The production of concentrated dispersions of few-layer graphene by the direct exfoliation of graphite in organosilanes

We report the formation and characterization of graphene dispersions in two organosilanes, 3-glycidoxypropyl trimethoxysilane (GPTMS) and phenyl triethoxysilane (PhTES) as new reactive solvents. The preparation method was mild and easy and does not produce any chemical modification. The dispersions, which exhibit the Tyndall effect, were characterized by TEM and Raman spectroscopy to confirm the presence of few-layer graphene. Concentrations as high as 0.66 and 8.00 mg/ml were found for PhTES and GPTMS, respectively. The latter is one of the highest values reported for a dispersion of graphene obtained by any method. This finding paves the way for the direct synthesis of polymer nanofiller-containing composites consisting of graphene and reactive silanes to be used in sol–gel synthesis, without any need for solvent removal, thus preventing graphene reaggregation to form graphite flakes.     

The production of graphene by direct liquid phase exfoliation of graphite at moderate sonication power by using low boiling liquid media: The effect of liquid media on yield and optimization

There are many production methods for graphene production. One of the most successful production methods in terms of scale-up is liquid phase exfoliation (LPE) method. In this study, after optimizing the sonication time and sonication power that are effective in the production to increase the efficiency of the LPE method, the experiments were continued at moderate sonication powers and the effect of liquid media, another important parameter, was examined. In this study, hexagonal graphite powders were subjected to direct liquid phase exfoliation process by using different liquid media (N-Methyl-2-Pyrrolidone (NMP), N,N-Dimethylformamide (DMF), ethanol, 2-propanol, acetone, methanesulfonic acid, ethanol + Sodium dodecyl sulphate (SDS), 2-propanol + SDS) and the obtained samples were characterized. As a result of the characterization, the liquid media with the highest efficiency was determined to be NMP. Besides, it was observed that a new hybrid solvent obtained by adding a surfactant such as SDS into low-cost and environmentally friendly liquid media such as ethanol and 2-propanol showed a higher efficiency than NMP. It was observed that 3–5 layer graphene ranged between 15 and 19 wt% in either graphene produced by using hybrid solvents containing NMP or SDS. The amount of double or single-layer graphene was negligibly small. The production with the lowest efficiency was observed in the use of acetone. The produced graphenes were dispersed in the liquid and their sedimentation time was observed. The sedimentation time of graphenes, produced using NMP and SDS-doped hybrid solvents, in liquid was more than 120 days. The sedimentation time of graphene produced using acetone was less than 20 days. In the use of graphene as a reinforcing material or adsorbent, large amounts of graphene are needed. In such applications, mass production of graphene is important rather than the number or quality of sheets of graphene. Therefore, optimization of production parameters of LPE method, which is suitable for mass production, is significance.     

In situ exfoliation of graphite oxide nanosheets in polymer nanocomposites using miniemulsion polymerization

Poly(styrene-co-butyl acrylate) (poly(St-co-BA)) nanocomposite latices based on graphene oxide (GO) were synthesized by miniemulsion polymerization. The polymerization procedure involved dispersing an aqueous solution of graphite oxide in a monomer phase, followed by emulsification in the presence of a hydrophobe and a surfactant into miniemulsions. The focus was to investigate the suitability of miniemulsion for the synthesis of polymer nanocomposites based on a graphene derivative (i.e., GO) with exfoliated structure in a one-step nano-incorporation technique. Poly(St-co-BA) nanocomposites containing the exfoliated GO nanoplatelets, which have improved mechanical and thermal properties were successfully synthesized by the miniemulsion process. The nanostructure of the nanocomposites was investigated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). TEM and XRD indicated that the nanocomposites mainly showed exfoliated morphologies, except at relatively high GO content. TEM also revealed that the nanocomposite latices had the so-called ‘‘armored’’ structure, where the nanosized GO sheets are distributed around the edges of the copolymer particles.     

