Ru(4+) ion in CeO(2) (Ce(0.95)Ru(0.05)O(2-delta)): A non-deactivating, non-platinum catalyst for water gas shift reaction

Hydrogen is a clean energy carrier and highest energy density fuel. Water gas shift (WGS) reaction is an important reaction to generate hydrogen from steam reforming of CO. A new WGS catalyst, Ce(1-x)Ru(x)O(2-delta) (0 <= x <= 0.1) was prepared by hydrothermal method using melamine as a complexing agent. The Catalyst does not require any pre-treatment. Among the several compositions prepared and tested, Ce(0.95)Ru(0.05)O(2-delta) (5% Ru(4+) ion substituted in CeO(2)) showed very high WGS activity in terms of high conversion rate (20.5 mu mol.g(-1).s(-1) at 275 degrees C) and low activation energy (12.1 kcal/mol). Over 99% conversion of CO to CO(2) by H(2)O is observed with 100% H(2) selectivity at >= 275 degrees C. In presence of externally fed CO(2) and H(2) also, complete conversion of CO to CO(2) was observed with 100% H(2) selectivity in the temperature range of 305-385 degrees C. Catalyst does not deactivate in long duration on/off WGS reaction cycle due to absence of surface carbon and carbonate formation and sintering of Ru. Due to highly acidic nature of Ru(4+) ion, surface carbonate formation is also inhibited. Sintering of noble metal (Ru) is avoided in this catalyst because Ru remains in Ru(4+) ionic state in the Ce(1-x)Ru(x)O(2-delta) catalyst.

Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta): New water gas shift (WGS) catalysts

Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) and Ce(0.67)Fe(0.33)O(2-delta) have been synthesized by a new low temperature sonochemical method using diethylenetriamine as a complexing agent. Due to the substitution of Fe and Pt ions in CeO(2), lattice oxygen is activated in Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). Hydrogen uptake studies show strong reduction peaks at 125 C in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) against a hydrogen uptake peak at 420 degrees C in Ce(0.67)Fe(0.33)O(2-delta). Fe substituted ceria, Ce(0.67)Fe(0.33)O(2-delta) itself acts as a catalyst for CO oxidation and water gas shift (WGS) reactions at moderate temperatures. The rate of CO conversion in WGS with Pt free Ce(0.65)Fe(0.33)O(2-delta) is 2.8 mu mol g(-1) s(-1) at 450 C and with Pt substituted Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) is 4.05 mu mol g(-1) s(-1) at 275 degrees C. Due to the synergistic interaction of the Pt ion with Ce and Fe ions in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta), the catalyst showed much higher activity for CO oxidation and WGS reactions compared to Ce(0.67)Fe(0.33)O(2-delta). A reverse WGS reaction does not occur over Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). The catalyst also does not deactivate even when operated for a long time. Nearly 100% conversion of CO to CO(2) with 100% H(2) selectivity is observed in WGS reactions even up to 550 degrees C. (C) 2011 Elsevier B.V. All rights reserved.

Improvement of power-system transient stability by phase-shift insertion

Computational studies of the transient stability of a synchronous machine connected to an infinite busbar by a double-circuit transmission line are used to illustrate the effect of relative phase-shift insertion between the machine and its associated power system. This method of obtaining a change in the effective rotor-excitation angle, and thereby the power transfer, is described, together with an outline of possible methods of implementation by a phase-shifting transformer in a power system.

Scheduling identical parallel machines with machine eligibility restrictions to minimize total weighted flowtime in automobile gear manufacturing

In this paper, we address a scheduling problem for minimizing total weighted flowtime, observed in automobile gear manufacturing. Specifically, the bottleneck operation of the pre-heat treatment stage of gear manufacturing process has been dealt with in scheduling. Many real-life scenarios like unequal release times, sequence dependent setup times, and machine eligibility restrictions have been considered. A mathematical model taking into account dynamic starting conditions has been proposed. The problem is derived to be NP-hard. To approach the problem, a few heuristic algorithms have been proposed. Based on planned computational experiments, the performance of the proposed heuristic algorithms is evaluated: (a) in comparison with optimal solution for small-size problem instances and (b) in comparison with the estimated optimal solution for large-size problem instances. Extensive computational analyses reveal that the proposed heuristic algorithms are capable of consistently yielding near-statistically estimated optimal solutions in a reasonable computational time.

