Effect of Chalcogens on Electronic and Photophysical Properties of Vinylene-Based Diketopyrrolopyrrole Copolymers

Three vinylene linked diketopyrrolopyrrole based donor acceptor (D-A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV-vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm(2) V-1 s(-1).

A Cause and Effect Analysis of Motion Trajectories for Modeling Actions

An action is typically composed of different parts of the object moving in particular sequences. The presence of different motions (represented as a 1D histogram) has been used in the traditional bag-of-words (BoW) approach for recognizing actions. However the interactions among the motions also form a crucial part of an action. Different object-parts have varying degrees of interactions with the other parts during an action cycle. It is these interactions we want to quantify in order to bring in additional information about the actions. In this paper we propose a causality based approach for quantifying the interactions to aid action classification. Granger causality is used to compute the cause and effect relationships for pairs of motion trajectories of a video. A 2D histogram descriptor for the video is constructed using these pairwise measures. Our proposed method of obtaining pairwise measures for videos is also applicable for large datasets. We have conducted experiments on challenging action recognition databases such as HMDB51 and UCF50 and shown that our causality descriptor helps in encoding additional information regarding the actions and performs on par with the state-of-the art approaches. Due to the complementary nature, a further increase in performance can be observed by combining our approach with state-of-the-art approaches.

In Situ Crystallographic Probing on Ameliorating Effect of Sulfide Additives and Carbon Grafting in Iron Electrodes

Beneficial effects of carbon grafting into the iron active material for rechargeable alkaline-iron-electrodes with and without Bi2S3 additive is probed by in situ X-ray diffraction in conjunction with Extended X-ray Absorption Fine Structure (EXAFS) and electrochemistry. EXAFS data unravel that the composition of pristine active material (PAM) for iron electrodes comprises 87% of magnetite and 13% of alpha-iron while carbon-grafted active material comprises 60% of magnetite and 40% of alpha-iron. In situ XRD patterns are recorded using a specially designed electrochemical cell. XRD data reflect that magnetite present in PAM iron electrode, without bismuth sulfide additive, is not reduced during charging while PAM iron electrode with bismuth sulfide additive is partially reduced to alpha-Fe/Fe(OH)(2). Interestingly, carbon-grafted-iron electrodes with bismuth sulfide exhibit complete conversion of active material to alpha-Fe/Fe(OH)2. The ameliorating effect of carbon grafting is substantiated by kinetic parameters obtained from steady-state potentiostatic polarization and Tafel plots. The mechanism for iron-electrode charge - discharge reactions are discussed in the light of the potential - pH diagrams for Fe - H2O, S - H2O and FeSads - H2O systems and it is surmised that carbon grafting into iron active material promotes its electrochemical utilization. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Die Filling Behaviour of Semi Solid A356 Al Alloy Slurry During Rheo Pressure Die Casting

The present work discusses the findings obtained from simulations of semi solid die filling of a steering knuckle, prior to actual component development using in-house developed rheo pressure die casting system. Die filling capability of A356 Al alloy at semi-solid state has been investigated using commercial software Flow-3Dcast to optimise the pouring temperature of semi-solid slurry into the die cavity, while all other variables such as gating design, die preheat temperature and injection velocity are kept constant based on the prior knowledge obtained from trial numerical simulations and experimentation. Efforts have been made to nullify the essence of costly, time consuming experiments towards obtaining high-quality castings out of the findings obtained from numerical simulations. The optimum pouring temperature identified in the present study is 610 A degrees C, which facilitates smoother slurry flow, minimum surface defect concentration, uniform temperature field and solid fraction distribution within the component cavity.

Crystal chemistry and photomechanical behavior of 3,4-dimethoxycinnamic acid: correlation between maximum yield in the solid-state topochemical reaction and cooperative molecular motion

A new monoclinic polymorph, form II (P2(1)/c, Z = 4), has been isolated for 3,4-dimethoxycinnamic acid (DMCA). Its solid-state 2 + 2 photoreaction to the corresponding alpha-truxillic acid is different from that of the first polymorph, the triclinic form I (P (1) over bar, Z = 4) that was reported in 1984. The crystal structures of the two forms are rather different. The two polymorphs also exhibit different photomechanical properties. Form I exhibits photosalient behavior but this effect is absent in form II. These properties can be explained on the basis of the crystal packing in the two forms. The nanoindentation technique is used to shed further insights into these structure-property relationships. A faster photoreaction in form I and a higher yield in form II are rationalized on the basis of the mechanical properties of the individual crystal forms. It is suggested that both Schmidt-type and Kaupp-type topochemistry are applicable for the solid-state trans-cinnamic acid photodimerization reaction. Form I of DMCA is more plastic and seems to react under Kaupp-type conditions with maximum molecular movements. Form II is more brittle, and its interlocked structure seems to favor Schmidt-type topochemistry with minimum molecular movement.

