Graphene Plates Research Articles

Graphene addition to MgB2 superconductor obtained by ex-situ spark plasma sintering technique

Graphene nanopowder (G) with average thickness particle size of about 6–8nm was added to MgB2 commercial powder. Starting composition was (MgB2)(1−x)(G)x, x=0.0125, 0.025, 0.05. Processing was performed by Spark Plasma Sintering (SPS) technique. All added samples have high density (above 95%). The critical temperature (Tc) and the lattice parameter a (c-axis lattice parameter is constant) show a small variation suggesting that carbon substitution for boron is low. TEM observations show the presence of un-reacted graphene plates supporting the Tc and structural results. It also indicates that G-addition does not modify the MgB2 microstructure. Despite this, there is an optimum doped sample (MgB2)0.9875(G)0.0125 for which the critical current density at temperatures below 25K is slightly higher at high magnetic fields than for the pristine sample. The addition of G is found as one of the least effective C-source additions enhancing Jc. We discuss results as being strongly related to variation of the residual stress.

Proton transfer in liquid water confined inside graphene slabs.

The microscopic structure and dynamics of an excess proton in water constrained in narrow graphene slabs between 0.7 and 3.1 nm wide has been studied by means of a series of molecular dynamics simulations. Interaction of water and carbon with the proton species was modeled using a multistate empirical valence bond Hamiltonian model. The analysis of the effects of confinement on proton solvation structure and on its dynamical properties has been considered for varying densities. The system is organized in one interfacial and a bulk-like region, both of variable size. In the widest interplate separations, the lone proton shows a marked tendency to place itself in the bulk phase of the system, due to the repulsive interaction with the carbon atoms. However, as the system is compressed and the proton is forced to move to the vicinity of graphene walls it moves closer to the interface, producing a neat enhancement of the local structure. We found a marked slowdown of proton transfer when the separation of the two graphene plates is reduced. In the case of lowest distances between graphene plates (0.7 and 0.9 nm), only one or two water layers persist and the two-dimensional character of water structure becomes evident. By means of spectroscopical analysis, we observed the persistence of Zundel and Eigen structures in all cases, although at low interplate separations a signature frequency band around 2500 cm^{-1} suffers a blue shift and moves to characteristic values of asymmetric hydronium ion vibrations, indicating some unstability of the typical Zundel-Eigen moieties and their eventual conversion to a single hydronium species solvated by water.

Interrelationship of thermal and mechanical properties of poly(ethylene terephthalate)/poly(ethylene 2,6-naphthalate)/graphene nanocomposites

In the present work, attempts were made to investigate the thermal and mechanical properties of melt-processed poly(ethylene terephthalate) (PET)/poly(ethylene 2,6-naphthalate) (PEN) blends and its nanocomposites containing graphene by using differential scanning calorimetry and tensile test experimenting. The results showed that crystallinity, which depends on a blend ratio, completely disappeared in a composition of 50/50. By introducing graphene to PET, even in low concentrations, the crystallinity of samples increased, while the nanocomposite of PEN indicated reverse behavior, and the crystallinity was reduced by adding graphene. In the case of PET-rich (75/25) nanocomposite blends, by increasing the nano content in the blend, the crystallinity of the samples was enhanced. This behavior was attributed to the nucleating effect of graphene particles in the samples. From the results of mechanical experiments, it was found in PET-rich blends that by increasing the PEN/PET ratio, the modulus of samples decreased, whereas in the case of PEN-rich blends, a slight increment of modulus is seen as a result of the increment of the PEN/PET ratio. The two contradicting behaviors were attributed to the reduction of crystallinity of PET-rich blends by enhancement of PEN/PET ratio and the rigid structure of PEN chains in PEN-rich blends. Unlike the different modulus change of PET-rich and PEN-rich blends, the nanocomposites of these blends similarly indicated an increment of modulus and characteristics of rigid materials by increasing the nano content. Furthermore, the same behavior was detected in nanocomposites of each polymer (PET and PEN nanocomposites). The alteration from ductile to rigid conduction was related to the impedance in the role of graphene plates against the flexibility of polymer chains and high values of graphene modulus. J. VINYL ADDIT. TECHNOL., 2015. © 2015 Society of Plastics Engineers

Effects of graphene plates' adoption on the microstructure, mechanical properties, and in vivo biocompatibility of calcium silicate coating.