Correlation of exfoliation performance with interlayer cations of montmorillonite in the preparation of two-dimensional nanosheets

Montmorillonite (MMT) can be exfoliated into nanosheets used in a wide range of applications as two-dimensional (2D) material. The exfoliated MMT nanosheets with high diameter–thickness ratio appear to show superior properties in preparation of nanocomposites and other functional materials. In this work, the correlation of exfoliation performance with interlayer cations of MMT in the preparation of 2D nanosheets was investigated. The thickness and lateral diameter of MMT nanosheets were quantitatively measured by atomic force microscopy (AFM) technique. AFM results showed the exfoliated K-MMT had larger lateral diameter and thinner thickness than the exfoliated Ca-MMT under the same exfoliation conditions. Molecular simulation was applied to investigate the interlayer-binding energy (IBE), population analysis and density of states. K-MMT structures tend to have higher in-plane chemical bond intensity than Ca-MMT because of the impact of antibonding. The IBE of K-MMT was higher than that of Ca-MMT after the sorption of water molecules into the neighboring monolayers, indicating that thinner naonosheets tend to be easier obtained from Ca-MMT than K-MMT in liquid exfoliation. These findings might be helpful for the preparation and application of 2D MMTNS through controlling interlayer cation species and the exfoliation properties of MMT.     

A note on using expanded graphite for achieving energy- and time-efficient production of graphene nanoplatelets via liquid phase exfoliation

Although easily scalable, the production of graphene nanoplatelets (GNP) by the means of liquid-phase exfoliation of graphite flakes (GF) remains an energy- and time-intensive process. In this work, we demonstrate that significant time and energy can be saved in GNP production when employing expanded graphite (EG) in a surfactant-assisted liquid phase exfoliation process. Owing to its increased interlayer distance, the exfoliation of EG can be accomplished in a much shorter time (<30 min) compared to GF (approximately 7 h in the present case). Moreover, the energy required for the EG exfoliation is close to 80-fold lower than that for GF exfoliation. Monitoring of the mean lateral dimension, specific surface area, and graphite flake-to-GNP transition during exfoliation was performed experimentally using several analytical techniques. The EG-derived GNPs are produced much faster and require less energy for exfoliation compared to GF, thus making it a more efficient alternative technique.     

Green and efficient production of boron nitride nanosheets via oxygen doping-facilitated liquid exfoliation

As the structural analogue of graphene, boron nitride nanosheets (BNNSs) are anticipated to have a wide range of potential applications. BNNSs exhibit good mechanical properties, outstanding thermal conductivity, oxidation and chemical stability and are excellent electrical insulators. While BNNSs have gained recognition as one of the most versatile 2D materials in recent years, their application in research and industry is still hampered by the lack of methods to produce BNNSs in large quantity and a cost-effective way. In this study, we report highly efficient h-BN exfoliation via the oxygen doping-facilitated liquid exfoliation. Oxygen atoms are introduced into the hexagonal boron nitride (h-BN) structure via a facile thermal treatment. The relationship of thermal treatment, structural changes and h-BN exfoliation are studied to elucidate the key factor for advancing the BNNS production. The optimum concentration of hydroxyl groups and weakening of interlayer interactions have synergistically facilitated the delamination of h-BN in water under mild exfoliation conditions, resulting in up to 1255% yield increment and without noticeable new defects in the BNNS structure as compared with the untreated control. An efficient and environmentally friendly exfoliation process of h-BN is a crucial starting point towards the cost-effective and mass production of BNNSs which is needed for the currently identified and myriad future applications of BNNSs.     

Utilization of multiple graphene layers in fuel cells. 1. An improved technique for the exfoliation of graphene-based nanosheets from graphite

An improved, safer and mild method was proposed for the exfoliation of graphene like sheets from graphite to be used in fuel cells. The major aim in the proposed method is to reduce the number of layers in the graphite material and to produce large quantities of graphene bundles to be used as catalyst support in polymer electrolyte membrane fuel cells. Graphite oxide was prepared using potassium dichromate/sulfuric acid as oxidant and acetic anhydride as intercalating agent. The oxidation process seemed to create expanded and leafy structures of graphite oxide layers. Heat treatment of samples led to the thermal decomposition of acetic anhydride into carbondioxide and water vapor which further swelled the layered graphitic structure. Sonication of graphite oxide samples created more separated structures. Morphology of the sonicated graphite oxide samples exhibited expanded the layer structures and formed some tulle-like translucent and crumpled graphite oxide sheets. The mild procedure applied was capable of reducing the average number of graphene sheets from 86 in the raw graphite to nine in graphene-based nanosheets. Raman spectroscopy analysis showed the significant reduction in size of the in-plane sp² domains of graphene nanosheets obtained after the reduction of graphite oxide.     

