Influence of the synthesis conditions on the microstructural,compositional and morphological properties of graphene oxide sheets

In this paper we report about the synthesis and characterization of graphene oxide (GO). We monitor the effects of the different synthetic processes on the morphological and structural properties of the materials. A modified Hummers' method is adopted to obtain GO powder; H₂SO₄ is employed as intercalating agent, to increase the distance between graphitic layers, while KMnO₄ is used as oxidizing reagent for introducing the oxygen functionalities in the graphitic structure. The oxidized graphite powder is treated in acid solution; different washing cycles are applied. The recovered powders are dispersed in aqueous solution and sonicated for 30 min or 60 min, respectively. Subsequently, these solutions are deposited on Si and SiO₂(317 nm)/Si substrates by means of dip coating. GO powders, GO solutions and GO on substrate are characterized through several analytical and spectroscopic techniques. These analyses reveal that the sonication time and the washing procedure of the samples can influence the structure and the morphology of the graphene oxide flakes. Moreover, when KOH is employed as alkaline agent in a chemical reducing treatment of the GO powder before sonication, a considerable alteration of the native structure of graphene oxide is observed. The detailed characterization indicates that the properties of the GO samples are strongly influenced by the chemical and physical treatments to which it is subjected.     

Easy preparation of ultrathin reduced graphene oxide sheets at a high stirring speed

This work explored the synthesis of rGO sheets from graphene oxide (GO) using hydrazine solvent as reducing agent through chemical reduction. Meanwhile, GO films with a 2D structure were prepared from graphite flakes (starting material with an average flake size of 150 nm) by an Improved Hummer׳s method. Results showed that the chemical oxidation of graphite flakes carried out at room temperature could be used to prepare GO sheets in the initial stage. The conversion of GO into large-area rGO sheets with ~85% of carbon content could then be achieved by chemical reduction. RGO sheets with a lateral dimension of up to ~45 nm were obtained, which indicated the formation of an extremely thin layer of rGO sheets. A high degree of GO reduction was also realized using a high stirring speed (1200 rpm) for 72 h in a mixture of acids and potassium permanganate, resulting in a high carbon content of rGO with a large lateral dimension and area. Overall, our Improved Hummer׳s method with a high stirring speed (1200 rpm) for 72 h provided an easy approach to the preparation of large-area and ultrathin rGO sheets.     

Polyacrylate-coated graphene-oxide and graphene solution via chemical route for various biological application

In this work, we have developed a polyacrylate-coated graphene-oxide and then chemically reduced them into graphene. We found that polyacrylate coating can improve the colloidal stability of both graphene-oxide/graphene. They show good colloidal stability in different aqueous buffer solution with pH ranging from 5 to 10, and these solutions are stable for more than a month. The polyacrylate-coated grapheme oxide/graphene has been characterized by X-ray photoemission spectroscopy (XPS) and micro-Raman spectroscopy. Based on good colloidal stability, this graphene-oxide/graphene is most suitable for the biological application.     

Synthesis of graphene oxides particle of high oxidation degree using a modified Hummers method

High-oxidation-degree graphene oxide particles were synthesized using a modified Hummers' method. Six different types of particles were synthesized by varying the operating conditions, including the temperature, the reactant ratios, and the oxidation time. The oxidation degree, represented by the oxygen content, and the atomic oxygen/carbon (O/C) ratio were determined using CHNSO elemental analysis, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy-universal attenuated total reflectance sensor (FTIR-UATR) and Raman spectroscopy. The structural morphology of graphene oxide was evaluated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The thermal stability of the particles was studied using thermogravimetric analysis (TGA). The SEM images showed that the prepared GO samples had different graphitic layer structures. The TEM images showed different stacking levels and transparency of GO flakes caused by the difference in oxidation level. The oxygen content and O/C ratios ranged between 34.7 and 50.0 wt% and 0.43 and 0.8, respectively. The highest oxygen content and O/C ratio were found to be 50 wt% and 0.8, respectively, for GO prepared at 95 °C with a 1-hr reaction time (GO2-a). A quantitative analysis on the FTIR-UATR spectra was performed and was in reasonable agreement with the CHNSO analysis results. The Raman spectra showed two characteristic bands (D and G) with different relative intensities, as characterized by the I_D/I_G ratio, suggesting that the prepared samples had different crystallite sizes and defects. The crystallite size (L_a) of the prepared GO particles was estimated using the Tuinstra-Koenig model and were ranging between 9 and 24 nm. The TGA results were correlated with the elemental analysis results and showed a clear dependence of the weight loss on the GO elemental compositions. GO2-a exhibited the lowest thermal stability because of a high oxygen content, whereas GO1-b exhibited the highest thermal stability.     

