Photochemical intramolecular gamma-hydrogen abstraction in a ketone and an alkene and the role of tunneling of hydrogen

Intramolecular gamma-hydrogen abstraction reactions were examined in pentane-2-one and 2-methyl-1-pentene in their lowest triplet states using the AM1 semi-empirical molecular orbital method with the complete geometry optimization in the unrestricted Hartree-Fock frame. The results reveal that the oxygen atom of the carbonyl group and the end carbon atom of the olefinic bond acquire high free valence and spin density indices in their respective lowest triplet states, leading to abstraction of hydrogen from the gamma-position relative to the carbonyl and olefinic bonds. The theoretical energy profiles fit with a polynomial and the probability of tunneling of hydrogen was estimated by the WKB (Wentzel, Kramer and Brillouin) method. The results, after thermal averaging of the rate constants, reveal that tunneling of hydrogen is significant at room temperature.

Exact free-surface flows for shallow-water equations .2. the compressible case

Exact free surface flows with shear in a compressible barotropic medium are found, extending the authors' earlier work for the incompressible medium. The barotropic medium is of finite extent in the vertical direction, while it is infinite in the horizontal direction. The ''shallow water'' equations for a compressible barotropic medium, subject to boundary conditions at the free surface and at the bottom, are solved in terms of double psi-series, Simple wave and time-dependent solutions are found; for the former the free surface is of arbitrary shape while for the latter it is a damping traveling wave in the horizontal direction, For other types of solutions, the height of the free surface is constant either on lines of constant acceleration or on lines of constant speed. In the case of an isothermal medium, when gamma = 1, we again find simple wave and time-dependent solutions.

Surface studies on uranium monocarbide using XPS and SIMS

The air-exposed surfaces of sintered and are-melted UC samples were examined by XPS and SIMS. XPS results indicate that the surface is covered with a very thin layer of UO2 mixed with free carbon, which would have formed along with the oxide during the reaction between UC and oxygen or moisture. From the SIMS depth profile of oxygen, the thickness of the oxide layer is found to be approximately 10 nm. The SIMS oxygen images of the surface as a function of etching time reveal that the surface of UC consists of a top layer of adsorbed moisture/oxygen; this contamination layer is followed by a layer containing uranium oxide, uranium hydroxide and free carbon and then grain boundary oxide and finally bulk UC. The behaviour of sintered and are-melted samples is similar.

Water Modeling Study Of The Jet Characteristics In A Continuous-Casting Mold

The jet characteristics and the fluid flow pattern in a continuous slab caster have been studied using a water model. The fluid jet is studied under free fall and submerged discharge conditions. In the latter case, the jet was followed by dye-injection technique and image analyser was used to find out the effect of nozzle parameters on jet-spread angle, jet-discharge angle and the volume entrainment by the jet. All free-fall jets with nozzle port angle zero and upward are found to be spinning. Some of the free-fall jets with downward nozzle-port angle are found to be spinning and rest are smooth. The spinning direction of the jets are found to change with time. The well depth, port diameter and the inner diameter of the nozzle have a clear effect on the free-fall jets with downward port angle. The jet-spread angle is found to be about 17-degrees for smooth jets. The spread angle for spinning jet increases as the nozzle-port angle is increased from downward 25 to upward 15-degrees. The jet-discharge angle is always downward even when the nozzle-discharge ports are angled upward. The extent of volume entrainment by the spinning jet is higher and it increases as the nozzle-port angle is increased from 25 downward to 15-degrees upward.

Estimation of surface free energy of pyrites by contact angle measurements

The surface properties of coal-pyrite play a major role in determining its separation from coal in processes such as flotation. The solution pH is an important parameter in determining the surface properties of both coal and coal-pyrite such as surface free energy and zeta-potential. In the present investigation, the effect of pH on the surface free energy of pyrites from different sources was studied. The surface free energy of solids is made up of two components, i.e. the dispersive surface free energy and the acid-base interaction energy. Various methods have been used by previous researchers to evaluate these two components for different solids. In the present study, a new approach was developed and used to study the surface free energy of pyrite surfaces. Results indicate that the dispersion surface free energy of various pyrites is independent of pH while the acid-base interaction energy is strongly dependent on the pH. The acid-base interaction energy is different for each pyrite sample and also the change with pH varies with the type of pyrite. Coal-pyrite was found to be more hydrophobic than ore-pyrite which may be attributed to the presence of carbon in coal-pyrites. The acid-base interaction energy varied little with pH for coal pyrites than ore-pyrite. Comparison of acid-base interaction energy with zeta-potential measurements shows a good correlation between the minimum in acid-base interaction energy and the pHpzc.

