface electric resistance (10⁴ Ω cm⁻¹). The surface morphology and formation of reduced graphene oxide (rGO) conductive networks of the two methods were analyzed. Results indicated that increasing content and the uniform distribution of rGO are beneficial to obtain a conductive network with low and durable surface electric resistance. This deduction was confirmed by loading amounts of rGO and AFM results. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48946.     

酪素基rGO复合乳液的制备及其对皮革阻燃增强效果的研究

为制备具有增强阻燃效果的皮革涂饰材料,本研究首先以天然石墨为原料,采用Hummers法制备氧化石墨烯,并采用NaBH4对其进行还原得到还原氧化石墨烯（rGO）。通过FTIR,XRD和TEM等对其进行表征。结果表明,成功制备了rGO纳米材料。随后,采用物理共混法将rGO引入天然蛋白质酪素体系,制备酪素基rGO复合乳液并将其应用于皮革涂饰,对涂饰后革样的阻燃性能、力学性能和耐干湿擦性能进行测试。结果表明,当rGO的含量为酪素体系溶质质量的0.5%时,与未含rGO的酪素体系相比,涂饰后革样的燃烧速率下降47.2%,极限氧指数（LOI）由24.2%增加至26.3%,热释放速率（HRR）下降53.1%,总热释放率（THR）也有所降低。rGO的引入对涂饰后革样的力学性能和耐干湿擦性能影响不大。     

Conducting glass fibers of giant thermosensitivity by cladding drawing

Strong and conducting glass fibers are produced from reduced graphene oxide and soda-lime-silica (rGO/SLS) glass by a novel process of cladding drawing. GO nanosheets are bound to the SLS glass particles through an electrostatic assembly and are well distributed in the hot-pressed rGO/SLS bulk composites. These bulks are subsequently BN-cladded, from which rGO/SLS fibers are drawn. Results confirm the rGO sheets are well dispersed inside the fibers and become wrinkled due to the contraction of glass matrix while cooling. Mechanical properties of as-prepared fibers have been greatly improved, with tensile strength two times that of pure SLS fibers. As rGO concentration increases, a conducting network of rGO sheets forms along the fibers, which can survive intensive wear. Thanks to the wrinkled configuration of rGO sheets, the conductivity of the composite fibers is extremely sensitive to temperature, nearly 25 times that of flat rGO sheets, making the fibers potential built-in temperature sensors.     

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.     

Accelerated differentiation of neural stem cells into neurons on ginseng-reduced graphene oxide sheets

Asian red ginseng was used for green reduction of chemically exfoliated graphene oxide (GO) into reduced graphene oxide (rGO). The reduction level and electrical conductivity of the ginseng-rGO sheets were comparable to those of hydrazine-rGO ones. Reduction by ginseng resulted in repairing the sp² graphitic structure of the rGO, while hydrazine-rGO showed more defects and/or smaller aromatic domains. The ginseng-rGO sheets presented a better stability against aggregation than the hydrazine-rGO ones in an aqueous suspension. Whilst the hydrophobic hydrazine-rGO films exhibited no toxicity against human neural stem cells (hNSCs), the hydrophilic GO and ginseng-rGO films (as more biocompatible films) showed proliferation of the stem cells after 3 days. On the other hand, the hydrazine-rGO and especially the ginseng-rGO films exhibited more differentiation of hNSCs into neurons (rather than glia) than the GO film, after 3 weeks. The accelerated differentiation on the rGO films was assigned to their higher capability for electron transfer. Meanwhile, the better differentiation on the ginseng-rGO film (as compared to the hydrazine-rGO film) was attributed to its higher biocompatibility, more hydrophilicity and the π−π attachment of ginsenoside molecules (as powerful antioxidants) on surface of the reduced sheets.     

Antibacterial activity of dithiothreitol reduced graphene oxide

A green and simple approach is described for the large scale synthesis of reduced graphene oxide (rGO). The transition of graphene oxide (GO) into graphene was confirmed using various analytical techniques. Raman spectroscopy data indicate the partial removal of oxygen-containing functional groups from the surface of GO and formation of graphene. X-ray diffraction (XRD) was used to investigate the crystallinity of graphene nanosheets. The antibacterial activity of GO and rGO was evaluated using cell viability, reactive oxygen species (ROS) production and DNA fragmentation assays. The results suggest that GO and rGO possessed an excellent antimicrobial activity against Escherichia coli.     

