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     

Chemically modified graphene oxide/polybenzimidazobenzophenanthroline nanocomposites with improved electrical conductivity

Graphene/polybenzimidazobenzophenanthroline nanocomposites were prepared through the liquid-phase exfoliation of graphene oxide (GO) and reduced graphene oxide (rGO) in methanesulfonic acid with subsequent solution mixing. Various chemical and combined chemical-thermal methods were examined to be effective for producing rGO with highly graphitic structure and excellent electrical conductivity. Raman and X-ray photoelectron spectroscopy showed higher degree of reduction of the GO with the combined chemical-thermal method compared to other chemical reduction processes. Structural characterization of the nanocomposites by X-ray diffraction, scanning electron microscopy and transmission electron microscopy showed good exfoliation and dispersion of both GO and rGO fillers in the polymer matrix. The thermogravimetric analysis found that the nanocomposites with rGO have higher onset and maximum weight loss temperatures than those with GO. Compared with the pure polymer, the electrical conductivity of the nanocomposites containing 10 wt% GO and GO reduced by the combined chemical-thermal treatment showed a remarkable increase by four and seven orders of magnitude, respectively. Long-term in-situ thermal reduction was performed to further improve the conductivities of the nanocomposites.     

Effects of graphene oxide and chemically reduced graphene oxide on the curing kinetics of epoxy amine composites

The curing kinetics of epoxy nanocomposites prepared by incorporating graphene oxide (GO) and chemically reduced graphene oxide (rGO) have been studied using isothermal and nonisothermal differential scanning calorimetry. The kinetic parameters of the curing processes in these systems have been determined by a Kamal and Sourour phenomenological model expanded by a diffusion factor. The predicted curves determined using the kinetic parameters fit well with the isothermal DSC thermograms revealing the proposed kinetic equation clearly explains the curing kinetics of the prepared epoxy amine nanocomposites. Experimental and modeling results demonstrate the presence of an accelerating effect of the GO on the cure of the resin matrix. The use of rGO instead of GO resulted in a slight acceleration reaction rate due to the reduced presence of oxidation groups in rGO. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44803.     

Highly soluble polyetheramine-functionalized graphene oxide and reduced graphene oxide both in aqueous and non-aqueous solvents

Among many methods to synthesize graphene, solution-based processing provides many advantages owing to its low cost, high productivity, chemical versatility, and scalability. In particular, graphene oxide (GO) is one of the most promising nanocarbons that enable the incorporation of graphene and related materials into bulk materials and nanocomposites. GO has hydrophilic nature that enables straightforward dispersion in aqueous solution by sonication, but GO show poor dispersibility in common organic solvents, which prevent much wider applications such as solution-mixing polymer nanocomposites. Here we prepared highly soluble, functionalized GO in both aqueous and non-aqueous solvents. This was achieved by reacting polyetheramine consisting of amphiphilic components, e.g., polypropylene oxide and polyethylene oxide, with carboxylic acid groups at GO edges. Moreover, the reduced GO (rGO) was also highly dispersible in aqueous solution as well as non-aqueous solutions. These functionalized GO and rGO can be used for many solution-processed graphene composites.     

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.     

Electrical conductivity of silicon carbonitride‐reduced graphene oxide composites

Silicon carbonitride ceramics–reduced graphene oxide (SiCN–rGO) composites are synthesized using polyvinylsilazne (PVSZ) and GO as precursors and N‐dimethylformamide (DMF) as a solvent. We find that the electrical conductivity of SiCN–rGO composites exhibits nonmonotonic changes as a function of GO concentrations, in which the conductivity increases by six orders of magnitude from 7.41E‐09 (Ω/cm)^?1 to 4.35E‐03 (Ω/cm)^?1 after the integration of 0.2 wt% GO, followed by three orders of magnitude drop to 3.34E‐06 (Ω/cm)^?1 when 0.3 wt% GO is integrated. Based on the energy‐dispersive spectroscopy and Raman spectroscopy analysis, we conclude that the conductive behavior of SiCN–rGO composites is controlled by both the concentration and the distribution of “free‐carbon” in the composites.     