Effect of graphene addition on the mechanical and electrical properties of Al2O3-SiCw ceramics

This paper presents a study on graphene-reinforced Al₂O₃-SiCw ceramic composites and the relationship between graphene oxide (GO) loading and the resulting mechanical and electrical properties. Well-dispersed ceramic-GO powders were fabricated using a colloidal processing route. Dense composites were obtained via spark plasma sintering, a technique that has the ability to reduce GO to graphene in situ during the sintering process. The mechanical properties of the sintered composites were investigated. The composite with only a small amount of graphene (0.5 vol.%) showed the highest flexural strength (904 ± 56 MPa), fracture toughness (10.6 ± 0.3 MPa·m^1/2) and hardness (22 ± 0.8 GPa) with an extremely good dispersion of graphene within the ceramic matrix. In addition to these exceptional mechanical properties, the sintered composites also showed high electrical conductivity, which allows the compacts to be machined using electrical discharge machining and thus facilitates the fabrication of ceramic components with sophisticated shapes while reducing machining costs.     

Facile preparation and characterization of poly(vinyl alcohol)/chitosan/graphene oxide biocomposite nanofibers

Poly(vinyl alcohol) (PVA)/chitosan (CS)/graphene oxide (GO) biocomposite nanofibers have been successfully prepared using aqueous solution by electrospinning. CS colloidal gel in 1% acetic acid can be changed to homogeneous solution by using electron beam irradiation (EBI). The uniform distributions of GO sheets in the nanofibers were investigated by field emission scanning electron microscopy (FESEM) and Raman spectroscopy. FESEM images illustrated that the spread single GO sheet embedding into nanofibers was formed via self-assembly of GO sheet and PVA/CS chains. And the average diameters of the biocomposite nanofibers decreased (200, 173, 160 and 123 nm) with increasing the contents of GO (0.05, 0.2, 0.4 and 0.6 wt%). Raman spectra verified the presence of GO in the biocomposite nanofibrous mats. The mechanical properties of as-prepared materials related with GO contents. It revealed that the highest tensile strength was 2.78 MPa, which was 25% higher than that of neat PVA/CS nanofibers. Antibacterial test demonstrated that the addition of GO to PVA/CS nanofiber had great ability to increase inhibition zone till 8.6 mm. Overall, these features of PVA/CS/GO nanofibers which were prepared by eco-friendly solvent can be a promising candidate material in tissue engineering, wound healing and drug delivery system.     

Effects of treatment temperature on the reduction of GO under alkaline solution during the preparation of graphene/geopolymer composites

Homogeneously dispersed reduced-graphene-oxide (rGO) reinforced geopolymer composites were successfully prepared through in-situ reduction of graphene oxide (GO) under alkaline geopolymeric condition. The effects of treatment temperatures on the reduction of GO under the alkaline solution during the rGO/geopolymer preparation process were characterized systematically. The results showed that GO could be in situ reduced under alkaline geopolymer solution at various temperatures (25–80 °C) for 3 h. The reduction degree of rGO was improved with increasing the reaction temperature. The rGO was well dispersed, and the rGO/geopolymer composites showed amorphous structure.     

Thinning and functionalization of few-layer graphene sheets by CF4 plasma treatment

ABSTRACT: Structural changes of few-layer graphene sheets induced by CF4 plasma treatment are studied by optical microscopy and Raman spectroscopy, together with theoretical simulation. Experimental results suggest a thickness reduction of few-layer graphene sheets subjected to prolonged CF4 plasma treatment while plasma treatment with short time only leads to fluorine functionalization on the surface layer by formation of covalent bonds. Raman spectra reveal an increase in disorder by physical disruption of the graphene lattice as well as functionalization during the plasma treatment. The F/CF3 adsorption and the lattice distortion produced are proved by theoretical simulation using density functional theory, which also predicts p-type doping and Dirac cone splitting in CF4 plasma-treated graphene sheets that may have potential in future graphene-based micro/nanodevices. PACS: 81.05.ue; 73.22.Pr; 52.40.Hf.     

