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.

The influence of temperature and strain rate on the deformation response and microstructural evolution during hot compression of a titanium alloy Ti-6Al-4V-0.1B

Hot deformation behavior of a hypoeutectic Ti-6Al-4V-0.1B alloy in (alpha + beta) phase field is investigated in the present study with special reference to flow response, kinetics and microstructural evolution. For a comparison, the base alloy Ti-6Al-4V was also studied under identical conditions. Dynamic recovery of alpha phase occurs at low temperatures while softening due to globularization and/or dynamic recrystallization dominates at high temperatures irrespective of boron addition. Microstructural features for both the alloys display bending and kinking of alpha lamellae for near alpha test temperatures. Unlike Ti-6Al-4V, no sign of instability formation was observed in Ti-6Al-4V-0.1B for any deformation condition except for cavitation around TiB particles, due to deformation incompatibility and strain accumulation at the particle-matrix interface. The absence of macroscopic instabilities and early initiation of softening mechanisms as a result of boron addition has been attributed to microstructural features (e.g. refined prior beta grain and alpha colony size, absence of grain boundary alpha layer, presence of TiB particles at prior beta boundaries, etc.) of the respective alloys prior to deformation. (C) 2012 Elsevier B.V. All rights reserved.

Urea-based constructs readily amplify and attenuate nonlinear optical activity in response to H-bonding and anion recognition

Urea-based molecular constructs are shown for the first time to be nonlinear optically (NLO) active in solution. We demonstrate self-assembly triggered large amplification and specific anion recognition driven attenuation of the NLO activity. This orthogonal modulation along with an excellent nonlinearity-transparency trade-off makes them attractive NLO probes for studies related to weak self-assembly and anion transportation by second harmonic microscopy.

The Role of Strain Rate Response on Tribological Behavior of Metals

In an effort to study the role of strain rate response on the tribological behavior of metals, room temperature experiments were conducted by sliding commercially pure titanium and a-iron pins against an H-11 die steel flats of various surface textures. The steel flat surface textures were specifically prepared to allow for imposing varying amounts of strain rates at the contacting interface during sliding motion. In the experiments, it was observed that titanium (a harder material than iron) formed a transfer layer on H-11 steel surface textures that produced higher strain rates. In contrast, the titanium pins abraded the steel surfaces that produced lower strain rates. The iron pins were found to abrade the H-11 steel surface regardless of the surface texture characteristics. This unique tribological behavior of titanium is likely due to the fact that titanium undergoes adiabatic shear banding at high strain rates, which creates pathways for lower resistance shear planes. These shear planes lead to fracture and transfer layer formation on the surface of the steel flat, which ultimately promotes a higher strain rate of deformation at the asperity level. Iron does not undergo adiabatic shear banding and thus more naturally abrades the surfaces. Overall, the results clear indicated that a materials strain rate response can be an important factor in controlling the tribological behavior of a plastically deforming material at the asperity level. DOI: 10.1115/1.4007675]

Dual emissive borane-BODIPY dyads: molecular conformation control over electronic properties and fluorescence response towards fluoride ions

Facile synthesis of two new dimesitylboryl appended BODIPYs is reported. The two dyads have similar fluorescent chromophores but differ in their molecular conformations. They exhibit dual fluorescence, intramolecular energy transfer between boryl and BODIPY chromophores and different fluorescence responses (emission enhancement and quenching) upon fluoride binding.

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.

Sensory-organ-like response determines the magnetism of zigzag-edged honeycomb nanoribbons

We present an analytical effective theory for the magnetic phase diagram for zigzag-edge terminated honeycomb nanoribbons described by a Hubbard model with an interaction parameter U. We show that the edge magnetic moment varies as ln U and uncover its dependence on the width W of the ribbon. The physics of this owes its origin to the sensory-organ-like response of the nanoribbons, demonstrating that considerations beyond the usual Stoner-Landau theory are necessary to understand the magnetism of these systems. A first-order magnetic transition from an antiparallel orientation of the moments on opposite edges to a parallel orientation occurs upon doping with holes or electrons. The critical doping for this transition is shown to depend inversely on the width of the ribbon. Using variational Monte Carlo calculations, we show that magnetism is robust to fluctuations. Additionally, we show that the magnetic phase diagram is generic to zigzag-edge terminated nanostructures such as nanodots. Furthermore, we perform first-principles modeling to show how such magnetic transitions can be realized in substituted graphene nanoribbons. DOI: 10.1103/PhysRevB.87.085412

Effect of frequency on seismic response of reinforced soil slopes in shaking table tests

This paper studies the effect of frequency of base shaking on the dynamic response of unreinforced and reinforced soil slopes through a series of shaking table tests. Slopes were constructed using clayey sand and geogrids were used for reinforcing the slopes. Two different slope angles 45 degrees and 60 degrees were used in tests and the quantity and location of reinforcement is varied in different tests. Acceleration of shaking is kept constant as 0.3 g in all the tests to maximize the response and the frequency of shaking was 2 Hz, 5 Hz and 7 Hz in different tests. The slope is instrumented with ultrasonic displacement sensors and accelerometers at different elevations. The response of different slopes is compared in terms of the deformation of the slope and acceleration amplifications measured at different elevations. It is observed that the displacements at all elevations increased with increase in frequency for all slopes, whereas the effect of frequency on acceleration amplifications is not significant for reinforced slopes. Results showed that the acceleration and displacement response is not increasing proportionately with the increase in the frequency, suggesting that the role of frequency in the seismic response is very important. Reinforced slopes showed lesser displacements compared to unreinforced slopes at all frequency levels. (C) 2012 Elsevier Ltd. All rights reserved.

