Organometallic chemistry of diphosphazanes. Part IX: Syntheses and spectroscopic studies of molybdenum and tungsten tetracarbonyl complexes of unsymmetrical diphosphazanes

The unsymmetrical diphosphazanes X2PN(Pr(i))PYY'(1a-1h) {X = Ph, YY' = O2 C6H4 (1a) or YY' = O2C12H8 (1b); X = Ph, Y = Ph, Y' = OC6H4Me-4 (1c), OC6H4Br-4 (1d), OC6H3Me2-3,5 (1e), OC5H4N-2 (1f), N2C3HMe2-3,5 (1g) or Cl (1h)} react with [M(CO)4(NHC5H10)2] (M = Mo, W) to yield the cis-chelate complexes [M(CO)4{X2PN(Pr(i)) PYY'}] {M = Mo (2a-2h); M = W (3-f,3-g)}. These complexes have been characterized by H-1, P-31 and C-13 NMR and IR spectroscopic studies.

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.

Influence of carbide particles on the dynamic recrystallization of as-cast 304 stainless steel: a study using secondary ion mass spectrometric (SIMS) analysis

The domain of dynamic recrystallization (DRX) in as-cast 304 stainless steel material occurs at higher temperatures (1250 degrees C) and lower strain rates (0.001 s(-1)) than in wrought 304 stainless steel (1100 degrees C and 0.01 s(-1)). The above result has been explained earlier on the basis of a simple theoretical DRX model involving the rate of nucleation versus rate of grain boundary migration. The present investigation is aimed at examining experimentally the influence of carbide particles on the DRX of ascast 304 using secondary ion mass spectrometric (SIMS) analysis. Isothermal compression tests at a constant true strain rate have been performed on wrought 304 and as-cast 304 materials in the temperature and strain rate ranges of 1000 to 1250 degrees C and 0.001 to 1 s(-1) respectively. The SIMS analysis carried out on the deformed samples revealed that the large carbides present in the as-cast 304 material strongly influence the DRX process. In as-cast 304 material, the presence of large carbide particles in the microstructure shifts the DRX domain to higher temperature and lower strain rate in comparison with wrought 304 material.

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.

Study of formation of silicon carbide in the Acheson process

Formation of silicon carbide in the Acheson process was studied using a mass transfer model which has been developed in this study. The century old Acheson process is still used for the mass production of silicon carbide. A heat resistance furnace is used in the Acheson process which uses sand and petroleum coke as major raw materials.: It is a highly energy intensive process. No mass transfer model is available for this process. Therefore, a mass transfer model has been developed to study the mass transfer aspects of the process along with heat transfer. The reaction kinetics of silicon carbide formation has been taken from the literature. It has been shown that reaction kinetics has a reasonable influence on the process efficiency. The effect of various parameters on the process such as total gas pressure, presence of silicon carbide in the initial charge, etc. has been studied. A graphical user interface has also been developed for the Acheson process to make the computer code user friendly.

Comparison of CVD and MOCVD-grown Al2O3 coatings in the performance of cemented carbide cutting tool inserts

Low-pressure MOCVD, with tris(2,4 pentanedionato)aluminum(III) as the precursor, was used in the present investigation to coat alumina on to cemented carbide cutting tools. To evaluate the MOCVD process, the efficiency in cutting operations of MOCVD-coated tools was compared with that of tools coated using the industry-standard CVD process.Three multilayer cemented carbide cutting tool inserts, viz., TiN/TiC/WC, CVD-coated Al2O3 on TiN/TiC/WC, and MOCVD-coated Al2O3 on TiN/TiC/WC, were compared in the dry turning of mild steel. Turning tests were conducted for cutting speeds ranging from 14 to 47 m/min, for a depth of cut from 0.25 to 1 mm, at the constant feed rate of 0.2 mm/min. The axial, tangential, and radial forces were measured using a lathe tool dynamometer for different cutting parameters, and the machined work pieces were tested for surface roughness. The results indicate that, in most of the cases examined, the MOCVD-coated inserts produced a smoother surface finish, while requiring lower cutting forces, indicating that MOCVD produces the best-performing insert, followed by the CVD-coated one. The superior performance of MOCVD-alumina is attributed to the co-deposition of carbon with the oxide, due to the very nature of the precursor used, leading to enhanced mechanical properties for cutting applications in harsh environment.

