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     

New Role of Layered Silicates as Phase Transfer Catalyst for In Situ Polymerization of Poly(ethylenetetrasulfide) Nanocomposite

In this study, polyethylenetetrasulfide/montmorillonite nanocomposite (PETS/nanoclay) is synthesized from ethylene dichloride and sodium tetrasulfide monomers by in situ polymerization method. The effect of phase-transfer catalyst (PTC) on polymerization kinetics in addition to the structure of resulting PETS containing nanoclay is investigated. The results show that surface-modified montmorillonites by methyl tallow bis-2-hydroxyethyl quaternary ammonium chloride could properly act as PTC. Therefore, it is demonstrated that the addition of nanoclay as PTC reduces the reaction time and increases the polymerization rate during the production of final nanocomposite. The samples were characterized using Fourier transform infrared and Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), nuclear magnetic resonance spectroscopy besides energy-dispersive X-ray spectroscopy (EDS) combined with SEM (SEM–EDX). In addition, thermal behavior of nanocomposite was perused by differential scanning calorimetry and thermogravimetric analysis. XRD and AFM results show proper dispersion of clay in PETS matrix and SEM–EDX results demonstrate suitable distribution of clay in polymer matrix. PETS/nanoclay nanocomposite show a better thermal stability, and also higher glass transition and melt temperature compared to pure polysulfide polymer. The solubility of nanocomposite is also studied and results show that the solubility depends on solvent concentration in addition to reinforcement (nanoclay) deals.     

Relevance of graphene oxide as nanofiller for geometrical variation in unidirectional carbon fiber/epoxy composite

Curved geometry in unidirectional CFRP (UD-CFRP) demands ideal shape optimization to attain superior performance while maintaining the desired high strength to weight ratio. Herein, the effect of graphene oxide (GO) as the potential filler to improve the mechanical and thermal properties of flat and curved specimens of UD-CFRP was investigated. The GO was synthesized using Hummer's method and introduced in the epoxy resin by wet transfer technique. Three-point and four-point bending analysis of UD-CFRP showed maximum flexural strength and modulus at 0.3 wt% GO addition in UD-CFRP. The improved interfacial adhesion of 0.3 wt% GO incorporated UD-CFRP was realized by calculating storage modulus, reinforcement efficiency factor (r), C-factor, adhesion factor, cross-linking density, and glass transition temperature (T_g) from dynamic mechanical analyzer. Fracture analysis by scanning electron microscope showed the superior interlocking in carbon fiber, and epoxy polymer at 0.3 wt% GO addition.     

Thin polymer films based on poly(vinyl alcohol) containing graphene oxide and reduced graphene oxide with functional properties

In this article, the effect of the addition of graphene oxide (GO) and reduced graphene oxide (rGO) on the mechanical properties, thermal stability, and electrical conductivity of polyvinyl alcohol (PVA) has been investigated. Different weight percentages of nanofillers ranging from 0.5 to 5 wt% have been combined with PVA. The ultrasonic technique has been applied to disperse nanofillers in the PVA solution. The nanocomposite films have been prepared via solution casting technique and the dispersion of nanofillers into the PVA has been studied through optical microscopy. The microstructure, crystallization behavior, and interfacial interaction were characterized through X-ray diffraction and Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis have been applied to study the thermal properties of the prepared nanocomposites. The DSC results revealed that the crystallization temperature and melting temperature were enhanced in the presence of GO nanofiller. Besides, the tensile strength at break was improved along with the addition of GO; however, elongation at break for PVA/GO and PVA/rGO was diminished. Moreover, all specimens showed insulating behavior and the only sample was electrically conducting, which contain a high amount of rGO (5 wt%).     

Development of a novel graphene oxide-blended polysulfone mixed matrix membrane with improved hydrophilicity and evaluation of nitrate removal from aqueous solutions

In this study, four types of mixed matrix membranes were fabricated using polysulfone (as the base polymer) and different contents of graphene oxide (GO) nanosheets (as modifier) through wet phase inversion method. Based on the amounts of GO (0, 0.5, 1, and 2?wt%), the synthesized membranes named as M1, M2, M3, and M4, respectively. The membranes characteristics were evaluated using FE-SEM, FT-IR, and water contact angle measurements. In addition, the performance of the prepared membranes was investigated in terms of basic parameters: filtrate water flux, nitrate removal efficiency, and antifouling properties. Results showed significant improvements of the characteristics of modified membranes with GO. Accordingly, the permeability and hydrophilicity were enhanced and water flux was considerably improved. At operating pressure of 4?bar and nitrate concentration of 110?mg/L, the removal efficiency for unmodified membrane (M1) was 15.5% and for modified M2, M3, and M4 membranes were 22.78%, 39.12%, and 41.37%, respectively. In addition, the results of flux recovery ratio (FRR) showed that the anti-fouling properties of the GO modified membranes were improved due to the increase in membrane surface hydrophilicity.     