A comparative study on different aqueous-phase graphite exfoliation methods for few-layer graphene production and its application in alumina matrix composites

Four different methods (attrition milling, shear mixing, low-power bath sonication and tip sonication) used for the aqueous-phase, surfactant-assisted exfoliation of graphite were compared. Few-layer graphene (FLG) concentration, yield and production rate were measured for each method at different production times and the quality of the as produced FLG was determined using Raman spectroscopy and X-ray diffraction. It was inferred from the results that a combined method comprising tip sonication and shear exfoliation would offer the best balance between quality and quantity of FLG for relatively short processing times (<6 h). FLG dispersions produced with this method were used to fabricate 1 wt.% FLG/Al₂O₃ nanocomposites by ball milling and extrusion, followed by pressure-less sintering. The influence of the FLG addition on the microstructure and mechanical properties was studied, with observed increases of 26.4% and 67.6% in flexural strength and fracture toughness,respectively, and a 25.3% decrease in average grain size.     

Graphene based composites prepared through exfoliation of graphite platelets in methyl methacrylate/poly(methyl methacrylate)

The use of methyl methacrylate/poly(methyl methacrylate) as a medium for the exfoliation of graphite platelets without any chemical treatment is reported. The dispersions, characterized by transmission electron microscopy and Raman spectroscopy, confirmed the obtainment of graphene sheets a few layers thick. We found that the electrical conductivity of such nanocomposites can be activated at temperature by the application of an external electric field, this effect being reversible after removal of the thermal stimulus. This result provides an initial understanding of how electric field assisted thermal annealing can be used to control the bulk physical properties of such composites. Copyright © 2012 Society of Chemical Industry     

Characterizing various types of defects in nuclear graphite using Raman scattering: Heat treatment,ion irradiation and polishing

Raman spectroscopy has proved to be an appropriate technique to probe defects in carbon-based materials owing to its high sensitivity, most often focused on the commonly used I_D/I_G parameter. However, this ratio may be activated by various types of defects and in a completely independent manner. Therefore, discriminating between defects is challenging. The central idea of the present work is to provide a better understanding of the Raman response to the various types of defects that may appear in nuclear graphite (carbon–carbon composite) during its manufacturing process, its operation in the nuclear reactor, or even during its preparation process such as polishing which is usually used prior to Raman characterization. This work also demonstrates the discrimination of the defect types using the combination of the I_D/I_G and FWHM(G), two structural disorder indicators evolving differently according to the type and the concentration of the introduced defects into the carbon network. The ion-beam irradiation was used here as an effective way for creating defects that could be similar to those created by neutrons in the nuclear reactor.     

Preparation of graphite nanosheets in different solvents by sand milling and their enhancement on tribological properties of lithiumbased grease

Graphite nanosheets with the average thicknesses ranging from 24.4 to 48.9 nm were prepared with the use of expanded graphite as the raw material by sand milling in deionized water, anhydrous ethanol, glycerol, and 1,4-butanediol, respectively. Anhydrous ethanol favored the formation of graphite nanosheets with a smaller average thickness. When the graphite nanosheets with the content of 2 wt% were added in lithium-based grease, the average friction coefficient decreased by 27% as compared with the pure lithium-based grease. The weld point and load wear index were 1.6 and 1.4 times those of the pure lithium-based grease, respectively. The tribological properties of the graphite nanosheet-containing lithium-based grease were comparable with those of the graphene-containing lithium-based grease.     

