Syntheses and studies on pyridinium pxofluorocomplexes of molybdenum, tungsten andiodine

(C5H5NH)2MO2F4 (M = Mo and W) and C5H5NHIO2F2 have been synthesized at room temperature by the reaction of molybdic, tungstic or iodic acid, respectively, with pyridinium poly(hydrogen fluoride). These complexes have been characterized by chemical analyses, H-1 nmr and infrared spectroscopy.

Nonaxisymmetric convection in stationary Gas Tungsten Arc Weld Pools

Observations of surface flow patterns of steel and aluminum GTAW pools have been made using a pulsed laser visualization system. The weld pool convection is found to be three-dimensional with the azimuthal circulation depending on the location of the clamp with respect to the torch. Oscillation of steel pools and undulating motion in aluminum weld pools are also observed even with steady process parameters. Current axisymmetric numerical models are unable to explain such phenomena. A three-dimensional computational study is carried out in this study to explain the rotational flow in aluminum weld pools.

Scaling analysis of momentum and heat transport in gas tungsten arc weld pools

A systematic procedure is outlined for scaling analysis of momentum and heat transfer in gas tungsten arc weld pools. With suitable selections of non-dimentionalised parameters, the governing equations coupled with appropriate boundary conditions are first scaled, and the relative significance of various terms appearing in them is analysed accordingly. The analysis is then used to predict the orders of magnitude of some important quantities, such as the velocity scene lit the top surface, velocity boundary layer thickness, maximum temperature increase in the pool, and time required for initiation of melting. Some of the quantities predicted from the scaling analysis can also be used for optimised selection of appropriate grid size and time steps for full numerical simulation of the process. The scaling predictions are finally assessed by comparison with numerical results quoted in the literature, and a good qualitative agreement is observed.

Molybdenum trioxide catalyzed oxidative cross-dehydrogenative coupling of benzylic sp(3) C-H bonds: synthesis of alpha-aminophosphonates under aerobic conditions

Molybdenum trioxide (MoO3) catalyzed efficient oxidative cross-dehydrogenative-coupling (CDC) method for C-H functionalization of N-aryl tetrahydroisoquinolines has been explored. This user-friendly method of synthesizing alpha-aminophosphonates employs 1.1 equiv of dialkyl-H-phosphonate under aerobic condition. Formation of new C-P bonds from unfunctionalized starting materials under environmentally benign conditions provides an excellent avenue for the synthesis of biologically active alpha-aminophosphonates. (C) 2012 Elsevier Ltd. All rights reserved.

Temperature dependent photoemission spectroscopy on lightly-doped sodium tungsten bronze

Temperature dependent photoemission studies on lightly doped (x = 0.025) sodium tungsten bronzes, NaxWO3 have been investigated by high-resolution photoemission spectroscopy. The experimental results show evidence for polaron formation at the valence band edge and the photoemission spectra taken in different modes of the electron analyzer suggest that the density of states at the valence band edge gradually moves to other k-points in the Brillouin zone with increasing temperature and explain the dynamics of polarons in the insulating disordered sodium tungsten bronzes. (C) 2012 Elsevier Ltd. All rights reserved.

Diffusion in tungsten silicides

Experiments are conducted in the W-Si system to understand the diffusion mechanism of the species. The activation energies from integrated diffusion coefficients are calculated as 152 +/- 7 and 301 +/- 40 kJ/mol in the WSi2 and W5Si3 phases, respectively. In both the phases, Si has a much higher diffusion rate compared to W. This is not surprising to find in the WSi2 phase, if we consider the number of nearest neighbors for both the elements in the crystal. The diffusion of W in this phase indicates the presence of W antisites. The faster diffusion rate of Si in the W5Si3 phase indicates the presence of higher concentration of vacancies on the Si sublattice compared to W sublattice.

Ozone and carbon trioxide synthesis by low energy ion implantation onto solid carbon dioxide and implications to astrochemistry

Ion implantation experiments were carried out on amorphous (30 K) and crystalline (80 K) solid CO2 using both reactive (D+, H+) and non-reactive (He+) ions, simulating different irradiation environments on satellite and dust grain surfaces. Such ion irradiation synthesized several new species in the ice including ozone (O-3), carbon trioxide (CO3), and carbon monoxide (CO) the main dissociation product of carbon dioxide. The yield of these products was found to be strongly dependent upon the ion used for irradiation and the sample temperature. Ion implantation changes the chemical composition of the ice with recorded infrared spectra clearly showing the coexistence of D-3h and C-2v isomers of CO3, for the first time, in ion irradiated CO2 ice. (C) 2013 AIP Publishing LLC.