Ultrasound Assisted Optical Tomography: Estimation of phase Shift experienced by photon on transit through US insonified region for detection of breast tumor

A Monte Carlo model of ultrasound modulation of multiply scattered coherent light in a highly scattering media has been carried out for estimating the phase shift experienced by a photon beam on its transit through US insonified region. The phase shift is related to the tissue stiffness, thereby opening an avenue for possible breast tumor detection. When the scattering centers in the tissue medium is exposed to a deterministic forcing with the help of a focused ultrasound (US) beam, due to the fact that US-induced oscillation is almost along particular direction, the direction defined by the transducer axis, the scattering events increase, thereby increasing the phase shift experienced by light that traverses through the medium. The phase shift is found to increase with increase in anisotropy g of the medium. However, as the size of the focused region which is the region of interest (ROI) increases, a large number of scattering events take place within the ROI, the ensemble average of the phase shift (Delta phi) becomes very close to zero. The phase of the individual photon is randomly distributed over 2 pi when the scattered photon path crosses a large number of ultrasound wavelengths in the focused region. This is true at high ultrasound frequency (1 MHz) when mean free path length of photon l(s) is comparable to wavelength of US beam. However, at much lower US frequencies (100 Hz), the wavelength of sound is orders of magnitude larger than l(s), and with a high value of g (g 0.9), there is a distinct measurable phase difference for the photon that traverses through the insonified region. Experiments are carried out for validation of simulation results.

Determination of C-13 Chemical Shift Anisotropy Tensors and Molecular Order of 4-Hexyloxybenzoic Acid

4-Alkoxy benzoic acids belong to an important class of thermotropic liquid crystals that are structurally simple and often used as starting materials for many novel mesogens. 4-Hexyloxybenzoic acid (HBA) is a homologue of the same series and exhibits an enantiotropic nematic phase. As this molecule could serve as an ideal model compound, high resolution C-13 NMR studies of HEA in solution, solid, and liquid crystalline phases have been undertaken. In the solid state, two-dimensional separation of undistorted powder patterns by effortless recoupling (2D SUPER) experiments have been carried out to estimate the magnitude of the components of the chemical shift anisotropy (GSA) tensor of all the aromatic carbons. These values have been used subsequently for calculating the orientational order parameters in the liquid crystalline phase. The GSA values computed by density functional theory (DFT) calculations showed good agreement with the 2D SUPER values. Additionally, C-13-H-1 dipolar couplings in the nematic phase have been determined by separated local field (SLF) spectroscopy at various temperatures and were used for computing the order parameters, which compared well with those calculated by using the chemical shifts. It is anticipated that the CSA values determined for MBA would be useful for the assignment of carbon chemical shifts and for the study of order and dynamics of structurally similar novel mesogens in their nematic phases.

Water gas shift reaction over multi-component ceria catalysts

This study reports the activity of ionic substituted bimetallic Cu-Ni-modified ceria and Cu-Fe-modified ceria catalysts for low-temperature water gas shift (WGS) reaction. The catalysts were synthesized in nano-crystalline size by a sonochemical method and characterized by XRD, TEM, XPS, TPR and BET surface analyzer techniques. Due to the ionic substitution of these aliovalent base metals, lattice oxygen in CeO2 is activated and these catalysts show high activity for WGS at low temperature. An increase in the reducibility and oxygen storage capacity of bimetallic substituted CeO2, as evidenced by H-2-TPR experiments, is the primary reason for the higher activity towards WGS reaction. In the absence of feed CO2 and H-2, 100% conversion of CO with 100% H-2 selectivity was observed at 320 degrees C and 380 degrees C, for Cu-Ni-modified ceria and Cu-Fe-modified ceria catalysts. Notably, in the presence of feed H2O. a reverse WGS reaction does not occur over these ceria modified catalysts. A redox reaction mechanism, involving oxidation of CO adsorbed on the metal was developed to correlate the experimental data and determine kinetic parameters. (C) 2012 Elsevier B.V. All rights reserved.

