Active guests in the MoS2/MoSe2 host lattice: efficient hydrogen evolution using few-layer alloys of MoS2(1-x)Se2x

Few-layer transition metal dichalcogenide alloys based on molybdenum sulphoselenides MoS2(1-x)Se2x] possess higher hydrogen evolution (HER) activity compared to pristine few-layer MoS2 and MoSe2. Variation of the sulphur or selenium content in the parent dichalcogenides reveals a systematic structure-activity relationship for different compositions of alloys, and it is found that the composition MoS1.0Se1.0 shows the highest HER activity amongst the catalysts studied. The tunable electronic structure of MoS2/MoSe2 upon Se/S incorporation probably assists in the realization of high HER activity.

Optimal Binary Power Control for Underlay CR With Different Interference Constraints and Impact of Channel Estimation Errors

Adapting the power of secondary users (SUs) while adhering to constraints on the interference caused to primary receivers (PRxs) is a critical issue in underlay cognitive radio (CR). This adaptation is driven by the interference and transmit power constraints imposed on the secondary transmitter (STx). Its performance also depends on the quality of channel state information (CSI) available at the STx of the links from the STx to the secondary receiver and to the PRxs. For a system in which an STx is subject to an average interference constraint or an interference outage probability constraint at each of the PRxs, we derive novel symbol error probability (SEP)-optimal, practically motivated binary transmit power control policies. As a reference, we also present the corresponding SEP-optimal continuous transmit power control policies for one PRx. We then analyze the robustness of the optimal policies when the STx knows noisy channel estimates of the links between the SU and the PRxs. Altogether, our work develops a holistic understanding of the critical role played by different transmit and interference constraints in driving power control in underlay CR and the impact of CSI on its performance.

Effect of epitaxial strain on phase separation in thin films

In epitaxially grown alloy thin films, spinodal decomposition may be promoted or suppressed depending on the sign of the epitaxial strain. We study this asymmetry by extending Cahn's linear theory of spinodal decomposition to systems with a composition dependent lattice parameter and modulus (represented by Vegard's law coefficients, GRAPHICS] and y, respectively), and an imposed (epitaxial) strain (e). We show analytically (and confirm using simulations) that the asymmetric effect of epitaxial strains arises only in elastically inhomogeneous systems. Specifically, we find good agreement between analytical and simulation results for the wave number GRAPHICS] of the fastest growing composition fluctuation. The asymmetric effect due to epitaxial strain also extends to microstructure formation: our simulations show islands of elastically softer (harder) phase with (without) a favourable imposed strain. We discuss the implications of these results to GeSi thin films on Si and Ge substrates, as well as InGaAs films on GaAs substrates.

Structural, magnetic and electrochemical investigation of novel binary Na2-x(Fe1-yMny)P2O7 (0 <= y <= 1) pyrophosphate compounds for rechargeable sodium-ion batteries

Pyrophosphate cathodes have been recently reported as a competent family of insertion compounds for sodium-ion batteries. In the current study, we have investigated the binary Na2 - x(Fe1 - yMny)P2O7 (0 <= y <= 1) pyrophosphate family, synthesized by the classical solid-state method. They form a continuous solid solution maintaining triclinic P-1 (#2) symmetry. The local structural coordination differs mainly by different degrees of Na site occupancy and preferential occupation of the Fe2 site by Mn. The structural and magnetic properties of these mixed-metal pyrophosphate phases have been studied. In each case, complete Fe3+/Fe2+ redox activity has been obtained centered at 3 V vs. Na. The Fe3+/Fe2+ redox process involves multiple steps between 2.5 and 3 V owing to Na-cation ordering during electrochemical cycling, which merge to form a broad single Fe3+/Fe2+ redox peak upon progressive Mn-doping. (C) 2014 Elsevier B.V. All rights reserved.