聚丙烯酸/氧化石墨烯自修复水凝胶的合成及性能

通过改进的Hummers方法成功制备了氧化石墨烯(GO)。以Fe3+为交联剂、丙烯酸(AA)为单体、GO为增强剂,采用原位聚合法制备了聚丙烯酸(PAA)/GO自修复水凝胶。考查了不同GO含量下,PAA/GO自修复水凝胶的溶胀性能,并探讨了GO含量、Fe3+含量和H2O含量对PAA/GO自修复水凝胶力学性能的影响,研究了PAA/GO自修复水凝胶的自修复性能。结果表明,Fe3+含量、GO含量和H2O单体含量分别为0.5 %（摩尔分数）、0.5 %（质量分数,下同）、80 %时,具有最佳力学性能（其拉伸强度为743.5 kPa,断裂伸长率为2940.5 %）;GO含量为0.25 %时,PAA/GO自修复水凝胶的吸水性能最大;PAA/GO自修复水凝胶具有优异的自修复性能。     

In situ Synthesis and mechanical,thermal properties of polyimide nanocomposite film by addition of functionalized graphene oxide

Polyimide (PI) and chemical modified graphene oxide nanocomposite films are prepared by in situ polymerization from solutions of pyromellitic dianhydride and 4,4′‐oxydianiline with various amount (0.5–2 wt%) of 3‐aminopropyltriethoxysilane (APTS) functionalized graphene oxide (GO) sheets in dimethylacetamide. The APTS functionalized GO (GO‐APTS) is a versatile platform for polymer grafting, improving excellent dispersion of GO in the PI matrix, and forming strong interaction with the PI matrix. The GO‐APTS/PI nanocomposites exhibited improvement in mechanical and thermal properties by addition of a small amount of GO‐APTS. With the addition of a small amount of GO‐APTS (1.5 wt%) to PI matrix, mechanical properties with the tensile strength and Young's modulus improved by 45% and 15%, respectively. The thermal analysis showed that the thermal stability of PI was slightly enhanced by the incorporation of GO‐APTS (1.5 wt%). This approach provides a strategy for developing high performance functionalized GO‐polymer composite materials. POLYM. COMPOS., 37:907–914, 2016. © 2014 Society of Plastics Engineers     

Microstructural and mechanical characteristics of graphene oxide-fly ash cenosphere hybrid reinforced epoxy resin composites

An experimental investigation into the influence of incorporation of graphene oxide (GO) and fly ash cenospheres (FACs) on the mechanical properties of epoxy resin (EP) composites. Two fillers were studied: GO-FAC hybrid and single GO. The GO-FAC hybrid was synthesized using a solution blending method, and characterized by FTIR, XRD, and scanning electron microscope (SEM). The modified EP composite specimens were prepared by adding different contents of GO and GO-FAC hybrid. The investigation showed that the FACs were successfully carried on the GO layer. The experimental data indicated that the addition of GO-FAC hybrid effectively improved the tensile property and the wear resistance of the EP composites, superior to the addition of single GO samples. The best tensile properties and lowest wear rate of EP composites were obtained when the hybrid content was 0.5 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47173.     

Synthesis and characterization of hybrid materials based on graphene oxide and silica nanoparticles and their effect on the corrosion protection properties of epoxy resin coatings