Electronic band structure and Fermi surfaces of the quasi-two-dimensional monophosphate tungsten bronze, P4W12O44

The electronic structure of quasi-two-dimensional monophosphate tungsten bronze, P4W12O44, has been investigated by high-resolution angle-resolved photoemission spectroscopy and density functional theoretical calculations. Experimental electron-like bands around Gamma point and Fermi surfaces have similar shapes as predicted by calculations. Fermi surface mapping at different temperatures shows a depletion of density of states at low temperature in certain flat portions of the Fermi surfaces. These flat portions of the Fermi surfaces satisfy the partial nesting condition with incommensurate nesting vectors q(1) and q(2), which leads to the formation of charge density waves in this phosphate tungsten bronzes. The setting up of charge density wave in these bronzes can well explain the anomaly observed in its transport properties. Copyright (C) EPLA, 2014

Tin-Incorporation Induced Changes in the Microstructural, Optical, and Electrical Behavior of Tungsten Oxide Nanocrystalline Thin Films Grown Via Spray Pyrolysis

Undoped and Sn-doped WO3 thin films were grown on cleaned glass substrates by chemical spray pyrolysis, using ammonium tungstate (NH4)(2)WO4 as the host precursor and tin chloride (SnCl4 center dot 5H(2)O) as the source of dopant. The XRD spectra confirm the monoclinic structure with a sharp narrow peak along (200) direction along with other peaks of low relative intensities for all the samples. On Sn doping, the films exhibit reduced crystallinity relative to the undoped film. The standard deviation for relative peak intensity with dopant concentration shows enhancement in heterogeneous nucleation growth. As evident from SEM images, on Sn doping, appearance of island-like structure (i.e., cluster of primary crystallites at few places) takes place. The transmittance has been found to decrease in all the Sn-doped films. The optical band gap has been calculated for both direct and indirect transitions. On Sn doping, the direct band gap shows a red shift and becomes 2.89 eV at 2 at.% doping. Two distinct peaks, one blue emission at 408 nm and other green emission at 533 nm, have been found in the PL spectra. Electrical conductivity has been found to increase with Sn doping.

Synthesis of a new tungsten-free gamma-gamma ` cobalt-based superalloy by tuning alloying additions

The paper presents the synthesis of a new class of gamma-gamma' cobalt-based superalloy that is free of tungsten as an alloying addition. It has much lower density and higher specific strength than the existing cobalt-based superalloys. The current superalloys have a base composition of Co-10Al and are further tuned by the addition of a binary combination of molybdenum and niobium, with the optimum composition of Co-10Al-5Mo-2Nb. The solvus temperature of the alloy (866 degrees C) can be further enhanced above 950 C by the addition of Ni to give the form Co-xNi-10Al-5Mo-2Nb, where x can be from 0 to 30 at.%. After heat treatment, these alloys exhibit a duplex microstructure with coherent cuboidal L1(2)-ordered precipitates (gamma') throughout the face-centred cubic matrix (gamma), yielding a microstructure that is very similar to nickel-based superalloys as well as recently developed Co-Al-W-based alloys. We show that the stability of the gamma' phase improves significantly with the nickel addition, which can be attributed to the increase in solvus temperature. A very high specific 0.2% proof stress of 94.3 MPa g(-1) cm(-3) at room temperature and 63.8 MPa g(-1) cm(-3) at 870 degrees C were obtained for alloy Co-30Ni-10Al-5Mo-2Nb. The remarkably high specific strength of these alloys makes this class of alloy a promising material for use at high temperature, including gas turbine applications. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A new tungsten-free gamma-gamma ` Co-Al-Mo-Nb-based superalloy