Observation of strain effect on the suspended graphene by polarized Raman spectroscopy

We report the strain effect of suspended graphene prepared by micromechanical method. Under a fixed measurement orientation of scattered light, the position of the 2D peaks changes with incident polarization directions. This phenomenon is explained by a proposed mode in which the peak is effectively contributed by an unstrained and two uniaxial-strained sub-areas. The two axes are tensile strain. Compared to the unstrained sub-mode frequency of 2,672 cm⁻¹, the tension causes a red shift. The 2D peak variation originates in that the three effective sub-modes correlate with the light polarization through different relations. We develop a method to quantitatively analyze the positions, intensities, and polarization dependences of the three sub-peaks. The analysis reflects the local strain, which changes with detected area of the graphene film. The measurement can be extended to detect the strain distribution of the film and, thus, is a promising technology on graphene characterization.     

Substrate interaction effects on optical and acoustical plasmons in bi-waveguides based on graphene

We theoretically study the dynamic dielectric response function of a gas of massless Fermions embedded in a coupled double quantum wire structure based on graphene. We write the dielectric function within the random phase approximation (RPA). We approach the system using the two-dimensional (2D) Dirac-like Hamiltonian in the first place, where a parameter β, accounting for the interaction between the substrate and the graphene sheet, is considered in an ad-hoc manner. We study the weak tunneling regime between the two ribbons and find the energy dispersion of the acoustical and optical plasmon modes. Our results show that different choices for the parameter β in the structure should induce spatial anisotropy effects on the plasmon modes.     

One-step hydrothermal synthesis and enhanced microwave absorption properties of Ni0.5Co0.5Fe2O4/graphene composites in low frequency band

Ni_0.5Co_0.5Fe₂O₄/graphene composites were synthesized successfully via one-step hydrothermal method. The crystal structure, morphology and corresponding elemental distribution, electromagnetic parameters and microwave absorption performances of the as-prepared composites were measured by XRD, SEM, TEM and VNA, respectively. The results indicated that the microwave absorbing performance can be obviously enhanced through the addition of graphene in a suitable range, the magnetic loss plays a dominant contribution for the microwave absorption of composites. The maximum reflection loss of ?30.92?dB at 0.84?GHz with a ?10?dB bandwidth over the frequency range of 0.58–1.19?GHz is obtained when the composite contains 12?wt% graphene and the thickness of sample is 4?mm. This investigation presents a simple method to prepare Ni_0.5Co_0.5Fe₂O₄/graphene composites with excellent microwave absorption performance in the low frequency band of 0.1–3?GHz.     

A novel electrochemical DNA biosensor based on graphene and polyaniline nanowires

A novel DNA biosensor based on oxidized graphene and polyaniline nanowires (PANIws) modified glassy carbon electrode was developed. The resulting graphene/PANIw layers exhibited good DPV current response for the complementary DNA sequences. The good electron transfer activity might be attributed to the effect of graphene and PANIw. Graphene and PANIw nanolayers film with highly conductive and biocompatible nanostructure were characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The immobilization of the probe DNA on the surface of electrode was largely improved due to the unique synergetic effect of graphene and PANIw. Under optimum conditions, the biosensor exhibited a fast amperometric response, high sensitivity and good storage stability for monitoring DNA. The current response of the sensor increases linearly with the concentration of target from 2.12 × 10⁻⁶ to 2.12 × 10⁻¹² mol l⁻¹ with a relative coefficient of 0.9938. The detection limit (3σ) is 3.25 × 10⁻¹³ mol l⁻¹. The results indicate that this modified electrode has potential application in sensitive and selective DNA detection.     