Influence of martensite content and morphology on the toughness and fatigue behavior of high-martensite dual-phase steels

A series of high-martensite dual-phase (HMDP) steels exhibiting a 0.3 to 0.8 volume fraction of martensite (V m ), produced by intermediate quenching (IQ) of a vanadium and boron-containing microalloyed steel, have been studied for toughness and fatigue behavior to supplement the contents of a recent report by the present authors on the unusual tensile behavior of these steels. The studies included assessment of the quasi-static and dynamic fracture toughness and fatigue-crack growth (FCG) behavior of the developed steels. The experimental results show that the quasi-static fracturetoughness (K ICV ) increases with increasing V m in the range between V m =0.3 and 0.6 and then decreases, whereas the dynamic fracture-toughness parameters (K ID , K D , and J ID ) exhibit a significant increase in their magnitudes for steels containing 0.45 to 0.60 V m before achieving a saturation plateau. Both the quasi-static and dynamic fracture-toughness values exhibit the best range of toughnesses for specimens containing approximately equal amounts of precipitate-free ferrite and martensite in a refined microstructural state. The magnitudes of the fatigue threshold in HMDP steels, for V m between 0.55 and 0.60, appear to be superior to those of structural steels of a similar strength level. The Paris-law exponents (m) for the developed HMDP steels increase with increasing V m , with an attendant decrease in the pre-exponential factor (C).

Growth and Characterization of GaAs Epitaxial Layers by MOCVD

technique, on both semi-insulating and semi-conducting CraAs substrates with (100) orientation, offset by 2° towards (110) direction. Systematic variation of As/Ga was performed to gain an understanding of growth process, type of formation and other related physical properties. The films were characterized by using the variety of techniques, such as SEM, EDAX, HRTEM, XRD, and PL. Optical and electrical properties of undoped CyaAs epilayers are presented with reference to the growth conditions and AsH3/TMGa ratio. Photoluminescence measurements of GaAs epilayers were recorded at 4.2K and shows the emission of free exciton and confirmed their high purity. The dominant residual impurities in GaAs are presented by using PL. Finally, electrochemical depth profiling exhibited almost homogeneous background carrier distribution and excellent abruptness between the thin GaAs epilayer and substrate.

3D Acoustic Analysis Of Spherical Chamber Having Single Inlet And Multiple Outlet: An Impedance Matrix Approach

The transmission loss (TL) performance of spherical chambers having single inlet and multiple outlet is obtained analytically through modal expansion of acoustic field inside the spherical cavity in terms of the spherical Bessel functions and Legendre polynomials. The uniform piston driven model based upon the impedance [Z] matrix is used to characterize the multi-port spherical chamber. It is shown analytically that the [Z] parameters are independent of the azimuthal angle (phi) due to the axisymmetric shape of the sphere; rather, they depend only upon the polar angle (theta) and radius of the chamber R(0). Thus, the effects of relative polar angular location of the ports and number of outlet ports are investigated. The analytical results are shown to be in good agreement with the 3D FEA results, thereby validating the procedure suggested in this work.

Synthesis and nonlinear optical properties of Lead Telluride nanorods

Lead Telluride (PbTe) nanorods have been uniformly grown on silicon substrates, using the thermal evaporation technique under high vacuum conditions. The structural and morphological studies are done using X-ray diffraction and scanning electron microscopy. Optical nonlinearity studies using the open aperture z-scan employing 5 ns and 100 fs laser pulses reveal a three-photon type absorption. For nanosecond excitation the nonlinear absorption coefficients (gamma) are in the order of 10(-22) m(3) W-2 and for femtosecond excitation it is in the order of 10(-29) m(3) W-2. The role of free carriers and excitons in causing the nonlinearity in both excitation time domains is discussed. Results indicate that PbTe nanorods are good optical limiters with potential device applications. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic properties and biological evaluation of transition metal complexes of salicylhydrazone of anthranilhydrazide: X-ray crystal structure of copper complex

The transition metal complexes of salicylhydrazone of anthranilhydrazide (H2L) were synthesised. The structures of metal complexes were characterized by various spectroscopic [IR, NMR, UV-Vis, EPR], thermal and other physicochemical methods. The single-crystal X-ray diffraction study of [Cu(HL)Cl]center dot H2O reveal its orthorhombic system with space group P2(1)2(1)2 and Z=4. The copper center has a distorted square planar geometry with ONO and Cl as the donor atoms. The ligand and its metal chelates have been screened for their antimicrobial and anti-tubercular activities using serial dilution method. Metal complexes in general have exhibited better antibacterial and antifungal activity than the free ligand and in few cases better than the standard used. Among the bacterial strains used, the complexes are highly potent against Gram-positive strains compared to Gram-negative. Anti-tubercular activity exhibited by the Co(II) complex is comparable with the standard used. (C) 2011 Elsevier B. V. All rights reserved.