An insight to the low temperature conduction mechanism of c-axis grown Al-doped ZnO, a widely used transparent conducting oxide

Al-doped ZnO thin films were synthesized from oxygen reactive co-sputtering of Al and Zn targets. Explicit doping of Al in the highly c-axis oriented crystalline films of ZnO was manifested in terms of structural optical and electrical properties. Electrical conduction with different extent of Al doping into the crystal lattice of ZnO (AZnO) were characterized by frequency dependent (40 Hz-50 MHz) resistance. From the frequency dependent resistance, the ac conduction of them, and correlations of localized charge particles in the crystalline films were studied. The dc conduction at the low frequency region was found to increase from 8.623 mu A to 1.14 mA for the samples AZnO1 (1 wt% Al) and AZnO2 (2 wt% Al), respectively. For the sample AZnO10 (10 wt% Al) low frequency dc conduction was not found due to the electrode polarization effect. The measure of the correlation length by inverse of threshold frequency (omega(0)) showed that on application of a dc electric field such length decreases and the decrease in correlation parameter(s) indicates that the correlation between potentials wells of charge particles decreases for the unidirectional nature of dc bias. The comparison between the correlation length and the extent of correlation in the doped ZnO could not be made due to the observation of several threshold frequencies at the extent of higher doping. Such threshold frequencies were explained by the population possibility of correlated charge carriers that responded at different frequencies. For AZnO2 (2% Al), the temperature dependent (from 4.5 to 288 K) resistance study showed that the variable range hopping mechanism was the most dominating conduction mechanism at higher temperature whereas at low temperature region it was influenced by the small polaronic hopping conduction mechanism. There was no significant influence found in these mechanisms on applications of 1, 2 and 3 V as biases.

A robust layer adapted difference method for singularly perturbed two-parameter parabolic problems

A finite difference method for a time-dependent singularly perturbed convection-diffusion-reaction problem involving two small parameters in one space dimension is considered. We use the classical implicit Euler method for time discretization and upwind scheme on the Shishkin-Bakhvalov mesh for spatial discretization. The method is analysed for convergence and is shown to be uniform with respect to both the perturbation parameters. The use of the Shishkin-Bakhvalov mesh gives first-order convergence unlike the Shishkin mesh where convergence is deteriorated due to the presence of a logarithmic factor. Numerical results are presented to validate the theoretical estimates obtained.

Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition

We explore the potential energy landscape of structure breaking binary mixtures (SBBM) where two constituents dislike each other, yet remain macroscopically homogeneous at intermediate to high temperatures. Interestingly, we find that the origin of strong composition dependent non-ideal behaviour lies in its phase separated inherent structure. The inherent structure (IS) of SBBM exhibits bi-continuous phase as is usually formed during spinodal decomposition. We draw analogy of this correlation between non-ideality and phase separation in IS to explain observation of non-ideality in real aqueous mixtures of small amphiphilic solutes, containing both hydrophilic and hydrophobic groups. Although we have not been able to obtain IS of these liquids, we find that even at room temperature these liquids sustain formation of fluctuating, transient bi-continuous phase, with limited lifetime (tau less than or similar to 20 ps). While in the model (A, B) binary mixture, the non-ideal composition dependence can be considered as a fluctuation from a phase separated state, a similar scenario is expected to be responsible for the unusually strong non-ideality in these aqueous binary mixtures.

Effect of Ni-Zr codoping on dielectric and magnetic properties of SrFe12O19 via sol-gel route

