Flash sintering of alumina/reduced graphene oxide composites

The flash sintering behavior of Al₂O₃/reduced graphene oxide (rGO) composites was investigated. rGO was used as a composite component and a conductive additive. Under the electric fields of 250–400 V cm⁻¹, the flash event occurred at extremely low temperatures of 236–249 °C. The current density limit played a significant role in the degree of densification. A larger current density resulted in a higher density of the sample. However, current densities larger than 33.33 A cm⁻² resulted in broken samples because of the localization of high current density coupled with the formation of hot spots. Flash sintering at a furnace temperature of 800 °C, electric field of 300 V cm⁻¹ and current density limit of 33.33 A cm⁻² produced nearly completely dense Al₂O₃/rGO composites. In addition to the current limit, the furnace temperature is also a key parameter that controls the degree of densification to achieve “safe” flash sintering.     

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.     

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.     

Preparation and mechanical properties of Si3N4 nanocomposites reinforced by Si3N4@rGO particles

A new type of reduced graphene oxide-encapsulated silicon nitride (Si₃N₄@rGO) particle was synthesized via an electrostatic interaction between amino-functionalized Si₃N₄ particles and graphene oxide (GO). Subsequently, the Si₃N₄@rGO particles were incorporated into a Si₃N₄ matrix as a reinforcing phase to prepare nanocomposites, and their influence on the microstructure and mechanical properties of the Si₃N₄ ceramics was investigated in detail. The microstructure analysis showed that the rGO sheets were uniformly distributed throughout the matrix and firmly bonded to the Si₃N₄ grains to form a three-dimensional carbon network structure. This unique structure effectively increased the contact area and load transfer efficiency between the rGO sheets and the matrix, which in turn had a significant impact on the mechanical properties of the nanocomposites. The results showed that the nanocomposites with 2.25 wt.% rGO sheets exhibited mechanical properties that were superior to monolithic Si₃N₄; the flexural strength increased by 83.5% and reached a maximum value of 1116.4 MPa, and the fracture toughness increased by 67.7% to 10.35 MPa·m^1/2.     

Reduced graphene oxide for Li–air batteries: The effect of oxidation time and reduction conditions for graphene oxide

Reduced graphene oxide (rGO) has shown great promise as an air-cathode for Li–air batteries with high capacity. In this article we demonstrate how the oxidation time of graphene oxide (GO) affects the ratio of different functional groups and how trends of these in GO are extended to chemically and thermally reduced GO. We investigate how differences in functional groups and synthesis may affect the performance of Li–O₂ batteries. The oxidation timescale of the GO was varied between 30 min and 3 days before reduction. Powder X-ray diffraction, micro-Raman, FE-SEM, BET analysis, and XPS were used to characterize the GO’s and rGO’s. Selected samples of GO and rGO were analyzed by solid state ¹³C MAS NMR. These methods highlighted the difference between the two types of rGO’s, and XPS indicated how the chemical trends in GO are extended to rGO. A comparison between XPS and ¹³C MAS NMR showed that both techniques can enhance the structural understanding of rGO. Different rGO cathodes were tested in Li–O₂ batteries which revealed a difference in overpotentials and discharge capacities for the different rGO’s. We report the highest Li–O₂ battery discharge capacity recorded of approximately 60,000 mAh/g_carbon achieved with a thermally reduced GO cathode.     

Preparation and characterization of reduced graphene oxide-reinforced boron carbide ceramics by self-assembly polymerization and spark plasma sintering

A self-assembly polymerization process was used to prepare graphene oxide/boron carbide (GO/B₄C) composite powders, spark plasma sintering (SPS) was used to fabricate reduced graphene oxide/boron carbide (rGO/B₄C) composites at 1800 °C and 30 MPa with a soaking time of 5 min. The effects of rGO addition on mechanical properties of the composites, such as Vickers hardness, flexural strength and fracture toughness, were investigated. The results showed that GO/B₄C composite powders were successfully self-assembled and a network structure was formed at high GO contents. The flexural strength and fracture toughness of rGO/B₄C composites were 643.64 MPa and 5.56 MPa m^1/2, respectively, at 1 and 2.5 wt.% rGO content, corresponding to an increase of 99.11% and 71.6% when compared to B₄C ceramics. Uniformly dispersed rGO in rGO/B₄C composites played an important role in improving their strength and toughness. The toughening mechanisms of rGO/B₄C composites were explained by graphene pull-out, crack deflection and bridging.     

