One‐pot synthesis,characterization, and field emission investigations of composites of polypyrrole with graphene oxide,reduced graphene oxide,and graphene nanoribbons

Pyrrole monomer was polymerized by a chemical oxidative route in the presence of graphene oxide (GO), reduced GO (rGO), and graphene nanoribbons (GNR) separately to prepare composites of polypyrrole (PPy) as PPy–GO, PPy–rGO, and PPy–GNR, respectively. The morphological, chemical, and structural characterization of the as‐synthesized products was carried out using scanning electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy. Field emission studies of the PPy–GO, PPy–rGO, and PPy–GNR emitters were performed at the base pressure of 1 × 10^?8 mbar in a planar “diode” configuration. The turn‐on field values, corresponding to an emission current density of 1 µA/cm², are observed to be 1.5, 2.2, and 0.9 V/µm for the PPy–GO, PPy–rGO, and PPy–GNR emitters, respectively. The maximum emission current density of 2.5 mA/cm² is drawn from PPy–GO at an applied electric field of 3.2 V/µm, 1.2 mA/cm² at 3.6 V/µm from the PPy–rGO, and 8 mA/cm² at 2.2 V/µm from the PPy–GNR emitters. All of the composites exhibit good emission stability over more than 2 h. The results indicate the potential for a facile route for synthesizing composites of conducting polymers and graphene‐based materials, with enhanced functionality. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45170.     

Single‐walled carbon nanotube/poly(methyl methacrylate) composites for electromagnetic interference shielding

Single‐walled carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) composites were prepared using coagulation method. The electrical conductivity and the electromagnetic interference (EMI) shielding of SWNT/PMMA composites over the X‐band (8–12 GHz) and the microwave (200–2000 MHz) frequency range have been investigated. The electrical conductivity of composites increases with SWNT loading by 13 orders of magnitude, from 10^?15 to 10^?2 Ω^?1 cm^?1 with a percolation threshold of about 3 wt% SWNTs. The effect of the sample thickness on the shielding effectiveness has been studied, and correlated to the electrical conductivity of composites. The data suggest that SWNT/PMMA composites containing higher SWNT loading (above 10 wt%) be useful for EMI shielding and those with lower SWNT loading be useful for electrostatic charge dissipation. The dominant shielding mechanism of SWNT/PMMA composites was also discussed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Structural,dielectric, and magnetic properties of reduced graphene oxide-wrapped MnFe2O4 composites synthesized by in-situ sol-gel autocombustion method

Herein, the reduced graphene oxide (rGO) wrapped MnFe₂O₄ (MFO@rGO) composites with different rGO content of 10, 20, 30, and 40 wt% have been synthesized by a one-step in-situ sol-gel autocombustion method. The synthesized composites have been tested for their structural, electrical, dielectric, and magnetic characteristics. The composites are characterized by using standard techniques (XRD, HR-TEM, FTIR, and Raman spectroscopy). The composite having 20 wt% of rGO exhibits the highest value of dielectric constant (ε′～1.32 × 10⁴ at 100 Hz, ε′～143 at 1 MHz) and dc conductivity (σ_dc = 4.31 × 10^?6 Ω^?1-cm^?1) among the investigated composites. The dipole polarization contribution to the dielectric relaxation behavior of MFO@rGO composites is observed, which arises from the increased vacancy defect dipoles in rGO sheets. The impedance studies show the existence of two different time relaxation phenomena in MFO@rGO composites. The magnetic measurements reveal the superparamagnetic behavior of composites. The saturation magnetization of composites decreases first with the increase in rGO content up to 20 wt% and then increases with a further increase in rGO content. The findings of this research make these composites a potential candidate for various applications such as EMI shielding and energy storage devices.     