Calcium silicate (CS) ceramic is a good coating candidate for biomedical implants to improve biocompatibility and accelerate early osseointegration. However, the poor fracture toughness and wear resistance of this ceramic material restricts the long-term performance of implants. In this study, graphene plates (GPs) were used as reinforcement to improve the mechanical properties of CS coating. Composite coating containing 1.5 weight % GPs was prepared by vacuum plasma spraying technology. The good survival of the GPs in the composite coating was demonstrated by Raman analysis, although the defects of the GPs were increased after plasma spraying. Effects of the GPs’ adoption on the microstructure of the coating were studied by scanning electron microscopy and transmission electron microscopy. Results showed that the GPs were homogenously distributed in the CS grains interface or enwrapped on the particles, and exhibited good wetting behavior with the CS matrix. The wear properties of the composite coating were obviously enhanced by the reinforcement of GPs. The reinforcement mechanism was attributed to the enhanced micro-hardness and interfacial bonding of the particles in the coating. In vivo experiments demonstrated that the composite coating possessed similarly good biocompatibility compared to pure CS coating. The bone-implant contact ratio reached 84.3%±7.4% for GPs/CS coating and 79.6%±9.4% for CS coating after 3 months’ implantation.

Highly Hydrophobic, Compressible, and Magnetic Polystyrene/Fe3O4/Graphene Aerogel Composite for Oil–Water Separation

A solvothermal technique to process novel graphene aerogel/Fe3O4/polystyrene composites with reticulated graphene structure is described. Porous Fe3O4 nanoparticles as a partial substitute for ethylenediamine assisted cross-linking and interconnections between graphene plates. Fe3O4 and polystyrene incorporation allowed a porous substructure to be formed on the reticulated graphene surfaces, effectively enhancing the hydrophobicity. The compressibility and directional recovery were achieved with the composite having an extremely low density of 0.005 g cm–3, corresponding to a volume porosity of 99.7%. The crude oil intake capacity for the composite was 40 times its own mass after 10 water–oil separation cycles, which is among the highest ever reported for oil absorbents. Furthermore, the incorporation of porous Fe3O4 nanoparticles enabled magnetism which, in combination with compressibility, allowed the oil-soaked graphene composite to be readily collected by a magnet and oil to be squeezed out before the...

The mechanical characterization of stacked, multilayer graphene cantilevers and plates

ABSTRACTThe mechanical properties of stacked graphene sheets with varying number of layers are examined. The stacked sheets are assembled by manually combining single layer CVD-grown graphene monolayers, resulting in a turbostratic multilayer graphene with irregular layer spacings greater than crystalline graphite. Due to the presence of multiple layers, the material is analyzed as a plate rather than a membrane. Bending stiffness is determined via the deflection of micron-scale cantilevers, prepared using focused ion beam milling, while in-plane tensile stiffness is characterized through center-loading of edge-supported circular specimens. Computational modeling and established analytical solutions are used to extract material and structural property information, and benchmark measured properties relative to complementary results from indentation tests. Stacked, few-layer CVD-grown graphene retains an in-plane elastic modulus of 350N/m/layer (corresponding to 1.04 TPa for an inter-layer spacing of 0.335nm), suggesting good load-sharing between stacked layers. Width-normalized bending stiffness was unmeasurable for cantilevers of 1 and 3 layers, while cantilevers of 5 and 10 layers had values of 11,100nN·nm and 1.3×106nN·nm respectively.

Why is the electroanalytical performance of carbon paste electrodes involving an ionic liquid binder higher than paraffinic binders? A simulation investigation.