Synthesis of a pyrene-functionalized hyperbranched polyethylene ternary copolymer for efficient graphite exfoliation in chloroform and formation of ethylene-vinyl acetate/graphene nanocomposites

A strategy for preparing ethylene-vinyl acetate (EVA)/graphene nanocomposites from liquid-phase exfoliated graphene has been explored with the use of a pyrene-functionalized hyperbranched polyethylene (HBPE) ternary copolymer, HBPE@Py@PMA, as stabilizer for graphite exfoliation. The HBPE@Py@PMA was synthesized by combining the Pd-diimine-catalyzed chain walking ternary ethylene copolymerization and atomic transfer radical polymerization techniques and has been confirmed to possess a HBPE core simultaneously bearing pyrene terminal groups and polymethacrylate side chains. As stabilizer, it is found to effectively promote graphite exfoliation in CHCl₃ to render high-quality few-layer graphene with an efficiency as high as 43%. Meanwhile, it can be steadily adsorbed on the exfoliated graphene surface to concurrently render functionalized graphene well dispersible in EVA matrix with strong interfacial interactions. This allows us to obtain EVA/graphene nanocomposites from resulting graphene dispersion through simple solution mixing process. By adding only 0.5 wt% of graphene, the dielectric constant of resulting composite increases by 55% compared to pure EVA, with a dielectric loss only 0.012. The role mechanism of the HBPE@Py@PMA for promoting graphite exfoliation in CHCl₃ and the formation of EVA/graphene nanocomposites from the resulting graphene has been proposed.     

Investigation of thermal residual stresses during laser ablation of tantalum carbide coated graphite substrates using micro-Raman spectroscopy and COMSOL multiphysics

Laser ablation of high-temperature ceramic coatings results in thermal residual stresses due to which the coatings fail by cracking and debonding. Hence, the measurement of such residual stresses during laser ablation process holds utmost importance from the view of performance of coatings in extreme conditions. The present research aims at investigating the effect of laser parameters such as laser pulse energy, scanning speed and line spacing on thermal residual stresses induced in tantalum carbide-coated graphite substrates. Residual stresses were measured using micro-Raman spectroscopy and correlated with Raman peak shifts. Transient thermal analysis was performed using COMSOL Multiphysics to model the single ablated track and residual stresses were reported at low, moderate and high pulse energy regimes. The results showed that the initial laser conditions caused higher tensile residual stresses. Moderate pulse energy regime comprised higher compressive residual stresses due to off centre overlapping of the laser pulses. Higher pulse energy (250 μJ), higher scanning speed (1000 mm/s) and moderate line spacing (20 μm) caused accumulation of tensile residual stresses during the final stage of laser ablation. The deviation of experimental residual stresses from COMSOL numerical model was attributed to unaccounted additional stresses induced during thermal spraying process and deformation potentials in the numerical model.     

Thermally and chemically induced structural transformations of Keggin-type heteropoly acid catalysts

Raman characterization revealed that the Keggin anion structure of H₄PVMo₁₁O₄₀ is inherently unstable upon heat treatment and loss of water. Vanadyl and molybdenyl species are expelled from the Keggin cage and defective Keggin structures are formed. These defective structures further disintegrate to presumably Mo₃O₁₃ triads of the former Keggin. These Keggin fragments oligomerize at later stages to molybdenum oxygen clusters comparable to hepta- or octamolybdates. The final disintegration and structural reorganization product is MoO₃. This disintegration and recondensation process seems to be strongly affected by the heating rate and hence the presence of water in the sample. Only partial expulsion of V occurred under moderate dehydration conditions. The absence of water during heat treatments stabilizes the intermediate defective structures. Raman spectroscopy proved that free polyacids are unstable under catalytic partial oxidation conditions. Therefore, it can be suggested that intact Keggin anions are not the active species within an operating partial oxidation catalyst. From this Raman spectroscopy study it may be inferred that the structurally reorganized intermediates are relevant for the catalytic action. The Raman investigations of the HPA decomposition additionally revealed a dependency of the decomposition process on the reactive atmosphere and the presence of Cs. The presence of Cs led to a partial stabilization of the structural disintegration products of PVMo₁₁ and to the formation of the thermodynamically stable, but catalytically inactive Cs₃-salt. Cs also inhibited the condensation of MoO₃-type oxides. O₂ present in the gas phase also led to stabilization of the structural reorganization intermediates. Importantly, the presence of water did not lead to a stabilization of the intact Keggin structure. In contrast, hydrolysis of the Keggin anions seemed to be enhanced compared to the water-free situation. This observation is of high importance because water is added to the feed in industrial partial oxidation reactions. Hence, under industrial conditions, HPA-derived catalysts are inherently unstable and cannot contain intact Keggin anions at their active surface. Catalytic partial oxidation conditions even led to a more pronounced structural reorganization and amorphous suboxides of the MoO_3−x type seemed to be formed. Hence, heteropolyacids have to be understood only as defined molecular precursor compound.     

