We uncover the interlayer shear mode of multi-layer graphene samples, ranging from bilayergraphene (BLG) to bulk graphite, and show that the corresponding Raman peak measures the interlayer coupling. This peak scales from∼43cm −1 in bulk graphite to∼31cm −1 in BLG. Its low energy makes it a probe of near-Dirac point quasi-particles, with a Breit-Wigner-Fano lineshape due to resonance with electronic transitions. Similar shear modes are expected in all layered materials, providing a direct probe of interlayer interactions.Single Layer Graphene (SLG) has high mobility and optical transparency, in addition to flexibility, robustness and environmental stability [1,2]. As the knowledge of the basic properties of SLG increases, an ever growing effort is being devoted to a deeper understanding of Few Layer Graphene (FLG) samples [3][4][5], and to their application in useful devices. For example, since SLG absorbs 2.3% of the incident light [6], FLG can be used to beat the transmittance of Indium Tin Oxide(∼90%) [2], and to engineer near-market transparent conductors [7], exploiting the lower sheet resistance afforded by combining more than one SLG [2,7]. Bilayer graphene (BLG) is a tunable band gap semiconductor [8], tri-layer graphene (TLG) has a unique electronic structure consisting, in the simplest approximation, of massless SLG and massive BLG subbands [9][10][11]. FLG with less than 10 layers do each show a distinctive band structure [11]. The layers can be stacked as in graphite, or have any orientation. This gives rise to a wealth of electronic properties, such as the appearance of a Dirac spectrum even in FLG [12].There is thus an increasing interest in the physics and applications of FLG. Optical microscopy can count the number of layers [13,14], but does not offer the insights of Raman spectroscopy, being this sensitive to quasiparticle interactions [15]. Raman spectroscopy is one of the most useful and versatile tools to probe graphene samples [15,16]. The measurement of the SLG, BLG, and FLG Raman spectra[15] triggered a huge effort to understand phonons, electron-phonon, magneto-phonon and electron-electron interactions, and the influence on the Raman process of number and orientation of layers, electric or magnetic fields, strain, doping, disorder, edges, and functional groups [16].The SLG phonon dispersions comprise three acoustic and three optical branches. A necessary, but not sufficient, condition for a phonon mode to be Raman active is to satisfy the Raman fundamental selection rule, i.e. to be at the Brillouin Zone centre, Γ, with wavevector q ≈ 0 [17]. SLG has six normal modes at Γ: [18]. There are two degenerate in-plane optical modes, E 2g , and one out-of-plane optical mode B 2g [18]. E 2g modes are Raman active, while B 2g is neither Raman nor IR active [18]. In the case of graphite there are 4 atoms per unit cell, and only half of them have fourth neighbors that either lie directly above or below in adjacent layers. Therefore the two atoms of the unit cell in each layer are now inequivalent. ...

Nanolaminated materials are important because of their exceptional properties and wide range of applications. Here, we demonstrate a general approach to synthesize a series of Zn-based MAX phases and Cl-terminated MXenes originating from the replacement reaction between the MAX phase and the late transition metal halides. The approach is a top-down route that enables the late transitional element atom (Zn in the present case) to occupy the A site in the pre-existing MAX phase structure. Using this replacement reaction between Zn element from molten ZnCl2 and Al element in MAX phase precursors (Ti3AlC2, Ti2AlC, Ti2AlN, and V2AlC), novel MAX phases Ti3ZnC2, Ti2ZnC, Ti2ZnN, and V2ZnC were synthesized. When employing excess ZnCl2, Cl terminated MXenes (such as Ti3C2Cl2 and Ti2CCl2) were derived by a subsequent exfoliation of Ti3ZnC2 and Ti2ZnC due to the strong Lewis acidity of molten ZnCl2. These results indicate that A-site element replacement in traditional MAX phases by late transition metal halides opens the door to explore MAX phases that are not thermodynamically stable at high temperature and would be difficult to synthesize through the commonly employed powder metallurgy approach.In addition, this is the first time that exclusively Cl-terminated MXenes were obtained, and the etching effect of Lewis acid in molten salts provides a green and viable route to prepare MXenes through an HF-free chemical approach.

The application of titanium (Ti) based biomedical materials which are widely used at present, such as commercially pure titanium (CP-Ti) and Ti-6Al-4V, are limited by the mismatch of Young's modulus between the implant and the bones, the high costs of products, and the difficulty of producing complex shapes of materials by conventional methods. Niobium (Nb) is a non-toxic element with strong β stabilizing effect in Ti alloys, which makes Ti-Nb based alloys attractive for implant application. Metal injection molding (MIM) is a cost-efficient near-net shape process. Thus, it attracts growing interest for the processing of Ti and Ti alloys as biomaterial. In this investigation, metal injection molding was applied to the fabrication of a series of Ti-Nb binary alloys with niobium content ranging from 10wt% to 22wt%, and CP-Ti for comparison. Specimens were characterized by melt extraction, optical microscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and transmission electron microscopy (TEM). Titanium carbide formation was observed in all the as-sintered Ti-Nb binary alloys but not in the as-sintered CP-Ti. Selected area electron diffraction (SAED) patterns revealed that the carbides are Ti2C. It was found that with increasing niobium content from 0% to 22%, the porosity increased from about 1.6% to 5.8%, and the carbide area fraction increased from 0% to about 1.8% in the as-sintered samples. The effects of niobium content, porosity and titanium carbides on mechanical properties have been discussed. The as-sintered Ti-Nb specimens exhibited an excellent combination of high tensile strength and low Young's modulus, but relatively low ductility.

