Gd1.96-xYxEu0.04O3 (x=0.0, 0.49, 0.98, 1.47, 1.96 mol%) nanophosphors: Propellant combustion synthesis, structural and luminescence studies

Gd1.96-xYxEu0.04O3 (x = 0.0, 0.49, 0.98, 1.47, 1.96 mol%) nanophosphors were synthesized by propellant combustion method at low temperature (400 degrees C). The powder X-ray diffraction patterns of as formed Gd1.96Eu0.04O3 showed monoclinic phase, however with the addition of yttria it transforms from monoclinic to pure cubic phase. The porous nature increases with increase of yttria content. The particle size was estimated from Scherrer's and W-H plots which was found to be in the range 30-40 nm. These results were in well agreement with transmission electron microscopy studies. The optical band gap energies estimated were found to be in the range 5.32-5.49 eV. PL emission was recorded under 305 nm excitation show an intense emission peak at 611 nm along with other emission peaks at 582, 641 nm. These emission peaks were attributed to the transition of D-5(0) —> F-7(J) (J = 0, 1, 2, 3) of Eu3+ ions. It was observed that PL intensity increases with increase of Y content up to x = 0.98 and thereafter intensity decreases. CIE color co-ordinates indicates that at x = 1.47 an intense red bright color can be achieved, which could find a promising application in flat panel displays. The cubic and monoclinic phases show different thermoluminescence glow peak values measured under identical conditions. The response of the cubic phase to the applied dose showed good linearity, negligible fading, and simple glow curve structure than monoclinic phase indicating that suitability of this phosphor in dosimetric applications. (C) 2014 Elsevier B.V. All rights reserved.

Approaches toward (eta(2)-HX) (X = H, SiR (R = Me-3 or Me2Ph), CH3) sigma-complexes of ruthenium

Two new Ru(II)-complexes RuH(Tpms)(PPh3)(2)] 1 (Tpms - (C3H3N2)(3)CSO3, tris-(pyrazolyl) methane sulfonate) and Ru(OTf)(Tpms)(PPh3)(2)] 2 (OTf = CF3SO3) have been synthesized and characterized wherein Ru-H and Ru-OTf are the key reactive centers. Reaction of 1 with HOTf results in the Ru(eta(2)-H-2)(Tpms)(PPh3)(2)]OTf] complex 3, whereas reaction of 1 with Me3SiOTf affords the dihydrogen complex 3 and complex 1 through an unobserved sigma-silane intermediate. In addition, an attempt to characterize the sigma methane complex via reaction of complex 1 with CH3OTf yields complex 2 and free methane. On the other hand, reaction of Ru(OTf)(Tpms)(PPh3)(2)] 2 with H-2 and PhMe2SiH at low temperature resulted in sigma-H-2, 3 and a probable sigma-silane complexes, respectively. However, no sigma-methane complex was observed for the reaction of complex 2 with methane even at low temperature. (C) 2014 Elsevier B. V. All rights reserved.

Phase transformation, improved ferroelectric and magnetic properties of (1-x) BiFeO3-xPb(Zr0.52Ti0.48)O-3 solid solutions

The authors prepared (1 - x) BiFeO3 - (x)Pb(Zr0.52Ti0.48)O-3 for x <= 0.30 by sol-gel method and investigated the material's structures, magnetic and electrical properties. Detailed Rietveld analysis of X-ray diffraction data revealed that the system retains distorted rhombohedral R3c structure for x <= 0.10 but transforms to monoclinic (Cc) structure for x > 0.10. Disappearance of some Raman modes corresponding to A1 modes and the decrease in the intensities of the remaining A1 modes with increasing x in the Raman spectra, which is a clear indication of structural modification and symmetry changes brought about by PZT doping. Enhanced magnetization with PZT doping content may be attributed to the gradual change and destruction in the spin cycloid structure of BiFeO3. The leakage current density at 3.5 kV/cm was reduced by approximately three orders of magnitude by doping PZT (x = 0.30), compared with BFO ceramics. (C) 2014 AIP Publishing LLC.

Structural refinement, optical and electrical properties of Ba1-x Sm-2x/3](Zr0.05Ti0.95)O-3 ceramics

Samarium doped barium zirconate titanate ceramics with general formula Ba1-x Sm-2x/3](Zr0.05Ti0.95)O-3 x = 0, 0.01, 0.02, and 0.03] were prepared by high energy ball milling method. X-ray diffraction patterns and micro-Raman spectroscopy confirmed that these ceramics have a single phase with a tetragonal structure. Rietveld refinement data were employed to model BaO12], SmO12], ZrO6], and TiO6] clusters in the lattice. Scanning electron microscopy shows a reduction in average grain size with the increase of Sm3+ ions into lattice. Temperature-dependent dielectric studies indicate a ferroelectric phase transition and the transition temperature decreases with an increase in Sm3+ ion content. The nature of the transition was investigated by the Curie-Weiss law and it is observed that the diffusivity increases with Sm3+ ion content. The ferroelectric hysteresis loop illustrates that the remnant polarization and coercive field increase with an increase in Sm3+ ions content. Optical properties of the ceramics were studied using ultraviolet-visible diffuse reflectance spectroscopy.