Recently, carbon paste electrodes (CPE) fabricated using an ionic liquid (IL) binder have shown enhanced electroanalytical performance over conventional paraffinic binders. Molecular dynamics (MD) simulations of graphite mixed with ionic liquid and with paraffin binder can unravel the potential atomistic factors responsible for such enhancement. Based on an experimentally optimized binder/graphite mass ratio, which has been reported to be crucial for such a performance, comprehensive simulations (at 323 K) are performed with the ensembles involving an ionic liquid binder (1-butyl-3-methylimidazolium hexafluorophosphate, [C4mim]PF6) and a paraffin binder (n-C20H42) mixed with graphite comprising large-size hexagonal-shaped double graphene plates. Structural analysis indicates both binders form only a monolayer on the graphite surface, covering the surface locally by IL but all-encompassing by paraffin. With charged and uncharged graphite, the IL monolayer tends to cover mainly the graphite center without approaching the edge planes. On the contrary, a monolayer of the paraffin binder covers uniformly the center, near the center, and the edge planes. Cations and anions of the IL form well-defined two dimensional pentagonal matrixes with characteristic high adsorption energy, almost 2.4 times higher than paraffin adsorption. The cation and anion coordination ability of the IL is responsible for such a local distribution. The simulation of these phenomena under experimental conditions unravels strong two-dimensional coordination properties inherent to the ionic liquid when distributed over the graphite surface. This direct MD simulation comparison of the IL properties with an organic liquid counterpart, made for the first time, can be used to explain the high electroanalytical performance (electron transfer) of CPEs involving an IL binder over paraffin binders.

A Scheme for Hydrogen Evolution from Natural Gas

We discuss one of the schemes of hydrogen evolution from a natural gas mixture. The scheme relies on the use of membranes formed by graphene plates containing calibrated pores in the crystalline structure. We provide the description scheme and the technology for calculating interaction between gas environment molecules and nanosized molecular structures. As an example, we consider mechanisms of hydrogen atoms penetration through defects in a graphene plate.

Thermophoresis of Graphene Plates

Thermophoresis of graphene plates in an air medium is discussed within the framework of a molecular-kinetic approach. Its rate is found to be independent of the plate area and the aspect ratio of a rectangular graphene. It does depend on the plate orientation in space, which is controlled by the principle of least resistance. The dependence is expressed via a geometrical parameter σ, whose limiting values within the variation interval are found to be 0.46 and 0.65. A solution of the Euler problem on the Brownian rotation of a plate around its center of mass as a result of collisions of molecules in the temperature gradient field allowed us to obtain for the graphene plates a statistical average of σ = 0.5. This value turned out to be the same as the one for spherical nanoparticles, for which rotations are irrelevant.

Shock responses of graphene reinforced composites via molecular dynamics simulations

Shock responses of graphene reinforced composites are investigated using molecular dynamics simulations. The first case studied is the response of spaced multilayer graphene plates under normal impact of a spherical projectile, focusing on the effect of the number of graphene monolayers per plate on the penetration resistance of the armor. The simulation results indicate that the penetration resistance increases with decreasing number of graphene monolayers per plate. The second case studied is the penetration resistance of laminated copper/graphene composites. The simulation results demonstrate that under normal impact by a spherical projectile the penetration resistance of copper can be improved significantly by laminating the copper plates with graphene. The results of this research have revealed the possibility that graphene might be used in hyper velocity-relevant armor systems to enhance their penetration resistance.