A weighted average-based external clock synchronisation protocol for wireless sensor networks

Wireless Sensor Networks (WSNs) have many application scenarios where external clock synchronisation may be required because a WSN may consist of components which are not connected to each other. In this paper, we first propose a novel weighted average-based internal clock synchronisation (WICS) protocol, which synchronises all the clocks of a WSN with the clock of a reference node periodically. Based on this protocol, we then propose our weighted average-based external clock synchronisation (WECS) protocol. We have analysed the proposed protocols for maximum synchronisation error and shown that it is always upper bounded. Extensive simulation studies of the proposed protocols have been carried out using Castalia simulator. Simulation results validate our above theoretical claim and also show that the proposed protocols perform better in comparison to other protocols in terms of synchronisation accuracy. A prototype implementation of the WICS protocol using a few TelosB motes also validates the above conclusions.

Model independent bounds on the modulus of the pion form factor on the unitarity cut below the omega pi threshold

We calculate upper and lower bounds on the modulus of the pion electromagnetic form factor on the unitarity cut below the omega pi inelastic threshold, using as input the phase in the elastic region known via the Fermi-Watson theorem from the pi pi P-wave phase shift, and a suitably weighted integral of the modulus squared above the inelastic threshold. The normalization at t = 0, the pion charge radius and experimental values at spacelike momenta are used as additional input information. The bounds are model independent, in the sense that they do not rely on specific parametrizations and do not require assumptions on the phase of the form factor above the inelastic threshold. The results provide nontrivial consistency checks on the recent experimental data on the modulus available below the omega pi threshold from e(+)e(-) annihilation and tau-decay experiments. In particular, at low energies the calculated bounds offer a more precise description of the modulus than the experimental data.

A Single-Stage Water-Gas Shift Reaction over Highly Active and Stable Si- and Al-Substituted Pt/CeO2 Catalysts

Ce0.88Si0.1Pt0.02O2-d and Ce0.88Al0.1Pt0.02O2-d catalysts were synthesized by using a low-temperature sonochemical method and characterized by using XRD, TEM, XPS, FTIR, and BET surface analyzer. The catalytic activities of these compounds were investigated for the watergas shift reaction in the temperature range of 140-440 degrees C. The substitution of Si in Ce0.98Pt0.02O2-d increased the releasing capacity of lattice oxygen, whereas the substitution of Al decreased the reducibility of Ce0.98Pt0.02O2-d, as evidenced by hydrogen temperature-programmed reduction studies. However, both the catalysts showed a considerable improvement in terms of activity and stability compared to Ce0.98Pt0.02O2-d. The combined activity measurement and characterization results suggest that the increase in the oxygen vacancy, which acts as a dissociation center for water, is the primary reason for the improvement in the activity of modified Ce0.98Pt0.02O2-d. Both the catalysts are 100?% selective toward H2 production, and approximately 99?% conversion of CO to CO2 was observed at 260 and 270 degrees C for Ce0.88Si0.1Pt0.02O2-d and Ce0.88Al0.1Pt0.02O2-d, respectively. These catalysts do not deactivate during the daily startup/shutdown operations and are sustainable even after prolonged reaction. Notably, these catalysts do not require any pretreatment or activation during startup/shutdown operations.

Spatial Modulation and Space Shift Keying in Single Carrier Communication

Spatial modulation (SM) and space shift keying (SSK) are relatively new modulation techniques which are attractive in multi-antenna communications. Single carrier (SC) systems can avoid the peak-to-average power ratio (PAPR) problem encountered in multicarrier systems. In this paper, we study SM and SSK signaling in cyclic-prefixed SC (CPSC) systems on MIMO-ISI channels. We present a diversity analysis of MIMO-CPSC systems under SSK and SM signaling. Our analysis shows that the diversity order achieved by (n(t), n(r)) SSK scheme and (n(t), n(r), Theta(M)) SM scheme in MIMO-CPSC systems under maximum-likelihood (ML) detection is n(r), where n(t), n(r) denote the number of transmit and receive antennas and Theta(M) denotes the modulation alphabet of size M. Bit error rate (BER) simulation results validate this predicted diversity order. Simulation results also show that MIMO-CPSC with SM and SSK achieves much better performance than MIMO-OFDM with SM and SSK.