Ball milling and annealing graphite in the presence of cobalt

When graphite is ball milled, Raman spectra and X-ray diffractograms of the products show increasing graphitic structural disorder with 1% and 10% cobalt addition. However, if sufficient cobalt (10% weight for weight) is added, this process is reduced in rate. This process is attributed to the cobalt stabilizing the graphitic structure during ball milling, thus reducing the degree of lattice-disorder.When the mixture is annealed, well-ordered carbon strips encapsulating cobalt nanoparticles are observed in the presence of cobalt.Annealing reorganizes the disordered structures and 10% cobalt loading is more effective than a 1% loading in this process. Transmission electron microscopic (TEM) analysis showed the formation and high abundance of well-ordered carbon strips encapsulating cobalt nanoparticles in samples that have been annealed with additional cobalt loading.     

The evaluation of the gross defects of carbon nanotubes in a continuous CVD process

Carbon nanotubes (CNTs) were prepared by ethylene decomposition on an Fe/Al₂O₃ catalyst in a fluidized bed reactor. Their gross defects at different growth periods are evaluated by using a combination of SEM, TGA and Raman spectroscopy. The initially grown CNTs have a much lower thermal stability and more defects as compared to the fully-grown ones. The difference in the defects of CNTs at different reaction times is attributed to the lift up of CNTs with the gradually crashing texture of catalyst and the increasing volume of CNTs in a limited reactor space.     

Microwave dielectric properties,low-temperature sintering mechanism,and defects behaviour of temperature stable (1-x)Li2Zn3Ti4O12-xSr3(VO4)2 ceramics

(1-x)Li₂Zn₃Ti₄O₁₂-xSr₃(VO₄)₂ (0.1 ≤ x ≤ 0.4) microwave dielectric ceramics were fabricated by solid-state sintering technology. The impact of SV addition on the microstructure, dielectric properties, sintering process, and defects behaviour was studied. The formation of SrTiO₃ and the glass phase were observed via XRD and TEM, and the latter resulted in a decrease in the sintering temperature. The variations in microwave dielectric properties were consistent with the empirical mixture rules calculated by XRD refinement, and a near-zero τ_f value was obtained. The Li, Zn and V elements of the glass phase and the liquid phase sintering model were deduced via DSC, TEM and Raman spectroscopy. Then, the defect behaviour, such as oxygen vacancies, Ti³⁺, and V⁴⁺, was investigated by XPS and complex impedance spectroscopy. It was found that the generation and migration of defects occurred much more easily in 0.7LZT-0.3 SV than in LZT, resulting in a higher dielectric loss. Finally, the 0.7Li₂Zn₃Ti₄O₁₂-0.3Sr₃(VO₄)₂ ceramic sintered at 900 °C exhibited excellent microwave dielectric properties of ε_r = 17.8, Q × f = 41,891 GHz, and τ_f = ?4.4 ppm/°C and good compatibility with silver electrode, showing a good potential application for LTCC.     