Investigation of electrical,mechanical, and thermal properties of functionalized multiwalled carbon nanotubes‐reduced graphene Oxide/PMMA hybrid nanocomposites

Electrical, mechanical, and thermal properties of the poly(methyl methacrylate) (PMMA) composites containing functionalized multiwalled carbon nanotubes (f‐MWCNTs) and reduced graphene oxide (rGO) hybrid nanofillers have been investigated. The observed electrical percolation threshold of FHC is 0.8 wt% with maximum conductivity of 1.21 × 10^?3 S/cm at 4 wt% of f‐MWCNTs. The electrical transport mechanism and magneto resistance studied of hybrid composites have also been investigated. Progressive addition of f‐MWCNTs in rGO/PMMA composite results increase in mechanical (tensile strength and Young's modulus) and thermal (thermal stability) properties of f‐MWCNTs‐rGO/PMMA hybrid nanocomposites (FHC). The increased mechanical properties are due to the efficient load transfer from PMMA matrix to f‐MWCNTs and rGO through better chemical interaction. The strong interaction between PMMA and f‐MWCNTs‐rGO in FHC is the main cause for improved thermal stability. POLYM. ENG. SCI., 59:1075–1083, 2019. © 2019 Society of Plastics Engineers     

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.     

Reduced graphene oxide/carbon nanotubes nanohybrids as preformed reinforcement for polystyrene composites

Three‐dimensional carbon nanohybrids constructed by reduced graphene oxide (rGO) and carbon nanotubes (CNTs) are prepared via simultaneous hydrothermal and chemical reduction reactions. The macroscopic rGO/CNTs monolith is used as the preformed reinforcement for polystyrene (PS) composites to function as the continuous conductive pathway. During hydrothermal reaction, interconnected network consisting of rGO and CNTs, driven by the hydrophobic and π‐π interactions, is formed and then frozen by the following freeze‐drying processing. Fourier transform infrared and X‐ray diffraction results confirm that CNTs play an important role in tuning the amphiphilicity and pore structure of the as‐prepared rGO/CNTs nanohybrids. rGO/CNTs/PS composites prepared via vacuum‐assisted impregnation process exhibit the highest electrical conductivity of 1.21 × 10^?3 S m^?1, which is 11 orders of magnitude higher than that of neat PS. The functional synergies of rGO and CNTs are identified to establish an efficient route for improving the electrical property of polymer based composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45054.     

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     

Synthesis of polythiophene/graphene oxide composites by interfacial polymerization and evaluation of their electrical and electrochemical properties

We report a new method for the synthesis of polythiophene (PTh)/graphene oxide (GO) nanocomposites by interfacial polymerization. Polymerization occurred at the interface of two immiscible solvents, i.e. n‐hexane containing thiophene and nitromethane containing GO and an initiator. Characterizations were done using Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and electrochemical and electrical conductivity measurements. Spectroscopic analyses showed successful incorporation of GO in the PTh matrix. Morphological analysis revealed good dispersion of GO sheets in the polymer matrix. The PTh/GO composites showed marked improvements in thermal stability and electrical conductivity (2.7 × 10^?4 S cm^?1) compared to pure PTh. The composites exhibited excellent electrochemical reversibility compared to pure PTh at a scan rate of 0.1 V s^?1. The composites were stable even up to 100 electrochemical cycles, indicating good cycle performance. The specific capacitance of the composites was calculated using cyclic voltammetry and was found to be 99 F g^?1. © 2014 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.     

Synthesis and characterization of polyarylureas. I. Potentially semiconducting polymers

Polyarylureas were synthesized from the reaction between phosgene with aromatic diamines. Depending on the pH, the polyarylureas presented different colors when the solvent used was pyridine. The polyarylureas were characterized by IR spectroscopy, elemental analysis, and X‐ray photoelectron spectroscopy (XPS). To study the thermal stability of the polymers, a thermal degradation was performed between 35 and 700°C. The polyarylureas decomposed above 350°C. Without doping, polyarylureas are considered as semiconductors [σ = 10^?9 (Ωcm)^{? 1}]; after doping with I₂, their electrical conductivity increases by several orders of magnitude. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 822–830, 2001     

Enhanced thermal conductivity and dimensional stability of flexible polyimide nanocomposite film by addition of functionalized graphene oxide

Polyimide (PI) nanocomposites with both enhanced thermal conductivity and dimensional stability were achieved by incorporating glycidyl methacrylate‐grafted graphene oxide (g‐GO) in the PI matrix. The PI/g‐GO nanocomposites exhibited linear enhancement in thermal conductivity when the amount of incorporated g‐GO was less than 10 wt%. With the addition of 10 wt% of g‐GO to PI (PI/g‐GO‐10), the thermal conductivity increased to 0.81 W m^?1 K^?1 compared to 0.13 W m^?1 K^?1 for pure PI. Moreover, the PI/g‐GO‐10 composite exhibited a low coefficient of thermal expansion (CTE) of 29 ppm °C^?1. The values of CTE and thermal conductivity continuously decreased and increased, respectively, as the g‐GO content increased to 20 wt%. Combined with excellent thermal stability and high mechanical strength, the highly thermally conducting PI/g‐GO‐10 nanocomposite is a potential substrate material for modern flexible printed circuits requiring efficient heat transfer capability.     