Compositional dependence properties change in S40Se60-x,Sb-x alloys

Bulk samples of S40Se60,Sb-x (with x=10, 20, 30 and 40 at. %) were prepared from high purity chemicals by melt quenching technique. The samples compositions were confirmed by using energy dispersive analysis of X-rays. X-ray diffraction studies revealed that all the samples have poly-crystalline phase. The variation in optical properties with compositional has been investigated by X-ray photoelectron spectroscopy and Raman spectroscopy. The optical band gap of the thin films is found to be decreased with composition. Increasing Sb content was found to affect the structural and optical properties of bulk samples. The intensity of core level spectra changes with the addition of Sb clearly interprets the optical properties change due to compositional variation. The Raman shift and new peak formation in these samples clearly show the structural modifications due to Sb addition.

Co-existence of tetragonal and monoclinic phases and multiferroic properties for x <= 0.30 in the (1-x)Pb(Zr0.52Ti0.48)O-3-(x)BiFeO3 system

Compositions with x <= 0.30 in the system (1- x)Pb(Zro(0.52)Ti(0.48))O-3-(x)BiFeO3 were synthesized by sol-gel method. Rietveld analysis of X-ray diffraction data reveals tetragonal structure (P4mm) for x <= 0.05 and monoclinic (Cm) phase along with the existence of tetragonal phase for 0.10 <= x <= 0.25 and monoclinic phase for x = 0.30. Transformation of E(2TO) and E + B1 vibrational modes in the range 210-250 cm(-1) (present for x <= 0.25) into A' + A `' modes at similar to 236 cm(-1) for x = 0.30, and occurrence of new vibrational modes A' and A `' in Raman spectra for x >= 0.10 unambiguously support the presence of monoclinic phase. Occurrence of remnant polarisation and enhanced magnetization with concentration of BiFeO3 indicates superior multiferroic properties. Variation of magneto-capacitance with applied magnetic field is a strong evidence of magneto-electric multiferroic coupling in these materials. (C) 2014 Elsevier B.V. All rights reserved.

Interference Alignment With Diversity for the 2 x 2 X-Network With Four Antennas

A transmission scheme based on the Alamouti code, which we call the Li-Jafarkhani-Jafar (LJJ) scheme, was recently proposed for the 2 x 2 X-network i.e., two-transmitter (Tx) two-receiver X-network] with two antennas at each node. This scheme was claimed to achieve a sum degrees of freedom (DoF) of 8/3 and also a diversity gain of two when fixed finite constellations are employed at each Tx. Furthermore, each Tx required the knowledge of only its own channel unlike the Jafar-Shamai scheme which required global CSIT to achieve the maximum possible sum DoF of 8/3. In this paper, we extend the LJJ scheme to the 2 x 2 X-network with four antennas at each node. The proposed scheme also assumes only local channel knowledge at each Tx. We prove that the proposed scheme achieves the maximum possible sum DoF of 16/3. In addition, we also prove that, using any fixed finite constellation with appropriate rotation at each Tx, the proposed scheme achieves a diversity gain of at least four.

Contrasting reactivity behaviour of the RuHCl(CO)(PNP)] complex with electrophilic reagents XOTf (X = H, CH3, Me3Si)

A new ruthenium pincer complex RuHCl(CO)(PNP)] (PNP = PhCH2N(CH2CH2PPh2)(2)) (1) was synthesized and characterized. The reactivity of complex 1 with electrophilic reagents XOTf (X = H, CH3, and Me3Si; OTf = CF3SO3) was studied by variable temperature NMR spectroscopy with an aim to observe and characterize sigma complexes of type Ru(eta(2)-HX)Cl(CO)(PNP)]OTf] (X = H (2), CH3 (3), Me3Si (4)). Reaction of complex 1 with HOTf resulted in the formation of the dihydrogen complex, Ru(eta(2)-H-2)Cl(CO)(PNP)OTf] (2). On the other hand, the reaction between complex 1 and MeOTf and Me3SiOTf resulted in the direct elimination of MeCl and Me3SiCl via a S(N)2 type of reaction without the intermediacy of the respective sigma complexes 3 and 4. This contrasting reactivity behaviour has been rationalized taking into consideration the approach of the relatively bulky electrophites CH3+ and Me3Si+ onto the hydride moiety of the ruthenium fragment, which is sterically hindered.