Neutron diffraction, Mossbauer effect and Electron Paramagnetic Resonance studies on multiferroic Pb(Fe2/3W1/3)O-3

Multiferroic Pb(Fe2/3W1/3)O-3 ceramics were synthesized via a modified two-stage Columbite method. Single phase formation was confirmed from the analysis of x-ray and neutron diffraction patterns recorded at room temperature. Structural analysis of the diffraction data reveals cubic phase (space group Pm-3m) for the title compound. Magnetic structure of the title compound at room temperature exhibits G-type antiferromagnetic structure. The Mossbauer spectroscopy and Electron Paramagnetic Resonance (EPR) studies were carried out at 300 K. The isomer shift and quadrupole splitting of the Mossbauer spectra confirms the trivalent state of iron (Fe3+). The Mossbauer spectra also suggest that the iron and tungsten are randomly distributed at the octahedral, B site. EPR spectra show a single broad line associated with Fe3+ ions. Both spectra clearly exhibit weak ferromagnetic behaviour of Pb(Fe2/3W1/3)O-3 ceramic at 300 K. Considering neutron diffraction, Mossbauer and EPR results together, it may be stated here that Pb(Fe2/3W1/3)O-3 exhibits antiferromagnetic behavior along with weak ferromagnetism at room temperature.

Effect of Te Addition into As2Se3 Thin Film: Optical Property Study by FTIR and XPS.

In the present work, we report the effect of Te deposition onto As2Se3 film which affects the optical properties. The Te/As2Se3 film was illuminated with 532 nm laser to study the photo induced diffusion. The prepared As2Se3, Te/As2Se3 films were characterized by X-ray diffraction which show a completely amorphous nature. On the basis of optical transmission data carried out by Fourier Transform infrared Spectroscopy, a non direct transition was found for these films. The optical bandgap is found to be decreased with Te deposition and photo darkening phenomena is observed for the diffused film. The change in the optical constants are also supported by the corresponding change in different types of bonds which are being analyzed by X-ray photoelectron spectroscopy.

Effect Of High Pressure On The Electrical Resistivity Of Ge-Te In Glasses

The variation in the electrical resistivity of the chalcogenide glasses Ge15Te85-x has been studied as a function of high pressure for pressures up to 8.5GPa. All the samples studied undergo a semi-conductor to metallic transition in a continuous manner at pressures between 1.5-2.5GPa. The transition pressure at which the samples turn metallic increases with increase in percentage of Indium. This increase is a direct consequence of the increase in network rigidity with the addition of Indium. At a constant pressure of 0.5GPa, the normalized resistivity shows some signature of the existence of the intermediate phase. Samples recovered after a pressure cycle remain amorphous suggesting that the semi-conductor to metallic transition arises from a reduction of the band gap due to pressure or the movement of the Fermi level into the conduction or valence band.

Effect of Ni content on the diffusion-controlled growth of the product phases in the Cu(Ni)-Sn system

A strong influence of Ni content on the diffusion-controlled growth of the (Cu,Ni)(3)Sn and (Cu,Ni)(6)Sn-5 phases by coupling different Cu(Ni) alloys with Sn in the solid state is reported. The continuous increase in the thickness ratio of (Cu,Ni)(6)Sn-5 to (Cu,Ni)(3)Sn with the Ni content is explained by combined kinetic and thermodynamic arguments as follows: (i) The integrated interdiffusion coefficient does not change for the (Cu,Ni)(3)Sn phase up to 2.5 at.% Ni and decreases drastically for 5 at.% Ni. On the other hand, there is a continuous increase in the integrated interdiffusion coefficient for (Cu,Ni)(6)Sn-5 as a function of increasing Ni content. (ii) With the increase in Ni content, driving forces for the diffusion of components increase for both components in both phases but at different rates. However, the magnitude of these changes alone is not large enough to explain the high difference in the observed growth rate of the product phases because of Ni addition. (iv) Kirkendall marker experiments indicate that the Cu6Sn5 phase grows by diffusion of both Cu and Sn in the binary case. However, when Ni is added, the growth is by diffusion of Sn only. (v) Also, the observed grain refinement in the Cu6Sn5 phase with the addition of Ni suggests that the grain boundary diffusion of Sn may have an important role in the observed changes in the growth rate.

Small-Signal Stability Analysis of an Open-Loop Induction Motor Drive Including the Effect of Inverter Deadtime

This paper demonstrates light-load instability in a 100-kW open-loop induction motor drive on account of inverter deadtime. An improved small-signal model of an inverter-fed induction motor is proposed. This improved model is derived by linearizing the nonlinear dynamic equations of the motor, which include the inverter deadtime effect. Stability analysis is carried out on the 100-kW415-V three-phase induction motor considering no load. The analysis brings out the region of instability of this motor drive on the voltage versus frequency (V-f) plane. This region of light-load instability is found to expand with increase in inverter deadtime. Subharmonic oscillations of significant amplitude are observed in the steady-state simulated and measured current waveforms, at numerous operating points in the unstable region predicted, confirming the validity of the stability analysis. Furthermore, simulation and experimental results demonstrate that the proposed model is more accurate than an existing small-signal model in predicting the region of instability.