Preparation and properties of reduced graphene oxide/fused silica composites

An in situ strategy for fabrication of reduced graphene oxide/fused silica (rGO/FS) composites using 3-aminopropyltriethoxysilane as surfactant is reported. GO nanosheets were bound to FS particles by an electrostatic assembly between ultra thin negatively charged GO sheets and positively charged amino-modified FS particles. After spark plasma sintering, rGO/FS bulk composites have been produced from the GO and FS composite particles with GO being reduced to rGO in vacuum at high temperatures. Results show that rGO sheets were well dispersed in the matrix, and conductivity of these rGO/FS composites at room temperature was strongly dependent on the rGO nanosheet concentration. i.e., the conductivity of rGO/FS was increased to 10⁻⁴ S/cm when a conducting network was formed inside the composites. The effect of GO nanosheets on the mechanical properties of rGO/FS bulk composites was also investigated. The addition of 1 wt.% GO sheets to FS resulted in 72% increase in Vickers hardness, indicating the stress transfering from the FS matrix to the rigid rGO sheets. With the same rGO content, the fracture toughness of the as-prepared composites was increased by 74%. The main toughening mechanisms were thought to be crack deflection, crack branching, pulling-out and bridging of the rGO sheets.     

Simultaneous reduction and surface functionalization of graphene oxide for enhancing flame retardancy and thermal conductivity of mesogenic epoxy composites

Graphene oxide (GO ) is reduced and surface functionalized by 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide simultaneously. This functional reduced graphene oxide (F‐rGO ) with better thermal stability can be used as a nano‐filler to improve the flame retardancy, mechanical properties and thermal conductivity of mesogenic epoxy (EO ). Due to the presence of an oriented structure, EO is an intrinsic highly thermal conductive polymer compared with common polymer. After being filled with F‐rGO , the ordered domains in the EO matrix are connected by F‐rGO . As a result, the thermal conductivity coefficient of F‐rGO /EO composite is increased by 30.8% compared with pure EO . The dynamic mechanical analysis results indicate that E ' of F‐rGO /EO is 26.7% higher than that of EO . Because of the stable structure of F‐rGO , F‐rGO /EO is self‐extinguishing. The total heat release of F‐rGO /EO ‐15 is 24.1 kJ g^?1, which is 5.6 kJ g^?1 lower than that of EO . © 2016 Society of Chemical Industry     

Electrical conductivity of epoxy/silicone/carbon black composites: Effect of composite microstructure

The objective of this work is to study the effect of electrical conductivity and physical‐mechanical properties of carbon black (CB) filled polymer composites. This goal is achieved by synthesizing epoxy/silicon phase separated blend structure of composites filled with CB. The percolation threshold of epoxy/silicone/CB composites decreased and the total conductivity increased compared to the pure epoxy/CB composite. A threefold increase was obtained with tensile strength of epoxy/silicone/CB composite with 25 wt% of silicone and 5 wt% of CB in comparison with epoxy/CB systems. This composite has conductivity of about 10⁻⁶ S/cm, which is six orders of magnitude higher than for epoxy/CB composites at the same concentration of CB. POLYM. COMPOS., 35:2234–2240, 2014. © 2014 Society of Plastics Engineers     

Multiwalled carbon nanotubes/polypyrrole/graphene/nonwoven fabric composites used as electrodes of electrochemical capacitor