干燥温度对纳米氧化石墨烯/PHBH复合膜结构及性能的影响

通过溶液浇铸法制备得到纳米氧化石墨烯（GO）/聚羟基丁酸-羟基己酸酯（PHBH）复合膜,利用SEM、XRD、DSC、拉伸测试、阻隔测试及透明度测试等检测手段,研究了不同干燥温度对复合膜结构及性能的影响,优化了制备工艺。结果表明：随着干燥温度的升高,GO在PHBH中的分散性以及复合膜的结晶度、断裂伸长率和阻隔性先增加后减小,而拉伸强度及透光率则随温度的增加而增加。当干燥温度为45℃→55℃梯度升温时,GO在PHBH中均匀分散,且复合膜的断面光滑,有良好的结晶度、热稳定性、力学及阻隔性能,其拉伸强度、断裂伸长率可分别达到20.11MPa、17.47%,且透氧系数及水蒸气透过系数分别为48cm³/(m²·d)、13.33g/(cm²·d),综合性能优于其他干燥温度下的复合膜。     

Physical and thermal characterization of graphene oxide modified gelatin‐based thin films

The incorporation of graphene oxide (GO) nanosheets into fish gelatin‐based films and the resulting effect on the structural, mechanical, and thermal properties of the film was investigated. Gelatin films were prepared using a casting method with d ‐sorbitol as the plasticizer and carrageenan as the stabilizer. GO nanofillers were dispersed into the gelatin network in different weight percentages. FTIR spectroscopy was used to characterize the molecular structure of gelatin films and revealed that there were no major changes in the functional groups of fish gelatin films after addition of GO and carrageenan. Tensile, differential scanning calorimetery (DSC), and thermo gravimetric analysis (TGA) tests were performed to study the effectiveness of GO nanofillers and the effect of sorbitol and carrageenan on the film properties. Addition of 1 wt% of GO significantly increased the tensile strength and the elongation modulus of the gelatin films (to 44 and 1320 MPa, respectively). This was attributed to the strong interfacial interactions between GO sheets and gelatine molecules. However, increasing the GO percentage to 2 wt% resulted in a considerable decrease in both properties (to 11 and 224 MPa, respectively). This might be due to the agglomeration of GO sheets in the gelatin network. DSC results showed a substantial increase in the T_m of the films as a result of adding carrageenan and GO to the gelatin network. This might be due to the strong combination of helical structure of carrageenan and oxygen containing groups of GO. POLYM. COMPOS., 35:2043–2049, 2014. © 2014 Society of Plastics Engineers     

Novel electroactive polyamide 12 based nanocomposites filled with reduced graphene oxide

Novel electroactive nanocomposites were prepared by adding to a polyamide 12 (PA12) matrix different amounts (from 1 to 8 wt%) of reduced graphene oxide (rGO), and the thermo‐electrical behavior of the prepared bulk materials was compared with that of the corresponding fibers. FESEM micrographs on bulk materials highlighted an evident aggregation of the rGO lamellae, proportional to the filler concentration. The presence of rGO stacks was responsible of a heavy embrittlement of the samples, with a strong reduction of the elongation at break, and of the limited electrical conductivity of the samples (about 10⁵ Ω·cm with a rGO amount of 4 wt%). Moreover, nanofiller addition determined an improvement of the thermal degradation resistance, associated to a slight drop of the glass transition temperature (about 7°C with a nanofiller concentration of 4 wt%) and of the crystallinity degree (up to 9% for an rGO loading of 4 wt%). The extrusion process adopted to prepare nanocomposite fibers caused a partial breakage of rGO aggregates and their progressive alignment along the drawing direction, determining thus an electrical resistivity increase with respect to the bulk samples. Therefore, the surface heating of the prepared fibers through Joule effect was possible only at elevated rGO amounts (i.e., 8 wt%). POLYM. ENG. SCI., 59:198–205, 2019. © 2018 Society of Plastics Engineers     

Interface adjustment between poly(ethylene terephthalate) and graphene oxide in order to enhance mechanical and thermal properties of nanocomposites

There is great interest in the use of graphene and derivatives in the production of polymer nanocomposites as it provides improvements in the properties of the materials to which they are associated. Such improvements depend heavily on filler dispersion and the interaction between the nanomaterials and the matrix. This work aimed to study the compatibility of graphene oxide (GO) with a poly(ethylene terephthalate) matrix. For this, graphite was modified using Hummers method, using reaction times of 3 and 6 h. The obtained GO was functionalized with amine, amide, and magnetite groups (FGO). The effects of the oxidation degree, functionalization and concentration of the nanofillers on the dispersion and consequently on the properties of the polymer nanocomposites were evaluated. The nanocomposites were synthesized by the solid–solid deposition method followed by the melt mixing technique. It was observed that lower concentrations of nanofiller associated with the lower degree of oxidation and functionalization improved the interaction of the nanofillers with the matrix, which resulted in better mechanical properties under tensile stresses for strain at break, maximum stress, Young's modulus and toughness. It was also observed that the glass transition and crystallization of nanocomposites increased due to a nucleating effect of the nanofillers.     