Mechanical and dielectric properties of reduced graphene oxide nanosheets/alumina composite ceramics

Reduced graphene oxide (rGO) nanosheets/alumina (Al₂O₃) composite ceramics were fabricated by hot-pressing sintering. The density, porosity, microhardness, flexural strength and complex permittivity were investigated to study their mechanical and dielectric properties. The results revealed that the rGO nanosheets were uniformly distributed in the Al₂O₃ matrix and that the composite ceramics were highly dense at 3.67–3.99 g/cm³. Due to low rGO hardness and elevated porosity, the microhardness exhibits a decreasing trend as the rGO content increases. The flexural strength first increased and then decreased with the escalation of rGO content, and the highest strength of 313.75 MPa was obtained at 3 wt%, increasing by 37.61% relative to that of the hot-pressing sintered Al₂O₃ ceramic. Owing to the enhanced interfacial polarization, dipole polarization, polarization relaxation loss and conductance loss, the real part and imaginary part of complex permittivity increase from 10.40 to 52.73 and from 0.08 to 28.86 as the rGO content rose from 0 wt% to 4 wt%, respectively.     

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.     

ZrO2 functionalized graphene Oxide/SEBS‐Based nanocomposites for efficient electromagnetic interference shielding applications

ZrO₂‐coated graphene oxide (GO)/SEBS(styrene‐ethylene‐butylene‐styrene)‐based nanocomposites were prepared for use as an electromagnetic interference (EMI) shielding material. Transmission electron microscopy (TEM) reveals almost every individual GO is fully and homogeneously covered with uniform ZrO₂. X‐ray diffraction (XRD) patterns and Differential scanning calorimetry (DSC) revealed increased ordering of ‐(CH₂‐CH₂)n segments in the poly(ethylene‐co‐1‐butene) block of the SEBS matrix in the case of SEBS/ZrO₂‐coated graphene oxide composites than in the SEBS/pristine graphene oxide nanocomposite. Thermogravimetric analysis (TGA) proved better oxidation resistance of SEBS/ZrO₂‐coated GO nanocomposite compared to that of SEBS/pristine GO nanocomposite. The present nanocomposites exhibited excellent EMI shielding effectiveness (SE) over X‐band (8.2 GHz–12.4 GHz) with EMI SE of 37.9 dB. J. VINYL ADDIT. TECHNOL., 25:E130–E136, 2019. © 2018 Society of Plastics Engineers     

Eco-friendly one-pot synthesis of gold decorated reduced graphene oxide using beer as a reducing agent

A facile, eco-friendly and economical approach was demonstrated for the synthesis of gold-decorated reduced graphene oxide nanocomposites (rGO–Au_nano) using beer as a reducing agent via a hydrothermal method. The phenolic compounds of beer play a key role in the reduction of graphene oxide and the gold precursor. The obtained rGO–Au_nano was characterized by X-ray diffraction, UV–vis absorption spectroscopy, electron microscopy, atomic force microscopy and the electrochemical impedance spectroscopy. Analysis revealed that the electron-transfer resistance of rGO–Au_nano/GCE was much lower than that of the GCE and GO/GCE. The proposed nanocomposites have excellent electrocatalytical properties for catalytic reduction of O₂ in solution.     

