Excellent Performance of Few-Layer Borocarbonitrides as Anode Materials in Lithium-Ion Batteries

Borocarbonitrides (BxCyNz) with a graphene-like structure exhibit a remarkable high lithium cyclability and current rate capability. The electrochemical performance of the BxCyNz materials, synthesized by using a simple solid-state synthesis route based on urea, was strongly dependent on the composition and surface area. Among the three compositions studied, the carbon-rich compound B0.15C0.73N0.12 with the highest surface area showed an exceptional stability (over 100cycles) and rate capability over widely varying current density values (0.05-1Ag(-1)). B0.15C0.73N0.12 has a very high specific capacity of 710mAhg(-1) at 0.05Ag(-1). With the inclusion of a suitable additive in the electrolyte, the specific capacity improved drastically, recording an impressive value of nearly 900mAhg(-1) at 0.05Ag(-1). It is believed that the solid-electrolyte interphase (SEI) layer at the interface of BxCyNz and electrolyte also plays a crucial role in the performance of the BxCyNz .

Shock-boundary layer interaction and transonic flutter

The transonic flutter dip of an aeroelastic system is primarily caused by compressibility of the flowing fluid. Viscous effects are not dominant in the pre-transonic dip region. In fact, an Euler solver can predict this flutter boundary with considerable accuracy. However with an increase in Mach number the shock moves towards the trailing edge causing shock induced separation. This shock-boundary layer interaction changes the flutter boundary in the transonic and post-transonic dip region significantly. We discuss the effect of viscosity in changing the flutter boundary in the post-transonic dip region using a RANS solver coupled to a two-degree of freedom model of the structural dynamics of a wing.

Effect of chemical treatment on surface characteristics of sputter deposited Ti-rich NiTi shape memory alloy thin-films

NiTi thin-films were deposited by DC magnetron sputtering from single alloy target (Ni/Ti: 45/55 aL.%). The rate of deposition and thickness of sputter deposited films were maintained to similar to 35 nm min(-1) and 4 mu m respectively. A set of sputter deposited NiTi films were selected for specific chemical treatment with the solution comprising of de-ionized water, HF and HNO3 respectively. The influence of chemical treatment on surface characteristics of NiTi films before and after chemical treatment was investigated for their structure, micro-structure and composition using different analytical techniques. Prior to chemical treatment, the composition of NiTi films using energy dispersive X-ray dispersive spectroscopy (EDS), were found to be 51.8 atomic percent of Ti and 48.2 atomic percent of Ni. The structure and morphology of these films were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD investigations, demonstrated the presence of dominant Austenite (110) phase along with Martensite phase, for untreated NiTi films whereas some additional diffraction peaks viz. (100), (101), and (200) corresponding to Rutile and Anatase phase of Titanium dioxide (TiO2) along with parent Austenite (110) phase were observed for chemically treated NiTi films. FTIR studies, it can be concluded that chemically treated films have higher tendency to form metal oxide/hydroxide than the untreated NiTi films. XPS investigations, demonstrated the presence of Ni-free surface and formation of a protective metal oxide (TiO2) layer on the surface of the films, in both the cases. The extent of the formation of surface oxide layer onto the surface of NiTi films has enhanced after chemical treatment. (C) 2014 Elsevier B.V. All rights reserved.

Few-Layer Borocarbonitride Nanosheets: Platinum-Free Catalyst for the Oxygen Reduction Reaction

The present study demonstrates the use of few-layer borocarbonitride nanosheets synthesized by a simple method as non-platinum cathode catalysts for the oxygen reduction reaction (ORR) in alkaline medium. Composition-dependent ORR activity is observed and the best performance was found when the composition was carbon-rich. Mechanistic aspects reveal that ORR follows the 4e(-) pathway with kinetic parameters comparable to those of the commercial Pt/C catalyst. Excellent methanol tolerance is observed with the BCN nanosheets unlike with Pt/C.

