Mechanical properties of carbon fiber composites modified with graphene oxide in the interphase

The surface topographies of carbon fibers treated by sizing agents with different graphene oxide (GO) content were investigated by scanning electron microscopy. The surface elements compositions of carbon fibers were determined by X‐ray photoelectron spectrometer. The interfacial properties of composites were studied by interfacial shear strength. The thermo‐mechanical properties of two typical specimens (CF‐G0 and CF‐G1 composites) were investigated by dynamic mechanical thermal analysis. The results showed the introduction of GO sheets on carbon fibers surfaces effectively improved the mechanical properties of carbon fibers/epoxy composites. POLYM. COMPOS., 38:2425–2432, 2017. © 2016 Society of Plastics Engineers     

Free-Standing Graphene Oxide and Carbon Nanotube Hybrid Papers with Enhanced Electrical and Mechanical Performance and Their Synergy in Polymer Laminates

Hybrid nanomaterials fabricated by the heterogeneous integration of 1D (carbon nanotubes) and 2D (graphene oxide) nanomaterials showed synergy in electrical and mechanical properties. Here, we reported the infiltration of carboxylic functionalized single-walled carbon nanotubes (C-SWNT) into free-standing graphene oxide (GO) paper for better electrical and mechanical properties than native GO. The stacking arrangement of GO sheets and its alteration in the presence of C-SWNT were comprehensively explored through scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. The C-SWNTs bridges between different GO sheets produce a pathway for the flow of electrical charges and provide a tougher hybrid system. The nanoscopic surface potential map reveals a higher work function of the individual functionalised SWNTs than surrounded GO sheets showing efficient charge exchange. We observed the enhanced conductivity up to 50 times and capacitance up to 3.5 times of the hybrid structure than the GO-paper. The laminate of polystyrene composites provided higher elastic modulus and mechanical strength when hybrid paper is used, thus paving the way for the exploitation of hybrid filler formulation in designing polymer composites.     

高电活性石墨烯/聚苯胺纳米复合材料的制备和表征

采用了一种简单有效地方法制备了高电活性的石墨烯/聚苯胺复合材料。首先,将苯胺在氧化石墨烯（GO）的水性分散液中氧化聚合,制备了氧化石墨烯/聚苯胺（GO/PANI）,再将GO/PANI与水合肼反应,制得还原-氧化石墨烯/聚苯胺（R（GO/PANI））。利用透射电子显微镜（TEM）,热失重分析（TGA）和循环伏安法（CV）对GO/PANI和R（GO/PANI的形貌,热稳定性和电化学性能进行了分析研究。结果表明,GO表面存PANI,且R（GO/PANI）的热稳定性和电活性都明显高于GO/PANI。     

Electrospinning of poly(ε‐caprolactone) solutions containing graphene oxide: Effects of graphene oxide content and oxidation level

The morphological appearance, fiber diameter, and structure of poly(ε‐caprolactone) (PCL) nanofibers produced by the electrospinning process were studied in the presence of different amounts of graphene oxide (GO) with different oxidation levels. Scanning electron microscope micrographs of electrospun fibers showed that the average fiber diameter decreases in the presence of GO with different loading and oxidation levels. The loading level of GO especially higher than 0.3 wt% was influential in decreasing the diameter of PCL electrospun fibers rather than oxidation level. Contact angle, infrared spectroscopy, and conductivity measurements on graphite oxide (GtO) samples, as well as rheological, conductivity, and surface tension experiments on PCLGO solutions were performed to describe the role of GO in the significant reduction of fiber diameter. It was found that three factors are involved in generating a driving force for more stretching of the electrospinning jet. One is the viscosity reduction of PCLGO solution, which intensifies by more GO content and less GO oxidation level. The second is solution conductivity which enhances by GO loading and the third is the charge relaxation time of the spinning solution, which grows with increasing the oxidation level of GO as well as the GO content. POLYM. COMPOS., 131–140, 2016. © 2014 Society of Plastics Engineers     

Mechanical property enhancement of non‐bonding electrospun mats via adhesive

In the present study, the effect of adhesive on the morphology of different electrospun polymeric mats was investigated. The modification of two polymers, poly(methyl methacrylate) and poly(vinyl chloride), was carried out by blending the polymers with different amounts of poly(butyl acrylate) (PBA) adhesive to investigate the effect of different amounts of adhesive with heat hardener in hybrid mats. The introduction of various concentrations of PBA into different polymer solutions led to the formation of point‐bonded electrospun fibrous mats. Scanning electron microscopy images indicated that point‐bonded polymer/adhesive fibers were uniformly distributed throughout the mats. Fourier transform infrared spectrometry, contact angle measurements and thermogravimetric analysis were used to study the different properties of the hybrid mats. The tensile strength of the blended fibrous electrospun mats was increased effectively. This enhancement of the mechanical properties of the mats due to the presence of adhesive increases the number of potential applications of the electrospun mats, especially for mechanically weak polymers. Copyright © 2012 Society of Chemical Industry     