Plumes Dynamics and Heat Transfer over Horizontal Grooved Surfaces

This study investigates the free convection and plumes dynamics over horizontal surfaces with parallel V-grooves. The convection is studied in a tank of water with the bottom surface being a smooth or grooved surface and the top of the water surface exposed to ambient. Two groove heights were used-10 mm and 3 mm-and the experiment was done with two values of aspect ratio-2.9 and 1.8 (aspect ratio is the width of the fluid layer/height of fluid layer). Heat flux at the bottom surface was from electrical heating. Beyond a certain critical temperature difference, enhanced heat transfer is obtained on the grooved surface compared to a smooth surface. Nusselt numbers are evaluated for both smooth and grooved surfaces and correlated using modified Rayleigh numbers. Visualization shows that the enhanced heat transport in the rough cavities cannot be ascribed to the increase in the contact area; rather, it must be the local dynamics of the thermal boundary layer.

Synthesis and characterization of high molecular weight polyaniline for organic electronic applications

High molecular weight polyaniline (PANI) was synthesized by a combined procedure incorporating various synthesis methods. Temperature and open circuit potential of the reaction mixture were collected to monitor the reaction progress. The polymer is characterized by various techniques including gel permeation chromatography, dynamic light scattering, infrared spectroscopy, solid-state nuclear magnetic resonance, and differential scanning calorimetry for elucidating the molecular architecture obtained by this method. As-synthesized PANI was found to possess high molecular weight, reduced branching, reduced cross-linking, and to predominantly consist of linear polymer chains. This polymer was also found to be more stable in solution form. JV characteristics of as-synthesized PANI films indicate a high current density which is due to increased free pathways and less traps for the charge transport to occur in PANI films. POLYM. ENG. SCI., 2012. (C) 2012 Society of Plastics Engineers

Sensitivity of polyvinylidene fluoride films to mechanical vibration modes and impact after optimizing stretching conditions

The β-phase of polyvinylidene fluoride (PVDF) is well known for its piezoelectric properties. PVDF films have been developed using solvent cast method. The films thus produced are in α-phase. The α-phase is transformed to piezoelectric β-phase when the film is hot-stretched with various different stretching factors at various different temperatures. The films are then characterized in terms of their mechanical properties and surface morphological changes during the transformation from α- to β-phases by using X-ray diffraction, differential scanning calorimeter, Raman spectra, Infrared spectra, tensile testing, and scanning electron microscopy. The films showed increased crystallinity with stretching at temperature up to 80°C. The optimum conditions to achieve β-phase have been discussed in detail. The fabricated PVDF sensors have been tested for free vibration and impact on plate structure, and its response is compared with conventional piezoelectric wafer type sensor. The resonant and antiresonant peaks in the frequency response of PVDF sensor match well with that of lead zirconate titanate wafer sensors. Effective piezoelectric properties and the variations in the frequency response spectra due to free vibration and impact loading conditions are reported. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers.

Dynamics of rotating composite beams: A comparative study between CNT reinforced polymer composite beams and laminated composite beams using spectral finite elements

This paper presents a spectral finite element formulation for uniform and tapered rotating CNT embedded polymer composite beams. The exact solution to the governing differential equation of a rotating Euler-Bernoulli beam with maximum centrifugal force is used as an interpolating function for the spectral element formulation. Free vibration and wave propagation analysis is carried out using the formulated spectral element. The present study shows the substantial effect of volume fraction and L/D ratio of CNTs in a beam on the natural frequency, impulse response and wave propagation characteristics of the rotating beam. It is found that the CNTs embedded in the matrix can make the rotating beam non-dispersive in nature at higher rotation speeds. Embedded CNTs can significantly alter the dynamics of polymer-nanocomposite beams. The results are also compared with those obtained for carbon fiber reinforced laminated composite rotating beams. It is observed that CNT reinforced rotating beams are superior in performance compared to laminated composite rotating beams. © 2012 Elsevier Ltd. All rights reserved.

Effect of isothermal aging and electromigration on the microstructural evolution of solder interconnections during thermomechanical loading

The effect of different pre-aging treatments on the microstructural evolution of lead-free solder and growth of interfacial intermetallic compound layers under thermal cycling has been investigated in this work. The results show that there are distinct differences in the microstructural changes between samples with no pretreatment, samples that have experienced thermal annealing at 125A degrees C for 750 h before thermal cycling, and those that have had direct current (DC) stressing for 750 h as pretreatment. The microstructural evolution of the solder matrix is rationalized by utilizing the science of microstructures and analysis of the influence of electron flow on the precipitation phenomena. The finite-element method is utilized to understand the loading conditions imposed on the solder interconnections during cyclic stressing. The growth of intermetallic reaction layers is further analyzed by utilizing quantitative thermodynamic calculations coupled with kinetic analysis. The latter is based on the changes in the intrinsic diffusion fluxes of elements induced by current flow and alloying elements present in the system. With this concurrent approach the differences seen in thermal cycling behavior between the different pre-aging treatments can be explained.