This study focuses on the use of tetraethyl orthosilicate (TEOS) as a silica source to decorate the surface of graphene oxide (GO) nanosheets and the use of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (Z-6020) as a coupling agent through a one-step in-situ sol-gel process. The results of the Fourier transform infrared spectroscopy (FT-IR), UV-visible, X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) revealed that fine SiO₂ nanoparticles have successfully been synthesized on the basal plane of GO by covalent bonding. The dispersion of GO sheets and GO–SiO₂ nanohybrids within the epoxy matrix was studied using XRD and SEM techniques. Then, the effect of incorporating 0.1?wt% GO sheets and GO–SiO₂ nanohybrids on the corrosion protection and barrier performance of the epoxy coating was also investigated. The results showed that the incorporation of GO–SiO₂ into the epoxy matrix improved its thermal stability. The electrochemical impedance spectroscopy (EIS) test, potentiodynamic polarization and cathodic disbonding test showed that the corrosion protection performance was significantly enhanced by the incorporation of GO–SiO₂ hybrids into the epoxy resin compared to epoxy/GO and neat epoxy resin, respectively. The water contact angle (CA) results confirmed the reduction of the hydrophobic nature of the surface after the incorporation of GO–SiO₂ hybrids.     

High acetic acid sensing performance of Mg-doped ZnO/rGO nanocomposites

Mg-doped ZnO/reduced graphene oxide (rGO) nanocomposites were synthesized using a facile and cost-effective sol-gel procedure to detect acetic acid vapor. Field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV–vis) diffuse reflectance spectroscopy, and photoluminescence (PL) analysis were utilized to characterize morphologies, compositions of the nanocomposites, and optical properties of the synthesized nanostructures. The gas sensing measurements of spin-coated Mg-doped ZnO/rGO thin films were carried out for a temperature range of 150–350?°C at various acetic acid vapor concentrations. It was found that the Mg-doped sample with 20?wt%/v of GO solution concentration exhibited the response/recovery time of 60?s/35?s with the best response of ~?200% for 100?ppm of acetic acid at 250?°C.     

Crystallization of calcium silicate hydrates on the surface of nanomaterials

The poorly crystalline calcium silicate hydrate (C‐S‐H) is the primary binding phase in portland cement concrete. In this paper, the influence of adding anatase phase nano‐TiO₂, nano‐SiO₂, graphene oxide (GO), and multiwalled carbon nanotubes (CNT) on the crystallization and morphology of C‐S‐H are systematically investigated through tests. C‐S‐H gels were prepared using the double decomposition method, and the nanomaterial additions of nano‐TiO₂, nano‐SiO₂, GO, and CNT were 2 wt%, 2 wt%, 0.5 wt%, and 0.5 wt%, respectively. X‐ray diffraction (XRD) results show that a more crystalline nanostructure of C‐S‐H is induced by the addition of nano‐TiO₂ or GO. This phenomenon is further confirmed by the transmission electron microscopy (TEM) observations. The TEM observations demonstrate that C‐S‐H would grow on the crystal face of TiO₂ to form nanocrystalline regions with a lattice fringe spacing of 3.0 Å. When incorporated with GO, it will form a square lattice structure with a lattice constant of 3.1 Å on the surface of GO and later change to the lattice fringe structure with a spacing of 3.1 Å on the region bit away the GO surface. However, when adding nano‐SiO₂ or CNT, these nanocrystalline regions are not observed. Further characterization through scanning electron microscopy (SEM) and atomic force microscopy (AFM) has been performed to investigate the effect of nanomaterials on C‐S‐H morphology. Different nanomaterials take a different morphology of C‐S‐H: sheet‐shape structures for pure C‐S‐H, rod‐shape with for C‐S‐H with nano‐TiO₂, and granular agglomeration for C‐S‐H with nano‐SiO₂. C‐S‐H with GO or CNT forms a structure of C‐S‐H growing on the templates.     

Characterization of reactive graphene oxide synthesized from ball – milled graphite: its enhanced reinforcing effects on cement nanocomposites

In this study, commercial graphite powder (GP) of particle size 100 micron was subjected to high energy ball-milling (HEBM) to produce ball-milled graphite powder (BMGP) of particle size 780 nm. Both GP and BMGP were converted to respective graphene oxides (GOs) (labeled as GO1 and GO2) using Hummer’s method, which were then characterized using techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X- ray diffraction (XRD). GO1 and GO2 were then investigated for their effects on compressive strength of cement mortar matrix at different curing times of 7, 14, and 28 days. Effect of variation of concentration (ranging between 0.125 and 1.00 wt% of cement) of GO1 and GO2 on the strength of matrix was examined. Microstructures of GO1-cement mortar nanocomposite and GO2-cement mortar nanocomposite were studied after 28 days of curing using SEM. Obtained results show that addition of 1.00 wt% GO1 and GO2 showed best performance by increasing the strength to 63 and 78%, respectively, in comparison to the unreinforced control sample. Improved performance of GO2 was attributed to more number of reactive sites of GO nanosheets induced by ball-milling treatment of graphite precursor.     