Free turbulent shear layer in a point vortex gas as a problem in nonequilibrium statistical mechanics

This paper attempts to unravel any relations that may exist between turbulent shear flows and statistical mechanics through a detailed numerical investigation in the simplest case where both can be well defined. The flow considered for the purpose is the two-dimensional (2D) temporal free shear layer with a velocity difference Delta U across it, statistically homogeneous in the streamwise direction (x) and evolving from a plane vortex sheet in the direction normal to it (y) in a periodic-in-x domain L x +/-infinity. Extensive computer simulations of the flow are carried out through appropriate initial-value problems for a ``vortex gas'' comprising N point vortices of the same strength (gamma = L Delta U/N) and sign. Such a vortex gas is known to provide weak solutions of the Euler equation. More than ten different initial-condition classes are investigated using simulations involving up to 32 000 vortices, with ensemble averages evaluated over up to 10(3) realizations and integration over 10(4)L/Delta U. The temporal evolution of such a system is found to exhibit three distinct regimes. In Regime I the evolution is strongly influenced by the initial condition, sometimes lasting a significant fraction of L/Delta U. Regime III is a long-time domain-dependent evolution towards a statistically stationary state, via ``violent'' and ``slow'' relaxations P.-H. Chavanis, Physica A 391, 3657 (2012)], over flow time scales of order 10(2) and 10(4)L/Delta U, respectively (for N = 400). The final state involves a single structure that stochastically samples the domain, possibly constituting a ``relative equilibrium.'' The vortex distribution within the structure follows a nonisotropic truncated form of the Lundgren-Pointin (L-P) equilibrium distribution (with negatively high temperatures; L-P parameter lambda close to -1). The central finding is that, in the intermediate Regime II, the spreading rate of the layer is universal over the wide range of cases considered here. The value (in terms of momentum thickness) is 0.0166 +/- 0.0002 times Delta U. Regime II, extensively studied in the turbulent shear flow literature as a self-similar ``equilibrium'' state, is, however, a part of the rapid nonequilibrium evolution of the vortex-gas system, which we term ``explosive'' as it lasts less than one L/Delta U. Regime II also exhibits significant values of N-independent two-vortex correlations, indicating that current kinetic theories that neglect correlations or consider them as O(1/N) cannot describe this regime. The evolution of the layer thickness in present simulations in Regimes I and II agree with the experimental observations of spatially evolving (3D Navier-Stokes) shear layers. Further, the vorticity-stream-function relations in Regime III are close to those computed in 2D Navier-Stokes temporal shear layers J. Sommeria, C. Staquet, and R. Robert, J. Fluid Mech. 233, 661 (1991)]. These findings suggest the dominance of what may be called the Kelvin-Biot-Savart mechanism in determining the growth of the free shear layer through large-scale momentum and vorticity dispersal.

Defect-Induced Enhancement and Quenching Control of Photocurrent in Few-Layer Graphene Photodetectors

A novel approach is presented for achieving an enhanced photo-response in a few layer graphene (FLG) based photodetector that is realized by introducing defect sites in the FLG. Fabrication induced wrinkle formation in graphene presented a four-fold enhancement in the photocurrent when compared to unfold PLC. Interestingly, it was observed that the addition of few multiwalled carbon nanotubes to an FLG improves the photocurrent by two-fold along with a highly stable response as compared to FLG alone.

Shock tunnel experiments on control of shock induced large separation bubble using boundary layer bleed