Fabrication and properties of reduced graphene oxide reinforced yttria-stabilized zirconia composite ceramics

Fully dense yttria-stabilized zirconia (YSZ) ceramics reinforced with reduced graphene oxide (RGO) were fabricated by spark plasma sintering (SPS), and their electrical, thermal, and mechanical properties were investigated. Graphene oxide (GO) was exfoliated by a short sonification in dimethylformamide (DMF)/water solution and uniformly mixed with ZrO₂ powders. The microstructure of the composites showed that undamaged RGO sheets were homogeneously distributed throughout matrix grains. The electrical conductivity of YSZ composites drastically increased with the addition of RGO, and it reached 1.2 × 10⁴ S/m at 4.1 vol.%. However, the thermal diffusivity increased only 12% with RGO addition. The hardness decreased slightly with RGO addition, whereas the fracture toughness significantly increased from 4.4 to 5.9 MPa^1/2. The RGO pull-out and crack bridging contributed to the improved fracture toughness.     

Flash sintering of Al2O3–ZrO2 ceramics under alternating current electric field

In this study, the influence of alternating current (AC) electric field on flash sintering and microstructural evolution of alumina–zirconia (Al₂O₃–ZrO₂) composite was systematically investigated at furnace temperature of 800 °C. Compared with direct current (DC) electric field, AC electric field not only promoted densification and grain growth of Al₂O₃–ZrO₂ composite, but also improved the uniformity of microstructure of ceramics. Grain size of AC flash-sintered samples was found to be inversely related to electric field, and positive correlation was observed with current density limit. Dense Al₂O₃–ZrO₂ composite ceramic was fabricated via AC flash sintering under 60 mA mm^?2 at low furnace temperature within 120 s, and as-sintered samples exhibited relatively good mechanical properties. The mechanism involving synergistic effect of Joule heating and defects generation under the influence of electric field was proposed to explain rapid densification during AC flash sintering. These results indicate the feasibility of preparation of dense composite ceramic with homogeneous microstructure via AC flash sintering.     

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     

Fabricating eco-friendly nanocomposites of SiC with morphologically-different nano-carbonaceous phases

A route based on aqueous colloidal processing followed by liquid-phase assisted spark-plasma-sintering (SPS) is described for fabricating eco-friendly nanocomposites of SiC with nano-carbonaceous phases (nanotubes, nanoplatelets, or nanoparticles). To this end, the conditions optimizing the aqueous colloidal co-dispersion of SiC nanoparticles, Y₃Al₅O₁₂ nanoparticles (acting as sintering additives), and carbon nanotubes (CNTs), graphene oxide (GO) nanoplatelets, or carbon black (CB) nanoparticles were first identified. Next, homogeneous powder mixtures were prepared by freeze-drying, and densified by liquid-phase assisted SPS, thus obtaining nanocomposites of SiC with CNTs, reduced GO (rGO) nanoplatelets, or pyrolized?+?graphitized CB (p?+?gCB) nanoparticles. It is also shown that these nanocomposites are dense and have a high hardness of ～20?GPa regardless of the nano-carbonaceous phase chosen, but are markedly tougher with CNTs and rGO (i.e., with high aspect ratio nano-carbonaceous phases). Finally, arguments are provided for the appropriate choice of nano-carbonaceous phases for engineering ceramic nanocomposites.     

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.     

In Situ Processing of Graphene/Leucite Nanocomposite Through Graphene Oxide/Geopolymer

Graphene/leucite nanocomposites (rGO/leucite) were prepared through in situ reduction of graphene oxide/geopolymer (rGO/KGP) composites. The effects of rGO on the microstructure and mechanical properties with respect to the geopolymer matrix after the high‐temperature treatment were investigated systematically. The results show that GO is first partially reduced in the geopolymeric solution and then completely under the post high‐temperature treatment. The rGO sheets undergo no interfacial reactions with the matrix even after thermal treatment. The rGO/geopolymer composites fully transform to rGO/leucite composites after being treated at 1000°C for 30 min in an argon atmosphere. Significant improvements in mechanical properties were achieved through rGO reinforcement giving flexural strength, elastic modulus, and fracture toughness of 91.1 MPa, 60.5 GPa, and 2.04 MPa·m^1/2, increased by 120%, 8%, and 1.5%, respectively, compared with the leucite matrix alone.     