Nanocrystalline strontium hexaferrites SrFe12-2x (Ni2+-Zr4+)(x)O-19] nanoparticles were successfully synthesized by sal gel process. For densification the powders were sintered at 950 degrees C/4 h. The sintered samples were characterized by X-ray diffraction (XRD), surface area measurement, and field emission scanning electron microscope (FESEM). The lattice parameter a is almost constant but c increased with x upto 0.8 and then decreased. The frequency dependent complex permittivity (epsilon and epsilon `' and permeability (mu' and mu `') and magnetic properties such as saturation magnetization (M-s), coercive field (H-c) were studied. If is observed that saturation magnetization increased gradually from 57.82 emuig to 67.2 emufg as x increased from 0.2 to 0.4 and then decreased from 672 emufg to 31.63 ernufg for x=1.0. In present study, x=0.4 shows high value of M-s 67.2 emu/g. The real part of permittivity (epsilon') remains constant upto a frequency 1 GHz and increases further with an increase of frequency, a resonance and anti resonance peak was observed above 1 GHz for all the samples. In real part of permeability (mu') the relaxation frequency is observed above 1 GHz for all the samples and it is attributed to the domain wall motion. It is well known that the permeability for polycrystalline ferrites can be described as the superposition of two different magnetizing mechanisms: spin rotation and domain wall motion. These low coercive strontium hexaferrites are suitable for magnetic recording applications in hard disks, floppy disks, video tapes, etc. (C) 2015 Elsevier B.V. All rights reserved.

Bayesian parameter identification in dynamic state space models using modified measurement equations

When Markov chain Monte Carlo (MCMC) samplers are used in problems of system parameter identification, one would face computational difficulties in dealing with large amount of measurement data and (or) low levels of measurement noise. Such exigencies are likely to occur in problems of parameter identification in dynamical systems when amount of vibratory measurement data and number of parameters to be identified could be large. In such cases, the posterior probability density function of the system parameters tends to have regions of narrow supports and a finite length MCMC chain is unlikely to cover pertinent regions. The present study proposes strategies based on modification of measurement equations and subsequent corrections, to alleviate this difficulty. This involves artificial enhancement of measurement noise, assimilation of transformed packets of measurements, and a global iteration strategy to improve the choice of prior models. Illustrative examples cover laboratory studies on a time variant dynamical system and a bending-torsion coupled, geometrically non-linear building frame under earthquake support motions. (C) 2015 Elsevier Ltd. All rights reserved.

Model and parameter uncertainty in IDF relationships under climate change

Quantifying distributional behavior of extreme events is crucial in hydrologic designs. Intensity Duration Frequency (IDF) relationships are used extensively in engineering especially in urban hydrology, to obtain return level of extreme rainfall event for a specified return period and duration. Major sources of uncertainty in the IDF relationships are due to insufficient quantity and quality of data leading to parameter uncertainty due to the distribution fitted to the data and uncertainty as a result of using multiple GCMs. It is important to study these uncertainties and propagate them to future for accurate assessment of return levels for future. The objective of this study is to quantify the uncertainties arising from parameters of the distribution fitted to data and the multiple GCM models using Bayesian approach. Posterior distribution of parameters is obtained from Bayes rule and the parameters are transformed to obtain return levels for a specified return period. Markov Chain Monte Carlo (MCMC) method using Metropolis Hastings algorithm is used to obtain the posterior distribution of parameters. Twenty six CMIP5 GCMs along with four RCP scenarios are considered for studying the effects of climate change and to obtain projected IDF relationships for the case study of Bangalore city in India. GCM uncertainty due to the use of multiple GCMs is treated using Reliability Ensemble Averaging (REA) technique along with the parameter uncertainty. Scale invariance theory is employed for obtaining short duration return levels from daily data. It is observed that the uncertainty in short duration rainfall return levels is high when compared to the longer durations. Further it is observed that parameter uncertainty is large compared to the model uncertainty. (C) 2015 Elsevier Ltd. All rights reserved.

Third post-Newtonian gravitational waveforms for compact binary systems in general orbits: Instantaneous terms

We compute the instantaneous contributions to the spherical harmonic modes of gravitational waveforms from compact binary systems in general orbits up to the third post-Newtonian (PN) order. We further extend these results for compact binaries in quasielliptical orbits using the 3PN quasi-Keplerian representation of the conserved dynamics of compact binaries in eccentric orbits. Using the multipolar post-Minkowskian formalism, starting from the different mass and current-type multipole moments, we compute the spin-weighted spherical harmonic decomposition of the instantaneous part of the gravitational waveform. These are terms which are functions of the retarded time and do not depend on the history of the binary evolution. Together with the hereditary part, which depends on the binary's dynamical history, these waveforms form the basis for construction of accurate templates for the detection of gravitational wave signals from binaries moving in quasielliptical orbits.