Epoxy/p‐phenylenediamine functionalized graphene oxide composites and evaluation of their fracture toughness and tensile properties

In an attempt to enhance the mechanical properties of epoxy/graphene‐based composites, the interface was engineered through the functionalization of graphene oxide (GO) sheets with p‐phenylenediamine; this resulted in p‐phenylenediamine functionalized graphene oxide (GO–pPDA). The morphology and chemical structure of the GO–pPDA sheets were studied by spectroscopic methods, thermal analysis, X‐ray diffraction, and transmission electron microscopy. The characterization results show the successful covalent functionalization of GO sheets through the formation of amide bonds. In addition, p‐phenylenediamine were polymerized on graphene sheets to form crystalline nanospheres; this resulted in a GO/poly(p‐phenylenediamine) hybrid. The mechanical properties of the epoxy/GO–pPDA composite were assessed. Although the Young's modulus showed improvement, more significant improvements were observed in the strength, fracture strain, and plane‐strain fracture toughness. These improvements were attributed to the unique microstructure and strong interface between GO–pPDA and the epoxy matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43821.     

Chemical Functionalization of Graphene Oxide by Poly(styrene sulfonate) Using Atom Transfer Radical and Free Radical Polymerization: A Comparative Study

Poly(sodium styrenesulfonate)-functionalized graphene was prepared from graphene oxide, using atom transfer radical polymerization and free radical polymerization. In atom transfer radical polymerization route, the amine-functionalized GO was synthesized through hydroxyl group reaction of GO with 3-amino propyltriethoxysilane. Atom transfer radical polymerization initiator was grafted onto modified GO (GO-NH₂) by reaction of 2-bromo-2-methylpropionyl bromide with amine groups, then styrene sulfonate monomers were polymerized on the surface of GO sheets by in situ atom transfer radical polymerization. In free radical polymerization route, the poly(sodium 4-styrenesulfonate) chains were grafted on GO sheets in presence of Azobis-Isobutyronitrile as an initiator and styrene sulfonate monomer in water medium. The resulting modified GO was characterized using range of techniques. Thermal gravimetric analysis, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy results indicated the successful graft of polymer chains on GO sheets. Thermogravimetric analysis showed that the amount of grafted polymer was 22.5 and 31?wt% in the free radical polymerization and atom transfer radical polymerization methods, respectively. The thickness of polymer grafted on GO sheets was 2.1?nm (free radical polymerization method) and 6?nm (atom transfer radical polymerization method) that was measured by atomic force microscopy analysis. X-ray diffractometer and transmission electron microscopy indicated that after grafting of poly(sodium 4-styrenesulfonate), the modified GO sheets still retained isolated and exfoliated, and also the dispersibility was enhanced.     

Templated patterning of graphene oxide using self-assembled monolayers

A cost-effective and efficient route for graphene oxide (GO) patterning through site-selective deposition of GO onto a photopatterned self-assembled monolayer (SAM) of octadecylphosphonic acid on the surface of native oxide of titanium was demonstrated. In this process, SAMs on titanium oxide was first patterned via ultraviolet light exposure through a mask, subsequent drop-casting of GO aqueous dispersion on the substrate resulted in the site-selective deposition of GO on the hydrophilic areas. The formation of GO patterns is evidenced by Raman mapping. Atomic force microscopy studies indicate that the thickness of patterned GO can be controlled by adjusting the concentration of the GO dispersion. Scanning electron microscopy, and inverted fluorescence microscopy of large area GO patterns demonstrate this process is scalable and that the fluorescent property of nanoscale GO sheets is still reserved after deposition.     

Improvement of interfacial properties in bismaleimide composites using functionalized graphene oxide grafted carbon fiber

A hierarchical reinforcement, which was used to improve the interfacial properties of bismaleimide (BMI) composites, was prepared by grafting functionalized graphene oxide (GO) onto a carbon fiber surface. The GO and carbon fibers were first functionalized separately to create interactional functional groups on their surfaces. The grafting process was then realized by an amidation reaction of the amine and acyl chloride function groups formed on GO and carbon fibers, respectively. The surface groups of functionalized GO and carbon fibers were identified by an X‐ray photoelectron spectroscopy (XPS). The resulting reinforcement was further characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and dynamic contact angle analysis. Experimental results showed that the functionalized GO were successfully grafted onto the carbon fibers surfaces and significantly increased the surface energy of carbon fibers. The study also indicated that the prepared hierarchical reinforcement could significantly improve the interfacial adhesion of resulting BMI composite. POLYM. ENG. SCI., 58:886–893, 2018. © 2017 Society of Plastics Engineers     