Nanodiamond particles/reduced graphene oxide composites as efficient supercapacitor electrodes

The paper reports on the preparation of reduced graphene oxide (rGO) modified with nanodiamond particles composites by a simple solution phase and their use as efficient electrode in electrochemical supercapacitors. The technique relies on heating aqueous solutions of graphene oxide (GO) and nanodiamond particles (NDs) at different ratios at 100 °C for 48 h. The morphological properties, chemical composition and electrochemical behavior of the resulting rGO/NDs nanocomposites were investigated using UV/vis spectrometry, Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, transmission electron microscopy (TEM) and electrochemical means. The electrochemical performance, including the capacitive behavior of the rGO/NDs composites were investigated by cyclic voltammetry and galvanostatic charge/discharge curves at 1 and 2 A g⁻¹ in 1 M H₂SO₄. The rGO/ND matrix with 10/1 ratio displayed the best performance with a specific capacitance of 186 ± 10 F g⁻¹ and excellent cycling stability.     

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

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

High-performance supercapacitor of manganese oxide/reduced graphene oxide nanocomposite coated on flexible carbon fiber paper

Although supercapacitors have higher power density than batteries, they are still limited by low energy density and low capacity retention. Here we report a high-performance supercapacitor electrode of manganese oxide/reduced graphene oxide nanocomposite coated on flexible carbon fiber paper (MnO₂–rGO/CFP). MnO₂–rGO nanocomposite was produced using a colloidal mixing of rGO nanosheets and 1.8 ± 0.2 nm MnO₂ nanoparticles. MnO₂–rGO nanocomposite was coated on CFP using a spray-coating technique. MnO₂–rGO/CFP exhibited ultrahigh specific capacitance and stability. The specific capacitance of MnO₂–rGO/CFP determined by a galvanostatic charge–discharge method at 0.1 A g⁻¹ is about 393 F g⁻¹, which is 1.6-, 2.2-, 2.5-, and 7.4-fold higher than those of MnO₂–GO/CFP, MnO₂/CFP, rGO/CFP, and GO/CFP, respectively. The capacity retention of MnO₂–rGO/CFP is over 98.5% of the original capacitance after 2000 cycles. This electrode has comparatively 6%, 11%, 13%, and 18% higher stability than MnO₂–GO/CFP, MnO₂/CFP, rGO/CFP, and GO/CFP, respectively. It is believed that the ultrahigh performance of MnO₂–rGO/CFP is possibly due to high conductivity of rGO, high active surface area of tiny MnO₂, and high porosity between each MnO₂–rGO nanosheet coated on porous CFP. An as-fabricated all-solid-state prototype MnO₂–rGO/CFP supercapacitor (2 × 14 cm) can spin up a 3 V motor for about 6 min.     

Reduced-graphene-oxide-reinforced boron carbide ceramics fabricated by spark plasma sintering from powder mixtures obtained by heterogeneous co-precipitation

Reduced graphene oxide (rGO) sheets were uniformly dispersed in boron carbide ceramics by a heterogeneous co-precipitation method. This approach was used to improve the fracture toughness of boron carbide ceramics and to address the problem of agglomeration of graphene in the boron carbide matrix. Cetyltrimethyl ammonium bromide was used as a heterogeneous co-precipitation reaction initiator to prepare a homogeneously dispersed graphene oxide/boron carbide (GO/B₄C) mixture. Reduced graphene oxide/boron carbide (rGO/B₄C) powder mixtures with good dispersion were obtained by high temperature heat treatment. Dense rGO/B₄C composite ceramics were fabricated by spark plasma sintering at 1800 °C and 50 MPa. The fracture toughness and flexural strength of the rGO/B₄C with an rGO content of 2 vol% composite increased by 42% (from 3.43 to 4.88 MPa·m^1/2) and 28% (from 372 to 476 MPa) compared with those of pure B₄C, respectively. The markedly improved fracture toughness and flexural strength of the boron carbide ceramics were attributed to the effect of crack bridging and crack deflection by graphene sheets, graphene interface sliding, and pulling out of graphene.