Local disorder investigation in NiS2-xSex using Raman and Ni K-edge x-ray absorption spectroscopies

We report on Raman and Ni K-edge x-ray absorption investigations of a NiS2-xSex (with x = 0.00, 0.50/0.55, 0.60, and 1.20) pyrite family. The Ni K-edge absorption edge shows a systematic shift going from an insulating phase (x = 0.00 and 0.50) to a metallic phase (x = 0.60 and 1.20). The near-edge absorption features show a clear evolution with Se doping. The extended x-ray absorption fine structure data reveal the evolution of the local structure with Se doping which mainly governs the local disorder. We also describe the decomposition of the NiS2-xSex Raman spectra and investigate the weights of various phonon modes using Gaussian and Lorentzian profiles. The effectiveness of the fitting models in describing the data is evaluated by means of Bayes factor estimation. The Raman analysis clearly demonstrates the disorder effects due to Se alloying in describing the phonon spectra of NiS2-xSex pyrites.

The X-C center dot center dot center dot pi (X = F, Cl, Br, CN) Carbon Bond

High-level ab initio calculations have been used to study the interactions between the CH3 group of CH3X (X = F, Cl, Br, CN) molecules and pi-electrons. These interactions are important because of the abundance of both the CH3 groups and pi-electrons in biological systems. Complexes between C2H4/C2H2 and CH3X molecules have been used as model systems. Various theoretical methods such as atoms in molecules theory, reduced density gradient analysis, and natural bond orbital analysis have been used to discern these interactions. These analyses show that the interaction of the p-electrons with the CH3X molecules leads to the formation of X-C...p carbon bonds. Similar complexes with other tetrel molecules, SiH3X and GeH3X, have also been considered.

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.

Experimental and theoretical studies on static and dynamic pressure-concentration isotherms of MmNi(5-x)Al(x) (x=0, 0.3, 0.5 and 0.8) hydrides

The static and dynamic pressure concentration isotherms (PCIs) of MmNi(5-x)Al(x). (x = 0, 0.3, 0.5 and 0.8) hydrides were measured at different temperatures using volumetric method. The effect of Al substitution on PCI and thermodynamic properties were studied. The plateau pressure and maximum hydrogen storage capacity decreased with Al content whereas reaction enthalpy increased. The plateau pressure, plateau slope and hysteresis effect was observed more for dynamic PCIs compared to static PCIs. Different mathematical models used for metal hydride-based thermodynamic devices simulation are compared to select suitable model for static and dynamic PCI simulation of MmNi(5)-based hydrides. Few important physical coefficients (partial molar volume, reaction enthalpy, reaction entropy, etc.) useful for development of thermodynamic devices were estimated. A relation has been proposed to correlate aluminium content and physical coefficients for the prediction of unknown PCI. The simulated and experimental PCIs were found matching closely for both static and dynamic conditions. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Dispersion of polymer grafted nanoparticles in polymer nanocomposite films: Insights from surface x-ray scattering and microscopy

Dispersion of nanoparticles in polymer nanocomposite films determines the application potential of these systems as novel materials with unique physical properties. Grafting polymers to, mostly inorganic, nanoparticles has been suggested as an effective strategy to enhance dispersion and hence the efficacy of materials. In this review, we discuss the various parameters which control dispersion of polymer grafted nanoparticles in polymer nanocomposite films. We discuss how surface x-ray scattering and microscopy can provide complementary and unique information in thin polymer nanocomposite films to unravel the subtle interplay of entropic and surface interactions, mediated by confinement, that leads to enhanced dispersion of the nanoparticles in these films. (C) 2014 AIP Publishing LLC.

Monopoles, Dirac operator, and index theory for fuzzy SU(3) / (U(1) x U(1))

The intersection of the ten-dimensional fuzzy conifold Y-F(10) with S-F(5) x S-F(5) is the compact eight-dimensional fuzzy space X-F(8). We show that X-F(8) is (the analogue of) a principal U(1) x U(1) bundle over fuzzy SU(3) / U(1) x U(1)) ( M-F(6)). We construct M-F(6) using the Gell-Mann matrices by adapting Schwinger's construction. The space M-F(6) is of relevance in higher dimensional quantum Hall effect and matrix models of D-branes. Further we show that the sections of the monopole bundle can be expressed in the basis of SU(3) eigenvectors. We construct the Dirac operator on M-F(6) from the Ginsparg-Wilson algebra on this space. Finally, we show that the index of the Dirac operator correctly reproduces the known results in the continuum.

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.