Graphene-reinforced calcium silicate coatings for load-bearing implants

Owing to the superior mechanical properties and low coefficient of thermal expansion, graphene has been widely used in the reinforcement of ceramics. In the present study, various ratios of graphene (0.5 wt%, 1.5 wt% and 4 wt%) were reinforced into calcium silicate (CS) coatings for load-bearing implant surface modification. Surface characteristics of the graphene/calcium silicate (GC) composite coatings were characterized by scanning electron microscopy. Results show that the graphene plates (less than 4 wt% in the coatings) were embedded in the CS matrix homogeneously. The surfaces of the coatings showed a hierarchical hybrid nano-/microstructure, which is believed to be beneficial to the behaviors of the cell and early bone fixation of the implants. Wear resistance measured by a pin-on-disc model exhibited an obvious enhancement with the adoption of graphene plates. The weight losses of the GC coatings decreased with the increase of graphene content. However, too high graphene content (4 wt% or more) made the composite coatings porous and the wear resistance decreased dramatically. The weight loss was only 1.3 ± 0.2 mg for the GC coating containing 1.5 wt% graphene (denoted as GC1.5) with a load of 10 N and sliding distance of 500 m, while that of the pure CS coating reached up to 28.6 ± 0.5 mg. In vitro cytocompatibility of the GC1.5 coating was evaluated using a human marrow stem cell (hMSC) culture system. The proliferation and alkaline phosphatase, osteopontin and osteocalcin (OC) osteogenesis-related gene expression of the cells on the GC1.5 coating did not deteriorate with the adoption of graphene. Conversely, even better adhesion of the hMSCs was observed on the GC1.5 coating than on the pure CS coating. All of the results indicate that the GC1.5 coating is a good candidate for load-bearing implants.

Surface Corrugation Effects on the Water–Graphene Interfacial and Confinement Behavior

We carried out a systematic molecular simulation study of the behavior of a pair of finite-size graphene plates immersed in water at isobaric–isothermal conditions to provide insights into the nature of the water–graphene (corrugated) surface interactions. The goal was to address the link between the corrugation-driven hydration free energy changes in the association process involving graphene plates and the resulting water–graphene interfacial tension, to interrogate the effect of the surface corrugation and confinement on the thermodynamic response functions and the dynamics of confined water and to put the observed behavior in the context of Wenzel’s modification of Young’s equation. We found that graphene confinement induces a significant increase in the isothermal compressibility and isobaric thermal expansivity as well as a pronounced slowdown of the dynamics of water over that of the corresponding bulk counterpart, whose magnitudes depend on the type of surface corrugation involved. Our simulation ...

The design of a Li-ion full cell battery using a nano silicon and nano multi-layer graphene composite anode

In this study, a Si–graphene composite, which is composed of nano Si particles and nano-sized multi-layer graphene particles, and micro-sized multi-layer graphene plate conductor, was used as the anode for Li-ion battery. The Si–graphene electrode showed the high capacity and stable cyclability at charge/discharge rate of C/2 in half cell tests. Nickel cobalt aluminum material (NCA) was used as a cathode in the full cell to evaluate the practicality of the new Si–graphene material. Although the Si–graphene anode has more capacity than the NCA cathode in this designed full cell, the Si–graphene anode had a greater effect on the full-cell performance due to its large initial irreversible capacity loss and continuous SEI formation during cycling. When fluoro-ethylene carbonate was added to the electrolyte, the cyclability of the full cell was much improved due to less SEI formation, which was confirmed by the decreases in the 1st irreversible capacity loss, overpotential for the 1st lithiation, and the resistance of the SEI.

Porous structures in stacked, crumpled and pillared graphene-based 3D materials

Graphene, an atomically thin material with the theoretical surface area of 2600m2g−1, has great potential in the fields of catalysis, separation, and gas storage if properly assembled into functional 3D materials at large scale. In ideal non-interacting ensembles of non-porous multilayer graphene plates, the surface area can be adequately estimated using the simple geometric law ∼2600 m2g−1/N, where N is the number of graphene sheets per plate. Some processing operations, however, lead to secondary plate–plate stacking, folding, crumpling or pillaring, which give rise to more complex structures. Here we show that bulk samples of multilayer graphene plates stack in an irregular fashion that preserves the 2600/N surface area and creates regular slot-like pores with sizes that are multiples of the unit plate thickness. In contrast, graphene oxide deposits into films with massive area loss (2600–40m2g−1) due to nearly perfect alignment and stacking during the drying process. Pillaring graphene oxide sheets by co-deposition of colloidal-phase particle-based spacers has the potential to partially restore the large monolayer surface. Surface areas as high as 1000m2g−1 are demonstrated here through colloidal-phase deposition of graphene oxide with water-dispersible aryl-sulfonated ultrafine carbon black as a pillaring agent.