Shock-Boundary Layer Interaction (SBLI) often occurs in supersonic/hypersonic flow fields. Especially when accompanied by separation (termed strong interaction), the SBLI phenomena largely affect the performance of the systems where they occur, such as scramjet intakes, thus often demanding the control of the interaction. Experiments on the strong interaction between impinging shock wave and boundary layer on a flat plate at Mach 5.96 are carried out in IISc hypersonic shock tunnel HST-2. The experiments are performed at moderate flow total enthalpy of 1.3 MJ/kg and freestream Reynolds number of 4 million/m. The strong shock generated by a wedge (or shock generator) of large angle 30.96 degrees to the freestream is made to impinge on the flat plate at 95 mm (inviscid estimate) from the leading edge, due to which a large separation bubble of length (75 mm) comparable to the distance of shock impingement from the leading edge is generated. The experimental simulation of such large separation bubble with separation occurring close to the leading edge, and its control using boundary layer bleed (suction and tangential blowing) at the location of separation, are demonstrated within the short test time of the shock tunnel (similar to 600 mu s) from time resolved schlieren flow visualizations and surface pressure measurements. By means of suction - with mass flow rate one order less than the mass flow defect in boundary layer - a reduction in separation length by 13.33% was observed. By the injection of an array of (nearly) tangential jets in the direction of mainstream (from the bottom of the plate) at the location of separation - with momentum flow rate one order less than the boundary layer momentum flow defect - 20% reduction in separation length was observed, although the flow field was apparently unsteady. (C) 2014 Elsevier Masson SAS. All rights reserved.

Effect of surfactants on the instability of a two-layer film flow down an inclined plane

The effect of insoluble surfactants on the instability of a two-layer film flow down an inclined plane is investigated based on the Orr-Sommerfeld boundary value problem. The study, focusing on Stokes flow P. Gao and X.-Y. Lu, ``Effect of surfactants on the inertialess instability of a two-layer film flow,'' J. Fluid Mech. 591, 495-507 (2007)], is further extended by including the inertial effect. The surface mode is recognized along with the interface mode. The initial growth rate corresponding to the interface mode accelerates at sufficiently long-wave regime in the presence of surface surfactant. However, the maximum growth rate corresponding to both interface and surface modes decelerates in the presence of surface surfactant when the upper layer is more viscous than the lower layer. On the other hand, when the upper layer is less viscous than the lower layer, a new interfacial instability develops due to the inertial effect and becomes weaker in the presence of interfacial surfactant. In the limit of negligible surface and interfacial tensions, respectively, two successive peaks of temporal growth rate appear in the long-wave and short-wave regimes when the interface mode is analyzed. However, in the case of the surface mode, only the long-wave peak appears. (C) 2014 AIP Publishing LLC.

Instabilities in a fluid overlying an inclined anisotropic and inhomogeneous porous layer

In this paper, linear stability analysis on a Newtonian fluid film flowing under the effect of gravity over an inclined porous medium saturated with the same fluid in isothermal condition is carried out. The focus is placed on the effect of the anisotropic and inhomogeneous variations in the permeability of the porous medium on the shear mode and surface mode instabilities. The fluid-porous system is modelled by a coupled two-dimensional Navier-Stokes/Darcy problem. The perturbation equations are solved numerically using the Chebyshev collocation method. Detailed stability characteristics as a function of the depth ratio (the ratio of the depth of the fluid layer to that of the porous layer), the anisotropic parameter (the ratio of the permeability in the direction of the basic flow to that in the direction transverse to the basic flow) and the inhomogeneity functions are presented.

Water Vapor Barrier Material by Covalent Self-Assembly for Organic Device Encapsulation

Development of barrier materials for organic device encapsulation is of key interest for the commercialization of organic electronics. In this work, we have fabricated barrier films with ultralow water vapor permeabilities by reactive layer-by-layer approach. Using this technique, alternative layers of polyethylene imine and stearic acid were covalently bonded on a Surlyn film. The roughness, transparency and thickness of the films were determined by atomic force microscopy, UV-visible spectroscopy and scanning electron microscopy, respectively. Water vapor transmission rates through these films and the ability of these films to protect the organic photovoltaic devices was investigated. The films with covalently assembled bilayers exhibited lower water vapor transmission rates and maintained higher organic photovoltaic device efficiencies compared to the neat Surlyn film.

How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as lm-n-lm], 2Br(-) (n = 2, 5, 6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units -(CH2)(n)-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units -(CH2)(n)-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. (C) 2014 Elsevier Inc. All rights reserved.