Flexible poly(styrene-b-(ethylene-co-butylene)-b-styrene) nanocomposites for electromagnetic interference shielding

In this report, multiwalled carbon nanotubes (CNT) embedded poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) microspheres (CNT/SEBS) were prepared by solvent evaporation method. Reduced graphene oxide (rGO) nanosheets were used to cover the surface of CNT/SEBS microspheres. The CNT/SEBS/rGO nanocomposites with special segregated conductive network were fabricated by hot pressing these as-prepared complex microspheres. The morphology, electrical percolation threshold, electrical conductivity, and electromagnetic interference (EMI) shielding effectiveness (SE) of CNT/SEBS/rGO composites were characterized. The shielding mechanisms were discussed in detail. Analysis of electrical conductive performance shows that the electrical percolation threshold of rGO is 0.22 vol %. Results of EMI shielding test confirmed the synergistic effect between CNT and rGO. The EMI SE of the composite filled by 2.1 vol % CNT and 3.35 vol % rGO can achieve 26 dB in 8.2− 12.4 GHz (X band), which exceeds the basic requirement for commercial application (20 dB). Its reflectance coefficient (19–41%) indicates that the most part of incident electromagnetic (EM) wave energy is attenuated through absorption mechanism. This kind of absorptive EMI shielding material can be applied without serious secondary EM radiation pollution problems. The effects of filler content, molding temperature on EMI SE, and shielding mechanism were also investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48542.     

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.     

Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.     

Wet-spinning assembly of continuous and macroscopic graphene oxide/polyacrylonitrile reinforced composite fibers with enhanced mechanical properties and thermal stability

Polyacrylonitrile (PAN) composite microfibers with different contents of graphene oxide (GO) were fabricated via wet-spinning route in this work. Based on nonsolvent-induced phase separation theory, N,N-dimethyl formamide/water mixture system was employed as coagulation bath, nonsolvent (water) diffused into PAN spinning solution and led to a quick PAN fiber solidification. Nematic liquid crystal state of GO dispersions and GO/PAN spinning solutions were determined via polarized optical microscopy images, and the morphology and structure of the composite fibers were characterized via scanning electron microscope, Transmission electron microscopy, Fourier transform infrared spectra, and X-ray diffraction. 1 wt % GO/PAN composite fibers exhibited outstanding mechanical properties, 40% enhancement in tensile strength and 34% enhancement in Young's modulus compared with pure PAN fiber. The results of dynamic mechanical analysis indicated that the composite fiber with 1 wt % GO performed the best thermal mechanical property with 5.5 GPa and 0.139 in storage modulus and loss tangent, respectively. In addition, thermogravimetric analysis showed that thermal stability of the composite fibers enhanced with the increasing GO contents. GO/PAN composite fibers can be as the candidate of carbon fiber precursor, high performance fibers, and textiles applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46950.     

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。     

The synthesis of rGO/RuO2, rGO/PANI,RuO2/PANI and rGO/RuO2/PANI nanocomposites and their supercapacitors

Polymer Bulletin - In this work, reduced graphene oxide (rGO) was obtained by chemical reduction of graphene oxide (GO) using sodium borohydride (NaBH4). Four different nanocomposites rGO/ruthenium...     

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.     

Preparation of functional reduced graphene oxide and its influence on the properties of polyimide composites

Homogeneous dispersion and strong filler–matrix interfacial interactions were vital factors for graphene for enhancing the properties of polymer composites. To improve the dispersion of graphene in the polymer matrix and enhance the interfacial interactions, graphene oxide (GO), as an important precursor of graphene, was functionalized with amine‐terminated poly(ethylene glycol) (PEG–NH₂) to prepare GO–poly(ethylene glycol) (PEG). Then, GO–PEG was further reduced to prepare modified reduced graphene oxide (rGO)–PEG with N₂H₄·H₂O. The success of the modification was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and Raman spectroscopy. Different loadings of rGO–PEG were introduced into polyimide (PI) to produce composites via in situ polymerization and a thermal reduction process. The modification of PEG–NH₂ on the surface of rGO inhibited its reaggregation and improved the filler–matrix interfacial interactions. The properties of the composites were enhanced by the incorporation of rGO–PEG. With the addition of 1.0 wt % rGO–PEG, the tensile strength of PI increased by 81.5%, and the electrical conductivity increased by eight orders of magnitude. This significant improvement was attributed to the homogeneous dispersion of rGO–PEG and its strong filler–matrix interfacial interactions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45119.     

Effect of graphene oxide on the molecules of a sodium alginate–krill protein composite system and characterization of the system's composite fiber morphology and mechanical properties

Graphene oxide (GO), sodium alginate (SA), and Antarctic krill protein (AKP) were blended to get functional fibers. These GO–SA–AKP composite fibers were obtained by conventional wet spinning with 5% calcium chloride as a coagulation solution. The intermolecular interactions of the GO–SA–AKP composite system were characterized by Fourier transform infrared spectroscopy. The morphology, crystallinity, thermal stability, and mechanical properties of the GO–SA–AKP composites were investigated with scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. The results show that the number of GO layers decreased gradually during the process of wet spinning. The addition of GO promoted an increase in intramolecular hydrogen bonding and a decrease in intermolecular hydrogen bonding in the composite system. With increasing GO mass fraction, the intermolecular hydrogen‐bond content, crystallinity, breaking strength, and thermal stability in the composite system increased first and then decreased. At the same time, the mass fraction of GO and the draw ratio had significant effects on the surface morphologies of the composite fibers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46642.