Preparation and characterization of graphene oxide reinforced PVA film with boric acid as crosslinker

PVA films were prepared through aqueous solution method, and boric acid (BA) as well as graphene oxide (GO) was added to improve the mechanical and thermal properties. It was found that 5 wt % BA could increase the tensile strength threefold (from 23.3 to 67.7 MPa), and the incorporation of 0.2 wt % GO would provide additional percentage growth of 30% (from 67.7 to 88.5 MPa). Moreover, an enhancement of thermal stability of PVA film was found when BA or GO filler was added. The reinforcement mechanisms of both BA and GO were investigated, and a competitive phenomenon that the addition of BA would influence the reinforcement effect of GO sheets was found. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42000.     

The reduction of graphene oxide

Graphene has attracted great interest for its excellent mechanical, electrical, thermal and optical properties. It can be produced by micro-mechanical exfoliation of highly ordered pyrolytic graphite, epitaxial growth, chemical vapor deposition, and the reduction of graphene oxide (GO). The first three methods can produce graphene with a relatively perfect structure and excellent properties, while in comparison, GO has two important characteristics: (1) it can be produced using inexpensive graphite as raw material by cost-effective chemical methods with a high yield, and (2) it is highly hydrophilic and can form stable aqueous colloids to facilitate the assembly of macroscopic structures by simple and cheap solution processes, both of which are important to the large-scale uses of graphene. A key topic in the research and applications of GO is the reduction, which partly restores the structure and properties of graphene. Different reduction processes result in different properties of reduced GO (rGO), which in turn affect the final performance of materials or devices composed of rGO. In this contribution, we review the state-of-art status of the reduction of GO on both techniques and mechanisms. The development in this field will speed the applications of graphene.     

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。     

Largely improved crystallization behavior and thermal stability of poly(L‐lactide) via the synergistic effects of graphene oxide and carbon nanotubes

Graphene oxide (GO) and carbon nanotubes (CNTs) and their compound were introduced into semicrystalline poly(l ‐lactide) (PLLA) to prepare the corresponding binary and/or ternary nanocomposites, respectively. The dispersion states of nanofillers in different nanocomposites were investigated using UV‐Vis spectroscopy, scanning electron microscopy (SEM) and rheological measurement. The results showed that when GO and CNTs were simultaneously present in the PLLA matrix, good dispersion states of both GO and CNTs could be achieved and the ternary nanocomposites exhibited percolated network structure. The effects of different nanofillers on the crystallization behavior of PLLA matrix were comparatively investigated under the different crystallization conditions including melt crystallization process (nonisothermal and isothermal crystallization from the melt) and cold crystallization (crystallization occurring from an amorphous state during the annealing process). The results showed that GO and CNTs exhibited apparent synergistic effects in improving crystallization ability and enhancing crystallinity of PLLA matrix. Study on the thermal stability of nanocomposites showed that the presence of nanofillers greatly improved the thermal stability of PLLA matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40143.     

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.     

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     

Mechanical,thermal conductive,and dielectric properties of fluoroelastomer/reduced graphene oxide composites in situ prepared by solvent thermal reduction

Fluoroelastomer (FKM)/reduced graphene oxide (rGO) composites are in situ prepared by solvent thermal reduction method in N,N‐dimethylformamide (DMF) solution. The reduction of graphene oxide (GO) is characterized by X‐Ray photoelectron (XPS), ultraviolet–visible (UV–vis), and Fourier transform infrared (FTIR) spectra. GO and rGO are both efficient fillers to improve the mechanical properties of FKM. The dispersibility of rGO is improved after solvent thermal reduction which is confirmed by scanning electron micrograph (SEM) and X‐ray diffraction (XRD). The homogenous suspension of FKM/rGO composites in DMF can stay stable for more than a month. The dielectric permittivity of FKM/rGO (5 phr) is 26.4 at the frequency of 10⁻¹ Hz, higher than the pure FKM (8.1). The thermal conductivity of rGO/FKM composites increases. POLYM. COMPOS., 35:1779–1785, 2014. © 2013 Society of Plastics Engineers     

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.     

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.     

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.