Nanostructures in silicon (Si) induced by phase transformations have been investigated during the past 50 years. Performances of nanostructures are improved compared to that of bulk counterparts. Nevertheless, the confinement and loading conditions are insufficient to machine and fabricate high-performance devices. As a consequence, nanostructures fabricated by nanoscale deformation at loading speeds of m/s have not been demonstrated yet. In this study, grinding or scratching at a speed of 40.2 m/s was performed on a custom-made setup by an especially designed diamond tip (calculated stress under the diamond tip in the order of 5.11 GPa). This leads to a novel approach for the fabrication of nanostructures by nanoscale deformation at loading speeds of m/s. A new deformation-induced nanostructure was observed by transmission electron microscopy (TEM), consisting of an amorphous phase, a new tetragonal phase, slip bands, twinning superlattices, and a single crystal. The formation mechanism of the new phase was elucidated by ab initio simulations at shear stress of about 2.16 GPa. This approach opens a new route for the fabrication of nanostructures by nanoscale deformation at speeds of m/s. Our findings provide new insights for potential applications in transistors, integrated circuits, diodes, solar cells, and energy storage systems.

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The Li−Co−O and Li−Ni−O systems, used as cathodes in lithium ion batteries, have been investigated by means of ab initio calculations and empirical methods. An approach based on ab initio calculations to obtain accurate enthalpies of formation for transition metal oxides is proposed. With the obtained enthalpies of formation and the empirical entropy data, the Gibbs energy functions of the binary and ternary oxides in the Li−Co−O and Li−Ni−O systems are determined. To prove the accuracy of this thermodynamic model, we calculate the cell voltages of lithium ion batteries. Compared to the previously calculated results, which underestimate the cell voltages of lithium ion batteries, our calculations are in good agreement with the experimental data. The present theoretical approaches are reliable to evaluate the thermodynamic and electrochemical properties of lithium-containing transition metal oxides. KEYWORDS: Li−Co−O system, Li−Ni−O system, ab initio, enthalpy of formation, metal oxides, cell voltage ■ INTRODUCTION Li−M−O (M = transition metal) phases are widely applied as cathodes in lithium ion batteries. Knowledge of thermodynamic properties of Li−M−O (M = transition metal) phases is fundamental to study the stability and capacity of lithium ion batteries. The Gibbs energy functions of these phases are essential to predict the cell voltages and study the electrochemical properties of lithium ion batteries. Thus, it is our aim to establish a thermodynamic database for multicomponent Licontaining oxide systems by the calculation of phase diagrams (CALPHAD) approach.Usually, the CALPHAD approach needs reliable experimentally thermodynamic data as input parameters to be optimized. When experimental information is scarce or completely lacking, it is necessary to estimate the thermodynamic data by ab initio calculations or empirical methods. It has been demonstrated that ab initio calculations provide a successful way of predicting the thermodynamic data, not only for metallic compounds, 1−3 but also for metal carbides. 4,5 However, extensive work by the Ceder Group shows that the pure density functional theory (DFT) method cannot directly be used to obtain accurate enthalpies of formation for metal oxides. 6,7 Also, their calculations on electrochemistry underestimate the cell voltages of lithium ion batteries. 8−12 To better understand the thermodynamic properties of metal oxides, Wang et al. 6 introduced a certain correction for the O 2 molecule and applied the DFT+U method. 13 However, it is not a universal method because the U value for a certain transition metal is unfixed. 6,14−18 For instance, when performing ab initio calculations on the thermodynamic property, phase diagram and electrochemical property of the Li−Co−O system, three different U values are determined for Co in their work. 6,14,16 Thus, if an inappropriate U value is set, inaccurate results will limit us to study the properties of cathodes in lithium ion batteries.The purpose of the present work is to (1) provide an appropriate approach to ac...

Friction and wear remain the primary modes for energy dissipation in moving mechanical components. Superlubricity is highly desirable for energy saving and environmental benefits. Macroscale superlubricity was previously performed under special environments or on curved nanoscale surfaces. Nevertheless, macroscale superlubricity has not yet been demonstrated under ambient conditions on macroscale surfaces, except in humid air produced by purging water vapor into a tribometer chamber. In this study, a tribological system is fabricated using a graphene‐coated plate (GCP), graphene‐coated microsphere (GCS), and graphene‐coated ball (GCB). The friction coefficient of 0.006 is achieved in air under 35 mN at a sliding speed of 0.2 mm s−1 for 1200 s in the developed GCB/GCS/GCP system. To the best of the knowledge, for the first time, macroscale superlubricity on macroscale surfaces under ambient conditions is reported. The mechanism of macroscale superlubricity is due to the combination of exfoliated graphene flakes and the swinging and sliding of the GCS, which is demonstrated by the experimental measurements, ab initio, and molecular dynamics simulations. These findings help to bridge macroscale superlubricity to real world applications, potentially dramatically contributing to energy savings and reducing the emission of carbon dioxide to the environment.

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