Graphene in Ionic Liquids: Collective van der Waals Interaction and Hindrance of Self-Assembly Pathway

Over the past decade, there has been much controversy regarding the microscopic mechanism by which the π-electron-rich carbon nanomaterials such as graphene and carbon nanotubes can be dispersed in ionic liquids. Through a combination of a quantum mechanical calculation on the level of density functional theory, an extensive molecular dynamics study on the time scale of microseconds, and a kinetic analysis at the experimental time scale, we have demonstrated that collective van der Waals forces between ionic liquids and graphene are able to describe both the short-ranged cation-π interaction and the long-ranged dispersion interaction and this microscopic interaction drives two graphene plates trapped in their metastable state while two graphene plates easily self-assemble into graphite in water.

Graphene for improved femtosecond laser based pluripotent stem cell transfection

Pluripotent stem cells are hugely attractive in the tissue engineering research field as they can self-renew and be selectively differentiated into various cell types. For stem cell and tissue engineering research it is important to develop new, biocompatible scaffold materials and graphene has emerged as a promising material in this area as it does not compromise cell proliferation and accelerates specific cell differentiation. Previous studies have shown a non-invasive optical technique for mouse embryonic stem (mES) cell differentiation and transfection using femtosecond (fs) laser pulses. To investigate cellular responses to the influence of graphene and laser irradiation, here we present for the first time a study of mES cell fs laser transfection on graphene coated substrates. First we studied the impact of graphene on Chinese Hamster Ovary (CHO-K1) cell viability and cell cytotoxicity in the absence of laser exposure. These were tested via evaluating the mitochondrial activity through adenosine triphosphates (ATP) luminescence and breakages on the cell plasma membrane assessed using cytosolic lactate dehydrogenase (LDH) screening. Secondly, the effects of fs laser irradiation on cell viability and cytotoxicity at 1064 and 532 nm for cells plated and grown on graphene and pure glass were assessed. Finally, optical transfection of CHO-K1 and mES cells was performed on graphene coated versus plain glass substrates. Our results show graphene stimulated cell viability whilst triggering a mild release of intracellular LDH. We also observed that compared to pure glass substrates; laser irradiation at 1064 nm on graphene plates was less cytotoxic. Finally, in mES cells efficient optical transfection at 1064 (82%) and 532 (25%) nm was obtained due to the presence of a graphene support as compared to pristine glass. Here we hypothesize an up-regulation of cell adhesion promoting peptides or laminin-related receptors of the extracellular matrix (ECM) in cell samples grown and irradiated on graphene substrates. By bringing together advances in optics and nanomaterial sciences we demonstrate pathways for enhancement of pluripotent stem cell biology.

Concentration Effects of Carbon Oxides on Sensing by Graphene Nanoribbons: Ab Initio Modeling

We study detection of CO and CO2 gas molecules by change in quantum conductance of armchair graphene nanoribbons (AGNR) with a width of ∼1 nm. Quantum conductance modulations are calculated by using the second-order Møller–Plesset (MP2) method and density functional theory (DFT) for geometry optimization and a hybrid approach for electronic structure calculations. We determine stable and metastable physisorption orientations of gas molecules with varying concentrations. Our MP2-calculated binding energies relate 8.33% and 16.33% surface coverages of CO and CO2, respectively, to 1.72 × 104 and 497 ppm. With such concentrations, adsorption of molecules results in conductance characteristics shifts on the order of few meV. As the concentrations detected in experiments are much less, other mechanisms including substrate and/or carrier gas doping as well as adsorption on defects or electrodes may contribute toward gas sensing using graphene plates. We also discuss temperature effects and propose possible methods for improving gas detection by GNRs.