Electrochemical oxidation of boron containing compounds on titanium carbide and its implications to direct fuel cells

Electrochemical oxidation of sodium borohydride (NaBH(4)) and ammonia borane (NH(3)BH(3)) (AB) have been studied on titanium carbide electrode. The oxidation is followed by using cyclic voltammetry, chronoamperometry and polarization measurements. A fuel cell with TiC as anode and 40 wt% Pt/C as cathode is constructed and the polarization behaviour is studied with NaBH(4) as anodic fuel and hydrogen peroxide as catholyte. A maximum power density of 65 mW cm(-2) at a load current density of 83 mA cm(-2) is obtained at 343 K in the case of borhydride-based fuel cell and a value of 85 mW cm(-2) at 105 mA cm(-2) is obtained in the case of AB-based fuel cell at 353 K. (C) 2011 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.

Enhanced Raman Spectroscopy of Molecules Adsorbed on Carbon-Doped TiO2 Obtained from Titanium Carbide: A Visible-Light-Assisted Renewable Substrate

Titanium carbide (TiC) is an electrically conducting material with favorable electrochemical properties. In the present studies, carbon-doped TiO2 (C-TiO2) has been synthesized from TiC particles, as well as TiC films coated on stainless steel substrate via thermal annealing under various conditions. Several C-TiO2 substrates are synthesized by varying experimental, conditions and characterized by UV-visible spectroscopy, photoluminescence, X-ray diffraction and X-ray photoelectron spectroscopic techniques. C-TiO2 in the dry state (in powder form as well as in film form) is subsequently used as a substrate for enhancing Raman signals corresponding to 4-mercaptobenzoic acid and 4-nitrothiophenol by utilizing chemical enhancement based on charge-transfer interactions. Carbon, a nonmetal dopant in TiO2, improves the intensities of Raman signals, compared, to undoped TiO2. Significant dependence of Raman intensity on carbon doping is observed. Ameliorated performance obtained using C-TiO2 is attributed to the presence of surface defects that originate due to carbon as a dopant, which, in turn,, triggers charge transfer between TiO2 and analyte. The C-TiO2 substrates are subsequently regenerated for repetitive use by illuminating an analyte-adsorbed substrate with visible light for a period of 5 h.

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.

Morphology dependent oxygen reduction activity of titanium carbide: bulk vs. nanowires

Titanium carbide (TiC) possesses fascinating properties like high electrical conductivity and high mechanical strength coupled with high corrosion resistance and stability in acidic and alkaline environments. The present study demonstrates the tunability of mechanistic aspects of oxygen reduction reaction (ORR) using TiC nanostructures. One dimensional TiC nanostructures (TiC-NW) have been synthesized using a simple, hydrothermal method and used as a catalyst for ORR. Shape dependent electroactivity is demonstrated by comparing the activity of TiC-NW with its bulk counterparts. Comparative studies reveal higher ORR activities in the case of 1D TiC-NW involving similar to 4 electrons showing efficient reduction of molecular oxygen. Excellent stability and high methanol tolerance with good selectivity for ORR is reported.

Fretting studies on self-mated stainless steel and chromium carbide coated surfaces under controlled environment conditions

Adhesive wear has been widely accepted as the type of wear which is most frequently encountered under fretting conditions. Present study has been carried out to study the mode of failure and mechanisms associated under conditions where strong adhesion prevails at the contact interface. Mechanical variables such as normal load, displacement amplitude, and environment conditions were controlled so as to simulate adhesion as the governing mechanism at the contact interface. Self-mated Stainless Steel (SS) and chromium carbide with 25% nickel chrome binder coatings using plasma spray and high-velocity oxy-fuel (HVOF) processes on SS were considered as the material for contacting bodies. Damage in the form of plastic deformation, fracture, and material transfer has been observed. Further, chromium carbide with 25% nickel chrome binder coatings using HVOF process on SS shows less fretting damage, and can be considered as an effective palliative against fretting damage, even under high vacuum conditions. (C) 2013 Elsevier B.V. All rights reserved.