Metal ion-directed solution-phase tailoring: from large-area graphene oxide into nanoscale pieces

Due to fascinating electronic properties and great potential in various applications, graphene has attracted great interest. Recently, much work have focused on the synthesis of different sizes and properties of graphene or graphene oxides (GOs), for example, graphene nanoribbons, nanosized graphene pieces, and nanosized triangular and hexagonal graphene sheets terminated by zigzag edges. Herein, we have demonstrated a widely available approach to fabricate the nanoscale GO pieces by directly solution-phase cutting a large-area GO sheet into nanoscale pieces via spontaneous redox reactions at room temperature. In this process, GO acts with dual functions as a model and a reducing reagent. With a typical example of silver ions, we have investigated in detail the influence of the reaction time and concentration of metal ions on yield and size of nanoscale GO pieces. Moreover, we also obtain Ag nanoparticle coating on the GO surface. Finally, a possible mechanism is suggested to explain the formation of nanoscale GO pieces.     

氧化石墨烯-壳聚糖纤维制备及其对染料吸附性能

选取壳聚糖和聚乙烯醇与氧化石墨烯共混复合,通过湿法纺丝工艺技术,制备不同氧化石墨烯含量的氧化石墨烯-壳聚糖复合纤维。利用扫描电镜和红外光谱表征了复合纤维的微观结构和化学组成,结果表明:复合纤维成形较好,氧化石墨烯与壳聚糖之间形成了稳定的氢键。通过染料吸附试验可知:氧化石墨烯可明显提高复合纤维对染料的吸附能力,当氧化石墨烯质量分数为1%时,吸附效果最理想,吸附量可达407 mg/g,有望用于印染废水的综合处理。     

Electrospun PVDF graphene oxide composite fibre mats with tunable physical properties

This article is aimed at a basic physical characterization of electrospun PVDF/graphene oxide (GO) composite non-woven fibre mats. The morphological characterization of the prepared fabrics was performed via SEM investigations. Introduction of the GO during the electrospinning process caused significant changes in the crystalline structure of PVDF, and a transformation from α- to β-crystalline phases was achieved. Addition of the GO particles into PVDF did not only improve the thermal stability of the polymer, but also acted as a reinforcing filler, giving rise to improved dynamic moduli and tensile strength. The dielectric properties were evaluated over a broad frequency range, and it was confirmed that the presence of small amounts of GO had little effect on the dielectric properties of the PVDF, since the GO has a dielectric character similar to that of the PVDF.     

Effect of organic solvent on morphology and mechanical properties of electrospun syndiotactic polypropylene nanofibers

We study the stress–strain behaviors of the electrospun sPP single nanofibers as well as nonwoven mats, which were electrospun from sPP solutions using two different solvents (decalin and cyclohexane) by electrospinning. The effects of organic solvents were explored on the morphologies and the mechanical properties of the corresponding electrospun sPP single nanofibers and nonwoven mats. It was found that the nature of organic solvents dramatically affected the surface morphologies, the circular and looping deposition of the electrospun sPP fibers, and the mechanical properties. The tensile strength of both electrospun sPP single nanofibers and nonwoven mats prepared from decalin-base solution was stronger than that of cyclohexane-base solution.     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.     

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     

Photovoltaic and UV detector applications of ZnS/rGO nanocomposites synthesized by a green method

The effect of graphene concentration on the photovoltaic and UV detector applications of ZnS/graphene nanocomposites was investigated. The nanocomposites were synthesized by a green, cost-effective, and simple co-precipitation method with different graphene concentrations (5, 10, and 15 wt%) using L-cysteine amino acid as a surfactant and graphene oxide (GO) powder as a graphene source. Transmission electron microscopy (TEM) images showed that the ZnS NPs were decorated on GO sheets and the GO caused a significant decrease in ZnS diameter size. The results of X-ray diffraction (XRD) patterns, Raman, and Fourier transform infrared (FTIR) spectroscopy indicated that the GO sheets were changed into reduced graphene oxide (rGO) during synthesis process. Therefore, L-cysteine amino acid played its role as a reducing agent to reduce the GO. Photovoltaic measurements showed that the graphene caused to increase the efficiency of solar-cell application of ZnS/rGO nanocomposites. In addition, our observation showed that the nanocomposites were suitable as ultraviolet (UV) detectors and graphene concentration increased the responsibility of the detectors.     