Spin-glass state in nanoparticulate (La0.7Sr0.3MnO3)(1-x) (BaTiO3)(x) solid solutions: Experimental and density-functional studies

We report the transition from robust ferromagnetism to a spin- glass state in nanoparticulate La0.7Sr0.3MnO3 through solid solution with BaTiO3. The field- and temperature-dependent magnetization and the frequency-dependent ac magnetic susceptibility measurements strongly indicate the existence of a spin- glass state in the system, which is further confirmed from memory effect measurements. The breaking of long-range ordering into short-range magnetic domains is further investigated using density-functional calculations. We show that Ti ions remain magnetically inactive due to insufficient electron leakage from La0.7Sr0.3MnO3 to the otherwise unoccupied Ti-d states. This results in the absence of a Mn-Ti-Mn spin exchange interaction and hence the breaking of the long-range ordering. Total-energy calculations suggest that the segregation of nonmagnetic Ti ions leads to the formation of short-range ferromagnetic Mn domains.

Modelling and analysis of an open-loop induction motor drive incorporating the effect of inverter dead-time

The objective of this paper is to study the influence of inverter dead-time on steady as well as dynamic operation of an open-loop induction motor drive fed from a voltage source inverter (VSI). Towards this goal, this paper presents a systematic derivation of a dynamic model for an inverter-fed induction motor, incorporating the effect of inverter dead-time, in the synchronously revolving dq reference frame. Simulation results based on this dynamic model bring out the impact of inverter dead-time on both the transient response and steady-state operation of the motor drive. For the purpose of steady-state analysis, the dynamic model of the motor drive is used to derive a steady-state model, which is found to be non-linear. The steady-state model shows that the impact of dead-time can be seen as an additional resistance in the stator circuit, whose value depends on the stator current. Towards precise evaluation of this dead-time equivalent resistance, an analytical expression is proposed for the same in terms of inverter dead-time, switching frequency, modulation index and load impedance. The notion of dead-time equivalent resistance is shown to simplify the solution of the non-linear steady-state model. The analytically evaluated steady-state solutions are validated through numerical simulations and experiments.

Novel synergistic photocatalytic degradation of antibiotics and bacteria using V-N doped TiO2 under visible light: the state of nitrogen in V-doped TiO2

We report the synthesis of vanadium and nitrogen co-doped TiO2 for photocatalysis mainly emphasizing the state of nitrogen doping into TiO2 in the presence of vanadium ions. Considering the increase in antibiotic resistance developed by microbes due to the excess of pharmaceutical waste in the ecosystem, the photocatalytic activity was measured by degrading an antibiotic, chloramphenicol. A novel experiment was conducted by degrading the antibiotic and bacteria in each other's vicinity to focus on their synergistic photo-degradation by V-N co-doped TiO2. The catalysts were characterized using XRD, DRS, PL, TEM, BET and XPS analysis. Both interstitial and substitutional nitrogen doping were achieved with V-TiO2, showing high efficiency under visible light for antibiotic and bacterial degradation. In addition, the effect of doping concentration of nitrogen and vanadium in TiO2 and catalyst loading was studied thoroughly. Reusability experiments show that the prepared V-N co-doped TiO2 was stable for many cycles.

Effect of temperature on dislocation emission from crack tip for BCC metal Mo

The effect of thermally activated energy on the dislocation emission from a crack tip in BCC metal Mo is simulated in this paper. Based on the correlative reference model on which the flexible displacement boundary scheme is introduced naturally, the simulation shows that as temperature increases the critical stress intensity factor for the first dislocation emission will decrease and the total number of emitted dislocations increase for the same external load. The dislocation velocity and extensive distance among partial dislocations are not sensitive to temperature. After a dislocation emission, two different deformation slates are observed, the stable and unstable deformation states. In the stable deformation slate, the nucleated dislocation will emit from the crack tip and piles up at a distance far away from the crack tip, after that the new dislocation can not be nucleated unless the external loading increases. In the unstable deformation state, a number of dislocations can be emitted from the crack lip continuously under the same external load.

The effect of an insoluble surfactant on the skin friction of a bubble

In this paper, we develop a novel moving mesh method suitable for solving axisymmetric free-boundary problems, including the Marangoni effect induced by surfactant or temperature variation. This method employs a body-fitted grid system where the gas-liquid interface is one line of the grid system. We model the surfactant equation of state with a non-linear Langmuir law, and, for simplicity, we limit ourselves to the situation of an insoluble surfactant. We solve complicated dynamic boundary conditions accurately on the gas-liquid interface in the framework of finite-volume methods. Our method is used to study the effect of a surfactant on the skin friction of a bubble in a uniaxial flow. For the limiting case where the surface diffusivity is zero, the effect of a tangential stress generated by the surface tension gradient, allows us to explain a new phenomenon in high concentration regimes: larger surface tension, but also larger deformation. Furthermore, this condition leads to the formation of boundary layers and flow separation at high Reynolds numbers. The influence of these complex flow patterns is examined. © 2005 Elsevier SAS. All rights reserved.