Parallel plate waveguide with anisotropic graphene plates: Effect of electric and magnetic biases

The performances of a parallel plate waveguide (PPWG) supported by perfect electric conductor (PEC)-graphene and graphene-graphene plates are evaluated. The graphene plate behavior is modeled as an anisotropic medium with both diagonal and Hall conductivities derived from Kubo formula. The PPWG modes supported by PEC-graphene and graphene-graphene plates are studied. Maxwell's equations are solved for these two waveguides, while the graphene layers are biased with an electric field only and with both electric and magnetic fields. It is shown that when both electric and magnetic biases are applied to the graphene, a hybrid mode (simultaneous transverse electric (TE) and transverse magnetic (TM) modes) will propagate inside the waveguide. The intensity of each TE and TM modes can be adjusted with the applied external bias fields. Study of different waveguides demonstrates that by decreasing the plate separation (d), the wave confinement improves. However, it increases the waveguide attenuation. A dielectric layer inserted between the plates can also be used to improve the wave confinement. The presented analytical procedure is applicable to other guiding structures having walls with isotropic or anisotropic conductivities.

Synergy among binary (MWNT, SLG) nano-carbons in polymer nano-composites: a Raman study

Load transfer and mechanical strength of reinforced polymers are fundamental to developing advanced composites. This paper demonstrates enhanced load transfer and mechanical strength due to synergistic effects in binary mixtures of nano-carbon/polymer composites. Different compositional mixtures (always 1 wt% total) of multi-wall carbon nanotubes (MWNTs) and single-layer graphene (SLG) were mixed in polydimethylsiloxane (PDMS), and effects on load transfer and mechanical strength were studied using Raman spectroscopy. Significant shifts in the G-bands were observed both in tension and compression for single as well as binary nano-carbon counterparts in polymer composites. Small amounts of MWNT0.1 dispersed in SLG0.9/PDMS samples (subscripts represent weight percentage) reversed the sign of the Raman wavenumbers from positive to negative values demonstrating reversal of lattice stress. A wavenumber change from 10 cm−1 in compression to 10 cm−1 in tension, and an increase in elastic modulus of ∼103% was observed for MWNT0.1SLG0.9/PDMS with applied uniaxial tension. Extensive scanning electron microscopy revealed the bridging of MWNT between two graphene plates in polymer composites. Mixing small amounts of MWNTs in SLG/PDMS eliminated the previously reported compressive deformation of SLG and significantly enhanced load transfer and mechanical strength of composites in tension. The orientation order of MWNT with application of uniaxial tensile strain directly affected the shift in Raman wavenumbers (2D-band and G-band) and load transfer. It is observed that the cooperative behavior of binary nano-carbons in polymer composites resulted in enhanced load transfer and mechanical strength. Such binary compositions could be fundamental to developing advanced composites such as nano-carbon based mixed dimensional systems.

Hypervelocity impact properties of graphene armor via molecular dynamics simulations

Hypervelocity impact properties of two different graphene armor systems are investigated using molecular dynamics simulations. One system is the so-called spaced armor which consists of a number of graphene plates spaced certain distance apart. Its response under normal impact of a spherical projectile is studied, focusing on the effect of the number of graphene monolayers per plate (denoted by n ) on the penetration resistance of the armor. We find that under normal impact by a spherical projectile the penetration resistance increases with decreasing number of monolayers per plate ( n ), and the best penetration resistance is achieved in the system with one graphene layer for each plate. Note that the monolayers in all the simulated multilayer graphene plates were AB-stacked. The second system being studied is the laminated copper/graphene composites with the graphene layers inside copper, on impact or back surface, or on both the impact and back surfaces. The simulation results show that under normal impact by a spherical projectile the laminated copper/graphene composite has much higher penetration resistance than the monolithic copper plate. The best efficiency is achieved when the graphene layers are on both the impact and back surfaces.