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.

Correlation between enhanced lattice polarizability and high piezoelectric response in BiScO3-PbTiO3

Piezoelectric and ex situ electric-field induced structural studies were carried out on closely spaced compositions in the morphotropic phase boundary region of (1 - x) PbTiO3-(x)BiScO3. While the common approach of zero field structural analysis failed to provide a unique relationship between the anomalous piezoresponse of x = 0.3725 and structural factor(s), ex situ study of electric-field induced structural changes revealed that the composition exhibiting the highest piezoelectric response is the one which also exhibits significantly enhanced polarizability of the lattices of both coexisting (monoclinic and tetragonal) phases. The enhanced lattice polarizability manifests as a significant fraction of the monoclinic phase transforming irreversibly to the tetragonal phase after electric poling. DOI: 10.1103/PhysRevB.87.064106

Nanostructured Pd modified Ni/CeO2 catalyst for water gas shift and catalytic hydrogen combustion reaction

Nanostructured Pd-modified Ni/CeO2 catalyst was synthesized in a single step by solution combustion method and characterized by XRD, TEM, XPS, TPR and BET surface analyzer techniques. The catalytic performance of this compound was investigated by performing the water gas shift (WGS) and catalytic hydrogen combustion (CHC) reaction. The present compound is highly active and selective (100%) toward H-2 production for the WGS reaction. A lack of CO methanation activity is an important finding of present study and this is attributed to the ionic substitution of Pd and Ni species in CeO2. The creation of oxide vacancies due to ionic substitution of aliovalent ions induces dissociation of H2O that is responsible for the improved catalytic activity for WGS reaction. The combined H-2-TPR and XPS results show a synergism exists among Pd, Ni and ceria support. The redox reaction mechanism was used to correlate experimental data for the WGS reaction and a mechanism involving the interaction of adsorbed H-2 and O-2 through the hydroxyl species was proposed for CHC reaction. The parity plot shows a good correspondence between the experimental and predicted reaction rates. (c) 2012 Elsevier B.V. All rights reserved.

Automatic road extraction using high resolution satellite images based on Level Set and Mean Shift methods

Analysis of high resolution satellite images has been an important research topic for urban analysis. One of the important features of urban areas in urban analysis is the automatic road network extraction. Two approaches for road extraction based on Level Set and Mean Shift methods are proposed. From an original image it is difficult and computationally expensive to extract roads due to presences of other road-like features with straight edges. The image is preprocessed to improve the tolerance by reducing the noise (the buildings, parking lots, vegetation regions and other open spaces) and roads are first extracted as elongated regions, nonlinear noise segments are removed using a median filter (based on the fact that road networks constitute large number of small linear structures). Then road extraction is performed using Level Set and Mean Shift method. Finally the accuracy for the road extracted images is evaluated based on quality measures. The 1m resolution IKONOS data has been used for the experiment.

Tribological response of soft materials sliding against hard surface textures at various numbers of cycles

In the present investigation, various kinds of textures were attained on the steel surfaces. Roughness of the textures was varied using different grits of emery papers or polishing powders. Pins made of pure Al, Al-4Mg alloy and pure Mg were then slid against prepared steel plate surfaces at various numbers of cycles using an inclined pin-on-plate sliding tester. Tests were conducted at a sliding velocity of 2mms(-1) in ambient conditions under both dry and lubricated conditions. Normal loads were increased up to 110N during the tests. The morphologies of the worn surfaces of the pins and the formation of transfer layer on the counter surfaces were observed using a scanning electron microscope. Surface roughness parameters of the plate were measured using an optical profilometer. In the experiments, it was observed that the coefficient of friction and formation of a transfer layer (under dry and lubricated conditions) only depended on surface texture during the first few sliding cycles. The steady-state variation in the coefficient of friction under both dry and lubrication conditions was attributed to the self-organisation of texture of the surfaces at the interface during sliding. Copyright (C) 2012 John Wiley & Sons, Ltd.

Experiments on thermal response of low aspect ratio packed beds at high Reynolds numbers with varying inflow temperature

An experimental study for transient temperature response of low aspect ratio packed beds at high Reynolds numbers for a free stream with varying inlet temperature is presented. The packed bed is used as a compact heat exchanger along with a solid propellant gas-generator, to generate room temperature gases for use in applications such as control actuation and air bottle pressurization. Packed beds of lengths similar to 200 mm and 300 mm were characterized for packing diameter based Reynolds numbers, Re-d ranging from 0.6 x 10(4) to 8.5 x 10(4). The solid packing used in the bed consisted of circle divide 9.5 mm and circle divide 5 mm steel spheres with suitable arrangements to eliminate flow entrance and exit effects. The ratios of packed bed diameter to packing diameter for 9.5 mm and 5 mm sphere packing were similar to 9.5 and 18 respectively, with the average packed bed porosities around 0.4. Gas temperatures were measured at the entry, exit and at three axial locations along centre-line in the packed beds. The solid packing temperature was measured at three axial locations in the packed bed. An average Nusselt number correlation of the form Nu(d) = 3.91Re(d)(05) for Re-d range of 10(4) is proposed. For engineering applications of packed beds such as pebble bed heaters, thermal storage systems, and compact heat exchangers a simple procedure is suggested for calculating unsteady gas temperature at packed bed exit for packing Biot number Bi-d < 0.1. (C) 2012 Elsevier Inc. All rights reserved.