Sintering behaviour and properties of manganese-doped alumina

The effect of manganese (0.1, 0.5 and 1.0?wt%) on the sintering and mechanical properties of alumina was studied. Sintering was carried out by the conventional heating method in a box furnace and in a hybrid multimode microwave furnace. XRD analysis revealed the precipitation of a spinel second phase (MnAl₂O₄) in manganese-doped samples as a result of manganese limited solubility in the corundum lattice. The addition of 0.1?wt% manganese was most beneficial in enhancing the densification of alumina (97.5% relative density when compared to 94.2% for the undoped sample), hindered grain growth, and improved the hardness of the ceramic when sintered at 1500?°C. The study also revealed that microwave sintering was effective in suppressing grain growth of alumina. In addition, the hardness was dependent on the sintered bulk density and that grain coarsening ensued as the density of the sintered alumina exceeded 95% of theoretical.     

Effect of Dodecyal Amine Functionalized Graphene on the Mechanical and Thermal Properties of Epoxy‐Based Composites

Simultaneous surface functionalization and reduction of graphene oxide (GO) was achieved by using dodecyl amine (DA) as surface modifying agent. The DA modified reduced GO (DA‐G) was used for subsequent preparation of DA‐G/epoxy composites by solution mixing. Fourier transform infrared spectroscopy analysis, X‐ray diffraction (XRD) and electrical conductivity measurements were conducted to establish the concurrent functionalization and reduction of GO. The effect of DA‐G on the epoxy composites at 0 to 0.75 wt% loadings was studied by investigating its static and dynamical mechanical properties. XRD study was performed to verify the dispersion of DA‐G in the epoxy polymer. Field emission scanning electron microscopy was used to investigate the fracture surface morphology of the composites and Transmission electron microscopy was employed to further confirm the dispersion of DA‐G in the matrix. It was found that the tensile strength of the composite was increased by 38.8% with the addition of 0.5 wt% of DA‐G. The good adhesion/interaction between DA‐G and epoxy resulted in the increase of storage modulus; however, glass transition temperature (T_g) value of the composites shifted to lower temperature in comparison to the neat epoxy. Thermogravimetric analysis showed small decrease in onset degradation temperature for the composites as compared to neat epoxy except for the composites containing 0.75 wt% of DA‐G. POLYM. ENG. SCI., 56:1221–1228, 2016. © 2016 Society of Plastics Engineers     

Nanocomposite powders of hydroxyapatite-graphene oxide for biological applications

The repair of bone fractures is a clinical challenge for patients with impaired healing, such as osteoporosis. Currently, different strategies have been developed to design new biomaterials, enhancing their interactions with biological systems and conducting the cellular behavior in the desired direction to help fracture healing. In the present work, hydroxyapatite-graphene oxide (HA-GO) nanocomposites were produced and the morphological and physicochemical influences of the addition of 0.5 wt%, 1.0 wt% and 1.5 wt% of GO to HA were observed. FEG-SEM and TEM analyses of HA-GO nanocomposites showed HA nanoparticles adhered to the surface of the GO sheets, suggesting an effective method to form nanostructured graphene-based biomaterials. As confirmation, physicochemical analyses by Raman, FTIR and TGA demonstrated a strong affinity between HA and GO, according to the increase of concentration from 0.5 wt% to 1.5 wt% GO in the HA-GO nanocomposites. Also, in order to evaluate the HA-GO nanocomposites behavior under biological microenvironment, in vitro bioactivity and indirect cytotoxicity tests were performed. FEG-SEM analyses confirmed the positive results for the bioactivity properties of HA-GO nanocomposite and indirect cytotoxicity demonstrated that even with a decrease in the hDPSCs viability and proliferation, when increasing to 1.5 wt% of GO concentration, high level of cell viability was exhibited by HA-GO nanocomposites. These biological results suggested the 0.5 wt% HA-GO nanocomposite as a potential bioactive bone graft and a promising biomaterial for bone tissue regeneration, when compared to the pure HA.     