Morphology-controlled synthesis of CdSe microspheres on graphene oxide sheets and their photocatalytic properties

Different morphologies of CdSe microspheres have been synthesized on reduced graphene oxide (rGO) sheets by a simple hydrothermal process using Cadmium nitrate and Se powder as the raw materials. The hybrid CdSe/rGO samples were intensively investigated by XRD, EDS, XPS, SEM and UV–vis absorption spectrum. It was found that the EDTA/Cd²⁺ molar ratio is crucial for the formation of morphology of CdSe grown on rGO sheets. The results of XRD reveal that the as-prepared CdSe microspheres have zinc blend structure. The results of Raman spectra, EDS, XPS and SEM show that the CdSe microspheres are grown on rGO sheets. In addition, UV–vis absorption spectrum indicates that the CdSe/rGO nanocomposites are believed to serve as photosensitizers to extend the absorption spectrum to visible light region. Superior photocatalytic activity of urchin-like CdSe microspheres grown on rGO sheets relative to those of other CdSe/rGO nanocomposites was observed under visible light irradiation. The growth mechanism for the formation of CdSe microspheres grown on rGO sheets was also described.     

Low temperature synthesis and effect of Co doping on structural,optical and dielectric properties of CuCrO2 hexagonal nanoplates

In this research work, delafossite oxide CuCrO₂ and its different Co doped compositions CuCr_1-xCo_xO₂ (x = 0.05, 0.1, 0.15) were successfully synthesized by low temperature hydrothermal method. X-ray diffraction (XRD) confirmed the formation of CuCrO₂ nanostructures with hexagonal structure having crystallite size less than 100 nm. The XRD peaks also confirmed that the fraction of Cr ions are perfectly replaced by the Co ions in the lattice structure. The crystallite size was found to decrease with increasing the doping concentration. The formation of nanoplates with hexagonal morphology was studied by using scanning electron microscope (SEM). The Fourier transform infrared spectroscopy (FTIR) was employed to analyze the occurrence of various functional groups, stretching and vibrational modes. Tauc's relation was used to calculate the optical band gap (E_g) of the samples from the absorbance spectra. E_g was observed to increase from 3.61eV to 3.95 eV which may be attributed to the reduction in crystallite size as a result of Co doping. The doping concentration also increases the density of grain boundaries which in turn induced the lattice strain in the crystal structure. The interplanar spacing d was observed to increase from 2.489 Å to 2.508 Å resulted due to induced strain. A maximum strain of 0.0132 was found in CuCr_0.85Co_0.15O₂. The impedance and dielectric dispersion of the material were measured using LCR meter. The Cole-Cole plots represent the perfect dielectric behaviour of these materials indicating the pre dominant grain boundary resistance. The dielectric constant showed the increasing behaviour with Co doping concentration. Our results show that manipulation of the band gap and dielectric properties of CuCrO₂ nanoplates with doping of Co ions can broadly enhance the efficiency and the applications of these oxide materials.     

Development of yttria-stabilized zirconia and graphene coatings obtained by suspension plasma spraying: Thermal stability and influence on mechanical properties

This study investigated the feasibility of depositing graphene nanoplatelet (GNP)-reinforced yttria-stabilized zirconia (YSZ) composite coatings. The coatings were deposited from an ethanol-based mixed YSZ and GNP suspension using suspension plasma spraying (SPS). Raman spectroscopy confirmed the presence of GNPs in the YSZ matrix, and scanning electron microscopy (SEM) analysis revealed a desired columnar microstructure with GNPs distributed predominantly in the inter-columnar spacing of the YSZ matrix. The as-deposited YSZ-GNP coatings were subjected to different isothermal treatments—400, 500, and 600 °C for 8 h—to study the thermal stability of the GNPs in the composite coatings. Raman analysis showed the retention of GNPs in specimens exposed to temperatures up to 500 °C, although the defect concentration in the graphitic structure increased with increasing temperature. Only a marginal effect on the mechanical properties (i.e., hardness and fracture toughness) was observed for the isothermally treated coatings.     