Low temperature CO oxidation and water gas shift reaction over Pt/Pd substituted in Fe/TiO2 catalysts

We demonstrate the activity of Ti0.84Pt0.01Fe0.15O2-delta and Ti0.73Pd0.02Fe0.25O2-delta catalysts towards the CO oxidation and water gas shift (VMS) reaction. Both the catalysts were synthesized in the nano crystalline form by a low temperature sonochemical method and characterized by different techniques such as XRD, FT-Raman, TEM, FT-IR, XPS and BET surface analyzer. H-2-TPR results corroborate the intimate contact between noble metal and Fe ions in the both catalysts that facilitates the reducibility of the support. In the absence of feed CO2 and H-2, nearly 100% conversion of CO to CO2 with 100% H-2 selectivity was observed at 300 degrees C and 260 degrees C respectively, for Ti0.84Pt0.01Fe0.15O2-delta and Ti0.73Pd0.02Fe0.25O2-delta catalyst. However, the catalytic performance of Ti0.73Pd0.02Fe0.25O2-delta deteriorates in the presence of feed CO2 and H-2. The change in the support reducibility is the primary reason for the significant increase in the activity for CO oxidation and WGS reaction. The effect of Fe addition was more significant in Ti0.73Pd0.02Fe0.25O2-delta than Ti0.84Pt0.01Fe0.15O2-delta. Based on the spectroscopic evidences and surface phenomena, a hybrid reaction scheme utilizing both surface hydroxyl groups and the lattice oxygen was hypothesized over these catalysts for WGS reaction. The mechanisms based on the formate and redox pathway were used to fit the ldnetic data. The analysis of experimental data shows the redox mechanism is the dominant pathway over these catalysts. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

A weighted average based external clock synchronization protocol for wireless sensor networks

Clock synchronization is an extremely important requirement of wireless sensor networks(WSNs). There are many application scenarios such as weather monitoring and forecasting etc. where external clock synchronization may be required because WSN itself may consists of components which are not connected to each other. A usual approach for external clock synchronization in WSNs is to synchronize the clock of a reference node with an external source such as UTC, and the remaining nodes synchronize with the reference node using an internal clock synchronization protocol. In order to provide highly accurate time, both the offset and the drift rate of each clock with respect to reference node are estimated from time to time, and these are used for getting correct time from local clock reading. A problem with this approach is that it is difficult to estimate the offset of a clock with respect to the reference node when drift rate of clocks varies over a period of time. In this paper, we first propose a novel internal clock synchronization protocol based on weighted averaging technique, which synchronizes all the clocks of a WSN to a reference node periodically. We call this protocol weighted average based internal clock synchronization(WICS) protocol. Based on this protocol, we then propose our weighted average based external clock synchronization(WECS) protocol. We have analyzed the proposed protocols for maximum synchronization error and shown that it is always upper bounded. Extensive simulation studies of the proposed protocols have been carried out using Castalia simulator. Simulation results validate our theoretical claim that the maximum synchronization error is always upper bounded and also show that the proposed protocols perform better in comparison to other protocols in terms of synchronization accuracy. A prototype implementation of the proposed internal clock synchronization protocol using a few TelosB motes also validates our claim.

Field extension code based dispersion matrices for coherently detected space-time shift keying

Motivated by the recent Coherent Space-Time Shift Keying (CSTSK) philosophy, we construct new dispersion matrices for rotationally invariant PSK signaling sets. Given a specific PSK signal constellation, the dispersion matrices of the existing CSTSK scheme were chosen by maximizing the mutual information over randomly generated sets of dispersion matrices. In this contribution we propose a general method for constructing a set of structured dispersion matrices for arbitrary PSK signaling sets using Field Extension (FE) codes and then study the attainable Symbol Error Rate (SER) performance of some example constructions. We demonstrate that the proposed dispersion scheme is capable of outperforming the existing dispersion arrangement at medium to high SNRs.