The influence of ZrO2 additive on sintering and microstructure of lithium and lithium-titanium-zinc ferrites

The effect of ZrO₂ addition (0–3?wt%) on sintering and microstructure of lithium and lithium-titanium-zinc ferrites was studied. The Vickers hardness and dc electrical resistivity were investigated and discussed in correlation with the structural properties. Ferrite powders with the chemical compositions of LiFe₅O₈ and Li_0.65Fe_1.6Ti_0.5Zn_0.2Mn_0.05O₄ were prepared by the conventional ceramic technique. The synthesized ferrites were doped with various amount of ZrO₂ and then were sintered at 1050?°C for 2?h. Dilatometric studies showed that the zirconia addition affects the densification process of ferrite ceramics so that the shrinkage rate of pressed ferrite powders during their heating decreased with an increase in ZrO₂ content. The bulk density of the sintered ferrites varied slightly as the concentration of the additive was increased from 0 to 2?wt%, while the density of ferrite doped with 3?wt% ZrO₂ significantly decreased. X-ray diffraction and scanning electron microscopy analyses showed that the lattice parameter of ferrites increases and their average grain size decreases as the additive content grows. It was established that small amounts of ZrO₂ additive (up to 2?wt%) improve significantly the hardness and the electrical resistivity of ferrites.     

Morphology,thermal, mechanical,and barrier properties of graphene oxide/poly(lactic acid) nanocomposite films

To improve the physical and gas barrier properties of biodegradable poly(lactic acid) (PLA) film, two graphene nanosheets of highly functionalized graphene oxide (0.3 wt% to 0.7 wt%) and low-functionalized graphene oxide (0.5 wt%) were incorporated into PLA resin via solution blending method. Subsequently, we investigated the effects of material parameters such as loading level and degree of functionalization for the graphene nanosheets on the morphology and properties of the resultant nanocomposites. The highly functionalized graphene oxide (GO) caused more exfoliation and homogeneous dispersion in PLA matrix as well as more sustainable suspensions in THF, compared to low-functionalized graphene oxide (LFGO). When loaded with GO from 0.3 wt% to 0.7 wt%, the glass transition temperature, degree of crystallinity, tensile strength and modulus increased steadily. The GO gave rise to more pronounced effect in the thermal and mechanical reinforcement, relative to LFGO. In addition, the preparation of fairly transparent PLA-based nanocomposite film with noticeably improved barrier performance achieved only when incorporated with GO up to 0.7wt%. As a result, GO may be more compatible with hydrophilic PLA resin, compared to LFGO, resulting in more prominent enhancement of nanocomposites properties.     

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     

Performance tuning of glass fiber/epoxy composites through interfacial modification upon integrating with dendrimer functionalized graphene oxide

In this study, glass fiber/epoxy composites were interfacially tailored by introducing polyamidoamine (PAM) dendrimer functionalized graphene oxide (GO) into epoxy matrix. Two different composites each containing varying loading fraction (0.5, 1.0, and 1.5 wt%) of GO and GO-PAM were fabricated via hot press processing. Composites were evaluated for interlaminar shear strength (ILSS), dynamic mechanical properties and thermal conductivity. The inclusion of 1.5 wt% GO-PAM resulted ~57.3%, ~42.7%, and ~54% enhancement in ILSS, storage modulus and thermal conductivity, respectively. Almost, ~71% reduction in coefficient of thermal expansion was also observed at same GO-PAM loading. Moreover, higher glass transition temperature was observed with GO-PAM addition. GO-PAM substantially improved fiber/matrix interfacial adhesion, which was witnessed through scanning electron microscopy. The enhanced thermo-mechanical performance was attributed to interfacial covalent interactions engendered by ring opening reaction between epoxy and amine moieties of PAM dendrimers. These multiscale composites with extraordinary functional properties can outperform conventional counterparts with improved reliability and performance.     

Mechanical properties of graphene oxide reinforced alumina matrix composites

Graphene oxide (GO) reinforced alumina matrix composites have been fabricated by using graphene oxide synthesized by a modified Hummer's method. Samples were prepared by powder metallurgy and consolidated by Spark Plasma Sintering (SPS). The influence of GO addition on the microstructure and mechanical properties of the composites was investigated. Results show a significant increase (almost 35%) of the fracture toughness for composites containing 0.5 wt% graphene oxide compared to sintered pure alumina. In order to find reasons for this improvement Scanning/Transmission Electron Microscopy (SEM/TEM) observations were carried out. They reveal a good interface between the reinforcement and the matrix as well as such mechanisms like branching, deflection and bridging of crack propagation.