Effect of incorporation of graphene oxide and graphene nanoplatelets on mechanical and gas permeability properties of poly(lactic acid) films

Nanocomposite thin films of poly(lactic acid) (PLA) were produced incorporating small amounts (0.2 to 1 wt%) of graphene oxide (GO) and graphene nanoplatelets (GNP). The films were prepared by solvent‐casting. Mechanical properties were evaluated for plasticized (by residual solvent) and unplasticized films. Plasticized nanocomposite films presented yield strength and Young's modulus about 100% higher than those of pristine PLA. For unplasticized films improvements in tensile strength and Young's modulus were about 15 and 85%, respectively. For both film types, a maximum in mechanical performance was identified for about 0.4 wt% loadings of the two filler materials tested. Permeabilities towards oxygen and nitrogen decreased, respectively, three‐ and fourfold in films loaded with both GO or GNP. The glass transition temperature showed maximum increases, in relation to unloaded PLA films, of 5 °C for 0.4 wt% GO and 7 °C for 0.4 wt% GNP, coinciding with the observed maxima in mechanical properties. Copyright © 2012 Society of Chemical Industry     

Non-congruence of high-temperature mechanical and structural behaviors of LaCoO3 based perovskites

This paper presents the mechanical behavior of LaCoO₃ and La_0.8Ca_0.2CoO₃ ceramics under four-point bending in which the two cobaltites are subjected to a low stress of ∼8 MPa at temperatures ranging from room temperature to 1000 °C. Unexpected stiffening is observed in pure LaCoO₃ in the 700–900 °C temperature range, leading to a significant increase in the measured Young’s modulus, whereas La_0.8Ca_0.2CoO₃ exhibits softening from 100 °C to 1000 °C, as expected for most materials upon heating. Neutron diffraction, X-ray diffraction and micro-Raman spectroscopy are used to study the crystal structure of the two materials in the RT–1000 °C temperature range. Despite a detailed study, there is no conclusive evidence to explain the stiffening behavior observed in pure LaCoO₃ as opposed to the softening behavior in La_0.8Ca_0.2CoO₃ at high temperatures (above 500 °C).     

Amplified immunosensing based on ionic liquid-doped chitosan film as a matrix and Au nanoparticle decorated graphene nanosheets as labels

This paper describes a new signal amplification strategy based on ionic liquid-doped chitosan film as a matrix and Au nanoparticle decorated graphene nanosheets (AuNP–graphene) as labels for the sensitivity improvement of an electrochemical immunosensor. At first, an ionic liquid was doped into ferrocene-branched chitosan film to obtain a novel redox composite, which was employed as an antibody immobilization matrix due to its better biocompatibility and higher electron transfer mobility. Then, the AuNP–graphene were prepared by a one-pot method in a aqueous-phase synthesis and were provided with a large surface area and multiple binding sites to allow high accessibility for the immobilization of secondary antibody (Ab2) and horseradish peroxidase (HRP). Based on the sandwich immunoassay format, the electrochemical signal could be amplified and adequately achieved, according to the catalytic reaction of the carried HRP towards the reduction of H₂O₂ with the aid of the IL and ferrocene synergistic effect. Using Immunoglobulin G (IgG) as a protein model, a good and repeatable linear relationship was found between the electrical signal outputs and human IgG concentration on a logarithm scale for a wide range of 2.0 × 10⁻¹⁰ to 5.0 × 10⁻⁷ g/mL, with a detection limit of 50 pg/mL. In conclusion, the use of ionic liquid-doped chitosan redox film and AuNP–graphene greatly enhances the electrochemical signal and shows high sensitivity.     

Dispersion of graphene nanoplatelets in poly(vinyl acetate) latex and effect on adhesive bond strength

Graphene nanoplatelets (GNPs) were directly dispersed in poly(vinyl acetate) (PVAc) latex in concentrations from 0.05 up to 2 wt% (based on dry weight), without using additional surfactants or dispersants. Stable dispersions were obtained due to interaction of the GNPs with protective colloids (poly(vinyl alcohol) and hydroxyethylcellulose) originally present in the latex. This caused an increase in viscosity and accentuated the pseudoplastic behavior of the latex, as evidenced by rheological measurements. Cryo‐SEM imaging showed that individual nanoplatelets were present in the aqueous phase. The equilibrium contact angle for water on dry PVAc films increased by 13° upon incorporation of 0.1 wt% GNPs due to the nanofiller hydrophobicity. However, this increase was lower for higher loadings, probably due to the occurrence of GNP agglomeration. Bond strength measurements performed with an automated bonding evaluation system setup on veneer lap joints showed more than 50% shear strength increase with incorporation of only 0.1–0.3 wt% GNPs. At higher loadings the bond strength decreased, indicating less efficient nanofiller dispersion in the polymer matrix. Raman spectroscopy analysis confirmed that GNP agglomeration was more significant at higher loadings.