The reduced graphene oxide/nonwoven fabric (rGO/NWF) composites have been fabricated through heating the NWF coated with the mixture of GO and HONH₂·HCl at 130°C, during which the GO is chemically reduced to rGO. Then the composites of polypyrrole (PPy)/rGO/NWF have been prepared through chemically polymerizing pyrrole vapor by using the FeCl₃·6H₂O adsorbed on rGO/NWF substrate as oxidant. Finally, multiwalled carbon nanotubes (MWCNTs) are used as conductive enhancer to modify PPy/rGO/NWF through dip‐dry process to obtain MWCNTs/PPy/rGO/NWF. The prepared composites have been characterized and their capacitive properties have been evaluated in 1.0M KCl electrolyte by using two‐electrode symmetric capacitor test. The results reveal that MWCNTs/PPy/rGO/NWF possesses a maximum specific capacitance (C_sc) of about 319 F g^?1 while PPy/rGO/NWF has a C_sc of about 277.8 F g^?1 at the scan rate of 1 mV s^?1 and that optimum MWCNTs/PPy/rGO/NWF retains 94.5% of initial C_sc after 1000 cycles at scan rate of 80 mV s^?1 which is higher than PPy/rGO/NWF (83.4%). Further analysis reveals that the addition of MWCNTs can increase the charger accumulation at the outer and inner of the composites, which is favorable to improve the stability and the rapid charge‐discharge capacity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41023.     

Preparation of highly conductive reduced graphite oxide/poly(styrene-co-butyl acrylate) composites via miniemulsion polymerization

Polymer/reduced graphite oxide (rGO) composite nanoparticles with a high electrical conductivity were synthesized using the miniemulsion polymerization technique. The rGO was modified with a reactive surfactant, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), to facilitate monomer intercalation into the rGO nanogalleries. The AMPS-modified rGO was emulsified in the presence of styrene (St) and butyl acrylate (BA) monomers, and the stable miniemulsion was polymerized to form poly(St-co-BA)/rGO composite latex nanoparticles. The transition in the composite nanoparticles from an electrical insulator to an electrical conductor occurred at an rGO content of 10 wt% (relative to the monolayer content), yielding an electrical conductivity of 0.49 S/cm. The electrical conductivity of the composite nanoparticles reached 2.22 S/cm at 20 wt% rGO, yielding a much better conductivity than other polymer composites prepared using a GO filler. Importantly, the miniemulsion polymerization method for fabricating poly(St-co-BA)/rGO composite nanoparticles is easy, green, low-cost, and scalable, providing a universal route to the rational design and engineering of highly conductive polymer composites.     

Enhanced toughness and strength of boron carbide ceramics with reduced graphene oxide fabricated by hot pressing

Boron carbide (B₄C) hybrids with different contents of graphene oxide (GO) were prepared by a heterogeneous co-precipitation method using cetyltrimethyl ammonium bromide (CTAB) as the cationic surfactant. The as-obtained mixtures were further hot-pressed at 1950 °C for 60 min under 30 MPa, by which B₄C–reduced GO (rGO) composites were fabricated. It was found that the addition of only 0.5 wt% rGO could alter the predominance of trans-granular fracture in monolithic B₄C ceramic material to mixed trans-granular and inter-granular modes in B₄C–rGO composites. The flexural strength and fracture toughness of the B₄C–2 wt% rGO were increased by 31% (from 350 to 455 MPa) and 83% (from 3.20 to 5.85 MPa·m^1/2), respectively, compared with those of pure B₄C. The improved mechanical properties are attributed to the mechanisms of pull-out and bridging of rGO and crack deflection, as evidenced by microstructural observations. The energy dissipation in the present B₄C–rGO composites was further verified using two micromechanical models.     

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     

The effect of graphite oxide on the thermoelectric properties of polyaniline

Graphite oxide (GO)/ordered polyaniline (PANI) composites have been prepared through an in situ polymerization. TEM, XRD, FTIR and XPS analyses show that the PANI grew along the surface of exfoliated GO as a template to form a more ordered structure with high crystallinity during polymerization. Compared with pure PANI, both higher electrical conductivity and higher Seebeck coefficient of GO/PANI composites result from the increased carrier mobility, which is confirmed by Hall measurement. Strong interactions exist between graphene oxide and PANI, including electrostatic forces, hydrogen bonding and π–π stacking. There is no significant difference in thermal conductivity between GO/PANI composites and PANI. The maximum electrical conductivity and Seebeck coefficient of the composites reach 751 S m^?1 and 28.31 μV K^?1, respectively. The maximum thermoelectric figure of merit is up to 4.86 × 10^?4, 2 orders of magnitude higher than that of pure PANI.     

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

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