Coexistence of Ferroelectric Phases and Phonon Dynamics in Relaxor Ferroelectric Na0.5Bi0.5TiO3 Based Single Crystals

A combination of polarized Raman technique, infrared reflectance spectra, and first‐principles density‐functional theoretical calculations were used to investigate structure transformation and lattice vibrations of Na_0.5Bi_0.5TiO₃, Na_0.5Bi_0.5TiO₃–5%BaTiO₃, and Na_0.5Bi_0.5TiO₃–8%K_0.5Bi_0.5TiO₃ single crystals. It was found that Na_0.5Bi_0.5TiO₃ is of a two‐phase mixture with rhombohedral and monoclinic structures at room temperature. Correspondingly, three Raman‐active phonon modes located at 395, 790, and 868 cm^?1, which were previously assumed as A₁ modes of rhombohedral phase have been reassigned as A^′′, A^′, and A^′ modes of monoclinic phase in the present work. In particular, a strong low‐frequency A^′′ mode at 49 cm^?1 was found and its temperature dependence was revealed. Two deviations from linearity for the abrupt frequency variation in the A^′′ mode and Ti–O bond have been detected at temperatures of ferroelectric to antiferroelectric phase transition T_F–AF and dielectric maximum temperature T_max. The appearance of Na–O vibrations at 150 cm^?1 was found below T_max, indicating the existence of nanosized Na⁺TiO₃ clusters. The observed Raman and infrared active modes belonging to distinct irreducible representations are in good agreement with group‐theory predictions, which suggests 9A₁+9E and 36A^′′+24A^′ modes for the rhombohedral and monoclinic phases of Na_0.5Bi_0.5TiO₃, respectively.     

Raman and dielectric spectroscopic analysis of magnetic phase transition in Y(Fe0.5Cr0.5)O3 multiferroic ceramics

Here, we report the Raman and dielectric spectroscopic studies as a function of temperature of orthorhombically distorted Y(Fe_0.5Cr_0.5)O₃ (YFC) ceramics, measured from 80 to 300 K. The dc-magnetization measurements under field cooled (FC)-zero field cooled (ZFC) protocol indicate a small onset of magnetic ordering at T_N∼270 K. The field dependent magnetization plot recorded at 50 K, 150 K and 200 K show a clear opening in hysteresis loops. The linear dependence of magnetization plot at high field without any saturation of magnetization indicates the coexistence of weak ferromagnetic (WFM) component within the canting antiferromagnetic (CAFM) matrix. Temperature evolution of Raman line-shape parameter of B_2g(4) phonon mode clearly exhibits an anomalous behavior of phonon shift near T_N∼270 K, indicating the spin-phonon coupling in the ceramics. From the temperature dependent dielectric permittivity (ε(T)) study, two dielectric relaxation peaks are detected below 200 K and above 250 K. The appearance of former relaxation peak is responsible for polaronic conduction mechanism, while the later one is associated with magnetic phase transition which might be relevant to the presence of magnetoelectric coupling in YFC ceramics. The observed P-E hysteresis loops at room temperature indicate weak ferroelectric nature of the ceramics.     

Probing the effect of R-cation radii on structural,vibrational, optical,and dielectric properties of rare earth (R=La,Pr, Nd) aluminates

The present study correlates the effect of R-cation radii on structural, vibrational, optical, and dielectric properties of rhombohedral rare earth aluminates RAlO₃ (R = La, Pr, Nd). The polycrystalline samples of RAlO₃ have been synthesized using sol-gel synthesis technique. Pure rhombohedral phase of RAlO₃ samples has been confirmed with X-ray diffraction. Systematic decrements in the lattice parameter, bond length, and bond angle have been observed, giving rise to structural distortion due to decrease in ionic radii of R-cation. The phononic properties of RAlO₃ have been investigated through Raman spectroscopy, where the degree of distortion of AlO₆ octahedra can be analyzed with the peak position of E_g and A_1g modes. An increase in the energy bandgap with decreasing R-cation radii shows an interconnection with the decrease in Al–O bond length. Interestingly, the decreasing dielectric constant with decreasing ionic radii of R-cation has been correlated with the difference in electronegativity of cation(R³⁺)-anion(O^2?) pair. Also, a positive linear relationship between dielectric constant and energy bandgap has been investigated using Penn model.