We present the first report of a tungsten-free cobalt-based superalloy having a composition Co-10Al-5Mo-2Nb. The alloy is strengthened by cuboidal precipitates of metastable Co-3(Al,Mo,Nb) distributed throughout the microstructure. The precipitates are coherent with the face-centred cubic gamma-Co matrix and possess ordered Ll(2) structure. The microstructure is identical to the popular gamma-gamma' type nickel-based superalloys and that of recently reported Co-Al-W-based alloys. Being tungsten free, the reported alloy has higher specific proof stress compared to existing cobalt-based superalloys. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Contrasting Electronic Requirements for C-H Binding and C-H Activation in d(6) Half-Sandwich Complexes of Rhenium and Tungsten

A computational study of the interaction half-sandwich metal fragments (metal=Re/W, electron count=d(6)), containing linear nitrosyl (NO+), carbon monoxide (CO), trifluorophosphine (PF3), N-heterocyclic carbene (NHC) ligands with alkanes are conducted using density functional theory employing the hybrid meta-GGA functional (M06). Electron deficiency on the metal increases with the ligand in the order NHC < CO < PF3 < NO+. Electron-withdrawing ligands like NO+ lead to more stable alkane complexes than NHC, a strong electron donor. Energy decomposition analysis shows that stabilization is due to orbital interaction involving charge transfer from the alkane to the metal. Reactivity and dynamics of the alkane fragment are facilitated by electron donors on the metal. These results match most of the experimental results known for CO and PF3 complexes. The study suggests activation of alkane in metal complexes to be facile with strong donor ligands like NHC. (C) 2015 Wiley Periodicals, Inc.

Tungsten-based nanomaterials (WO3 & Bi2WO6): Modifications related to charge carrier transfer mechanisms and photocatalytic applications

Heterogeneous photocatalysis is an ideal green energy technology for the purification of wastewater. Although titania dominates as the reference photocatalyst, its wide band gap is a bottleneck for extended utility. Thus, search for non-TiO2 based nanomaterials has become an active area of research in recent years. In this regard, visible light absorbing polycrystalline WO3 (2.4-2.8 eV) and Bi2WO6 (2.8 eV) with versatile structure-electronic properties has gained considerable interest to promote the photocatalytic reactions. These materials are also explored in selective functional group transformation in organic reactions, because of low reduction and oxidation potential of WO3 CB and Bi2WO6 VB, respectively. In this focused review, various strategies such as foreign ion doping, noble metal deposition and heterostructuring with other semiconductors designed for efficient photocatalysis is discussed. These modifications not only extend the optical response to longer wavelengths, but also prolong the life-time of the charge carriers and strengthen the photocatalyst stability. The changes in the surface-bulk properties and the charge carrier transfer dynamics associated with each modification correlating to the high activity are emphasized. The presence of oxidizing agents, surface modification with Cu2+ ions and synthesis of exposed facets to promote the degradation rate is highlighted. In depth study on these nanomaterials is likely to sustain interest in wastewater remediation and envisaged to signify in various green energy applications. (C) 2015 Elsevier B.V. All rights reserved.

Temperature dependent vibrational lifetimes in supercritical fluids near the critical point

Vibrational relaxation measurements on the CO asymmetric stretching mode (similar to 1980 cm(-1)) of tungsten hexacarbonyl (W(CO)(6)) as a function of temperature at constant density in several supercritical solvents in the vicinity of the critical point are presented. In supercritical ethane, at the critical density, there is a region above the critical temperature (Tc) in which the lifetime increases with increasing temperature. When the temperature is raised sufficiently (similar to T-c + 70 degrees C), the lifetime decreases with further increase in temperature. A recent hydrodynamic/thermodynamic theory of vibrational relaxation in supercritical fluids reproduces this behavior semiquantitatively. The temperature dependent data for fixed densities somewhat above and below the critical density is in better agreement with the theory. In fluoroform solvent at the critical density, the vibrational lifetime also initially increases with increasing temperature. However, in supercritical CO2 at the critical density, the temperature dependent vibrational lifetime decreases approximately linearly with temperature beginning almost immediately above T-c. The theory does not reproduce this behavior. A comparison between the absolute lifetimes in the three solvents and the temperature trends is made.

In situ transmission electron microscopy study of deformation of an aluminum alloy tribolayer

Nanoscale deformation in the tribolayer of an Al–Mg alloy is studied using an in situ mechanical probe in a transmission electron microscope. The sample is strained locally at room temperature and the deformation is observed in real time. It is observed that when the tungsten probe comes into contact with the tribolayer, the material exhibits further hardening followed by material removal.