Hydrodynamic instability and shear layer effect on the response of an acoustically excited laminar premixed flame

Combustion instabilities can cause serious problems which limit the operating envelope of low-emission lean premixed combustion systems. Predicting the onset of combustion instability requires a description of the unsteady heat release driving the instability, i.e., the heat release response transfer function of the system. This study focuses on the analysis of fully coupled two-way interactions between a disturbance field and a laminar premixed flame that incorporates gas expansion effects by solving the conservation equations of a compressible fluid. Results of the minimum and maximum flame front deflections are presented to underline the impact of the hydrodynamic instability on the flame and the shear layer effect on the initial flame front wrinkling which is increased at decreasing gas expansion. These phenomena influence the magnitude of the burning area and burning area rate response of the flame at lower frequency excitation more drastically than reduced-order model (ROM) predictions even for low temperature ratios. It is shown that the general trend of the flame response magnitudes can be well captured at higher frequency excitation, where stretch effects are dominant. The phase response is influenced by the DL mechanism, which cannot be captured by the ROM, and by the resulting discrepancy in the flame pocket formation and annihilation process at the flame tip. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved,

How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as Im-n-Im], 2Br(-) (n = 2, 5,6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units -(CH2)(n)-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units (CH2)(n)-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. (C) 2014 Elsevier Inc. All rights reserved.

Pressure-Dependent Optical and Vibrational Properties of Mono layer Molybdenum Disulfide

Controlling the band gap by tuning the lattice structure through pressure engineering is a relatively new route for tailoring the optoelectronic properties of two-dimensional (2D) materials. Here, we investigate the electronic structure and lattice vibrational dynamics of the distorted monolayer 1T-MoS2 (1T') and the monolayer 2H-MoS2 via a diamond anvil cell (DAC) and density functional theory (DFT) calculations. The direct optical band gap of the monolayer 2H-MoS2 increases by 11.7% from 1.85 to 2.08 eV, which is the highest reported for a 2D transition metal dichalcogenide (TMD) material. DFT calculations reveal a subsequent decrease in the band gap with eventual metallization of the monolayer 2H-MoS2, an overall complex structureproperty relation due to the rich band structure of MoS2. Remarkably, the metastable 1T'-MoS2 metallic state remains invariant with pressure, with the J(2), A(1g), and E(2)g modes becoming dominant at high pressures. This substantial reversible tunability of the electronic and vibrational properties of the MoS2 family can be extended to other 2D TMDs. These results present an important advance toward controlling the band structure and optoelectronic properties of monolayer MoS2 via pressure, which has vital implications for enhanced device applications.

Space-Time Coded Spatial Modulated Physical Layer Network Coding for Two-Way Relaying

Using the spatial modulation approach, where only one transmit antenna is active at a time, we propose two transmission schemes for two-way relay channel using physical layer network coding with space time coding using coordinate interleaved orthogonal designs (CIODs). It is shown that using two uncorrelated transmit antennas at the nodes, but using only one RF transmit chain and space-time coding across these antennas can give a better performance without using any extra resources and without increasing the hardware implementation cost and complexity. In the first transmission scheme, two antennas are used only at the relay, adaptive network coding (ANC) is employed at the relay and the relay transmits a CIOD space time block code (STBC). This gives a better performance compared to an existing ANC scheme for two-way relay channel which uses one antenna each at all the three nodes. It is shown that for this scheme at high SNR the average end-to-end symbol error probability (SEP) is upper bounded by twice the SEP of a point-to-point fading channel. In the second transmission scheme, two transmit antennas are used at all the three nodes, CIOD STBCs are transmitted in multiple access and broadcast phases. This scheme provides a diversity order of two for the average end-to-end SEP with an increased decoding complexity of O(M-3) for an arbitrary signal set and O(M-2 root M) for square QAM signal set. Simulation results show that the proposed schemes performs better than the existing ANC schemes under perfect and imperfect channel state information.