A pseudo-binary interdiffusion study in the beta-Ni(Pt)Al phase

Interdiffusion study is conducted in the Ni-rich part of the beta-Ni(Pt)Al phase following the pseudo-binary approach. Interdiffusion coefficients over the whole composition range considered in this study increases with increase in Pt content, which is in line with the theoretical study predicting the decrease in vacancy formation and migration energy because of Pt addition. The trend of change in diffusion coefficient with the increase in Ni and Pt contents indicates that Pt preferably replaces Ni antisites.

Estimation of intrinsic diffusion coefficients in a pseudo-binary diffusion couple

Major drawback of studying diffusion in multi-component systems is the lack of suitable techniques to estimate the diffusion parameters. In this study, a generalized treatment to determine the intrinsic diffusion coefficients in multi-component systems is developed utilizing the concept of a pseudo-binary approach. This is explained with the help of experimentally developed diffusion profiles in the Cu(Sn, Ga) and Cu(Sn, Si) solid solutions. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Spatial modulation of the composition of a binary liquid near a repulsive wall

When a binary liquid is confined by a strongly repulsive wall, the local density is depleted near the wall and an interface similar to that between the liquid and its vapor is formed. This analogy suggests that the composition of the binary liquid near this interface should exhibit spatial modulation similar to that near a liquid-vapor interface even if the interactions of the wall with the two components of the liquid are the same. The Guggenheim adsorption relation quantifies the concentrations of two components of a binary mixture near a liquid-vapor interface and qualitatively states that the majority (minority) component enriches the interface for negative (positive) mixing energy if the surface tensions of the two components are not very different. From molecular dynamics simulations of binary mixtures with different compositions and interactions we find that the Guggenheim relation is qualitatively satisfied at wall-induced interfaces for systems with negative mixing energy at all state points considered. For systems with positive mixing energy, this relation is found to be qualitatively valid at low densities, while it is violated at state points with high density where correlations in the liquid are strong. This observation is validated by a calculation of the density profiles of the two components of the mixture using density functional theory with the Ramakrishnan-Yussouff free-energy functional. Possible reasons for the violation of the Guggenheim relation are discussed.

Effect of Manganese (II) Oxide on microstructure and ionic transport properties of nanostructured cubic zirconia

Effect of MnO addition on microstructure and ionic transport properties of nanocrystalline cubic(c)-ZrO2 is reported. Monoclinic (m) ZrO2 powders with 10-30 mol% MnO powder are mechanically alloyed in a planetary ball mill at room temperature for 10 h and annealed at 550 degrees C for 6 h. In all compositions m-ZrO2 transforms completely to nanocrystalline c-ZrO2 phase and MnO is fully incorporated into c-ZrO2 lattice. Rietveld's refinement technique is employed for detailed microstructure analysis by analyzing XRD patterns. High resolution transmission electron microscopy (HRTEM) analysis confirms the complete formation of c-ZrO2 phase. Presence of stoichiometric Mn in c-ZrO2 powder is confirmed by Electron Probe Microscopy analysis. XPS analysis reveals that Mn is mostly in Mn2+ oxidation state. A correlation between lattice parameter and oxygen vacancy is established. A detailed ionic conductivity measurement in the 250 degrees-575 degrees C temperature range describes the effect of MnO on conductivity of c-ZrO2. The ionic conductivity (s) of 30 mol% MnO alloyed ZrO2 at 550 degrees C is 0.04 s cm(-1). Electrical relaxation studies are carried out by impedance and modulus spectroscopy. Relaxation frequency is found to increase with temperature and MnO mol fraction. Electrical characterization predicts that these compounds have potentials for use as solid oxide fuel cell electrolyte material. (C) 2015 Elsevier Ltd. All rights reserved.