Electrical conductivity studies on water‐soluble polypyrrole–graphene oxide composites

Polypyrrole (PPy)–graphene oxide (GO) composites are synthesized via a soft‐chemical in situ method at different GO concentrations (10, 20, 30, 40, and 50 wt%) and with ammonium persulfate (APS) as the oxidant. The synthesized composites were characterized using Fourier transform infrared (FTIR) and ultraviolet‐visible light (UV–vis) spectroscopic studies, and their surface properties were analyzed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Characterization and surface morphology results indicate that PPy is adsorbed onto the graphene surfaces and/or fills the GO sheets. The temperature‐dependent DC conductivity of the polymer composite films in the 300–500 K range indicates a semiconducting behavior with increasing GO concentration in the PPy polymer. Based on morphological and conductivity studies, the large surface area and high aspect ratio of the in situ‐generated GO may have played an important role in the noticeable improvement in the electrical conductivity of the prepared composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation of polyacrylonitrile/graphene oxide by in situ polymerization

Highly oriented molecular structure is essential for high‐performance carbon fibers. The addition of a small amount of graphene sheets may enhance the degree of molecular orientation of precursor fibers during spinning and stabilization by limiting the disorientation of the chain segments. Graphene sheets merge into the carbon fiber structure during carbonization. The structure and properties of polyacrylonitrile containing graphene oxide (GO) prepared by in situ polymerization were investigated. With increasing GO loading, the molecular weight of the polymer decreased gradually from 69 000 g mol^?1 for the sample without GO to 60 600 g mol^?1 for the sample with 2.5 wt% loading of GO. Scanning electron microscopy and X‐ray diffraction results indicated that GO was dispersed in single layers in the polymer matrix. The degree of crystallization of the polymer with 0.5 wt% GO was increased by 8%. Moreover, differential scanning calorimetry and thermogravimetric analysis showed that an appropriate amount of GO, e.g. 0.5 wt%, made the carbon yield of the polymer increase by 5.0 wt%, because the GO in the composite improved the intermolecular crosslinking reaction. Copyright © 2012 Society of Chemical Industry     

Properties of carbon fiber and composites modified with different‐sized graphene oxide sheets

The graphene oxide (GO) sheets with different size distributions were effectively separated by a centrifugation method. The exfoliated single‐layer structure and the size of GO sheets were verified by scanning electron microscopy (SEM), atomic force microscope (AFM), and metallurgical microscope, respectively. Two different‐sized GO sheets water suspensions were obtained, which were then directly dispersed in carbon fiber (CF) sizing agent, respectively. The influences of the different‐sized GO sheets on CF and CF composites were explored. The workability in later process of CF and CF surface morphology were characterized by abrasion resistance, fluffs and breakage, stiffness, and SEM. SEM micrographs demonstrated that a nonuniform distribution of the large‐sized GO was lapped on CF whereas the small‐sized GO was uniformly leaned on CF. The interlaminar shear strength of the small‐sized GO/CF reinforced composite could reaches the maximum value. It indicated that the interfacial region between CF and polymer matrix could be enhanced by adjusting the size of GO sheets. POLYM. COMPOS., 37:2719–2726, 2016. © 2015 Society of Plastics Engineers     

Studying the Potential Application of Electrospun Polyethylene Terephthalate/Graphene Oxide Nanofibers as Electroconductive Cardiac Patch

Nowadays, engineering‐based cardiac patches aim to accelerate cardiac regeneration in myocardial infarcted tissues. Considering the fundamental role of cardiac electrophysiology in myocardial function, this study aims to investigate graphene oxide (GO) incorporation in the polyethylene terephthalate (PET) nanofibrous scaffold, as a conductive cardiac patch. The PET/GO nanocomposites are prepared using the uniaxial nozzle and coaxial nozzle electrospinning processes and comprehensively evaluated. The morphological observation indicates a uniform beaded free morphology with an average diameter of 147 ± 38 and 253 ± 67 nm for solid and core–shell nanocomposite fibers, respectively. Addition of GO to the PET nanofibers in a concentration of 0.05 wt% remarkably increases the Young modulus of mats from 30 ± 0.03 to 60 ± 0.02 and 69 ± 0.08 MPa for solid and core–shell nanofibers, respectively. Also, the electroconductivity is improved from 0.7 × 10^?6 to 1.175 × 10^?6 and 1.3 × 10^?6 S cm^?1 for solid and core–shell nanofibers, which are in the range of cardiac electroactivity values. PET/GO substrate interestingly supports human umbilical vein endothelial cells’ spreading morphology and cardiomyocyte elongated morphology, mainly where the GO nanosheets are distributed near the surface of nanofibers. In conclusion, the core–shell electrospun PET/GO nanocomposite fibers are suggested as a potential electroactive cardiac patch to improve cardiac cell attachment and proliferation.