An XPS study on oxidation states of Pt and its alloys with Co and Cr and its relevance to electroreduction of oxygen

Cathodic reduction of oxygen in fuel cells is known to be enhanced on platinum alloys in relation to the platinum metal. The higher performance of the platinum alloys is as a result of the improved oxygen-reduction kinetics on the alloys but there is hardly any increase in the electrode platinum-surface-areas for the platinum alloys as compared to the platinum metal, and thus the higher performance is solely due to the enhanced electrocatalytic activity of the alloys as compared to the platinum metal. The present X-ray photoelectron spectroscopic (XPS) study on carbon-supported Pt, Pt–Co and Pt–Co–Cr electrocatalysts suggests the presence of a relatively lower Pt-oxide content on the alloys. The X-ray powder diffraction patterns for these electrocatalysts show that while the carbon-supported platinum electrocatalyst has a face-centered cubic (fcc) phase, carbon-supported Pt–Co and Pt–Co–Cr electrocatalysts exhibit a face-centered tetragonal (fct) phase. But, Pt electrocatalyst has a lower particle-size and, hence, a higher dispersion. Previous studies have shown higher activities on the Pt-alloys than on Pt, and have attributed it to changes in the electronic and structural characteristics of Pt. These changes can be correlated with the lower oxidation-state of Pt sites, as found in this study.

Crack formation due to annealing of Al2O3 films grown on Si(100) by MOCVD

We report crack formation in alumina films grown on Si(100), caused by annealing in a controlled oxidizing ambient. The films were grown in a low-pressure CVD reactor, using aluminium acetylacetonate as precursor. High purity argon and nitrous oxide were employed as carrier and oxidizing gas, respectively. The films were characterized by optical microscopy and SEM/EDAX. The proportion and chemical nature of the heteroatoms, namely C and H, incorporated into the films from the precursor, were characterized by XPS, and FTIR. As-deposited films do not exhibit any cracks, while post-deposition annealing results in cracks. Apart from the delamination of the films, annealing in nitrous oxide ambient leads to an unusual crack geometry, which we term the “railway-track”. These twin cracks are very straight and run parallel to each other for as much as several millimeters. Often, two such linear tracks meet at exactly 90°. Between some of these tracks lie bullet-like structures with very sharp tips, oriented in a specific direction. As cracks are generally activated by residual stress, both thermal and intrinsic, the origins of the stresses that generate these linear cracks are discussed. The redistribution of stress, arising from the removal of C and H during annealing, will also be discussed. An attempt has been made to correlate the formation of cracks with the crystal structure of the film.

A Systematic Approach to Synthesis of Verification Test-suites for Modular SoC Designs

Verification is one of the important stages in designing an SoC (system on chips) that consumes upto 70% of the design time. In this work, we present a methodology to automatically generate verification test-cases to verify a class of SoCs and also enable re-use of verification resources created from one SoC to another. A prototype implementation for generating the test-cases is also presented.

Explorations en route to synthesis of tashironins: singlet oxygen cycloaddition to 1,3-cyclopentadienes embedded within allo-cedrane framework

In an approach directed toward a tashironin based complex natural product, efficacy of the singlet oxygen mediated [4+2]-cycloaddition to a tetracyclic cyclopentadiene has been evaluated to install the key cis-1,4-dihydroxy functionality. (C) 2011 Elsevier Ltd. All rights reserved.

An Accurate Model for EESM and its Application to Analysis of CQI Feedback Schemes and Scheduling in LTE

The Effective Exponential SNR Mapping (EESM) is an indispensable tool for analyzing and simulating next generation orthogonal frequency division multiplexing (OFDM) based wireless systems. It converts the different gains of multiple subchannels, over which a codeword is transmitted, into a single effective flat-fading gain with the same codeword error rate. It facilitates link adaptation by helping each user to compute an accurate channel quality indicator (CQI), which is fed back to the base station to enable downlink rate adaptation and scheduling. However, the highly non-linear nature of EESM makes a performance analysis of adaptation and scheduling difficult; even the probability distribution of EESM is not known in closed-form. This paper shows that EESM can be accurately modeled as a lognormal random variable when the subchannel gains are Rayleigh distributed. The model is also valid when the subchannel gains are correlated in frequency or space. With some simplifying assumptions, the paper then develops a novel analysis of the performance of LTE's two CQI feedback schemes that use EESM to generate CQI. The comprehensive model and analysis quantify the joint effect of several critical components such as scheduler, multiple antenna mode, CQI feedback scheme, and EESM-based feedback averaging on the overall system throughput.

Time delay to firing of a triggered vacuum gap with barium titanate in trigger gap

The time delay to the firing of a triggered vacuum gap (t.v.g.) containing barium titanate in the trigger gap is investigated as a function of the main gap voltage, main gap length, trigger pulse duration, trigger current and trigger voltage. The time delay decreases steadily with increasing trigger current and trigger voltage until it reaches saturation. The effect of varying the main gap length and voltage on the time delay is not strong. Before `conditioning�¿ the t.v.g. two groups of time delays, long (>100�¿s) and short (<10�¿s), are simultaneously observed when a large number of trials are conducted. After conditioning, only the group of short time delays are present. This is attributed to the marked reduction of the resistance of the trigger gap across the surface of the solid dielectric resulting directly from the conditioning effect.

Exciting forces due to interaction of water waves with a submerged sphere in an ice-covered two-layer fluid of finite depth

Scattering of water waves by a sphere in a two-layer fluid, where the upper layer has an ice-cover modelled as an elastic plate of very small thickness, while the lower one has a rigid horizontal bottom surface, is investigated within the framework of linearized water wave theory. The effects of surface tension at the surface of separation is neglected. There exist two modes of time-harmonic waves - the one with lower wave number propagating along the ice-cover and the one with higher wave number along the interface. Method of multipole expansions is used to find the particular solution for the problem of wave scattering by a submerged sphere placed in either of the layers. The exciting forces for vertical and horizontal directions are derived and plotted against different values of the wave number for different submersion depths of the sphere and flexural rigidity of the ice-cover. When the flexural rigidity and the density of the ice-cover are taken to be zero, the numerical results for the exciting forces for the problem with free surface are recovered as particular cases. (C) 2011 Elsevier Ltd. All rights reserved.

Synthesis of zero valent iron nanoparticles and application to removal of arsenic(III) and arsenic(V) from water

Recently nano scale zero valent iron particles (nZVI) have been considered as smart adsorbent for environmental and groundwater remediation. Although several synthetic methods are available for the preparation of nZVI, air stable nZVI are not available for remediation works. Further, challenges demand synthesis of nZVI without stabilizers and capping agents. A modified methodology for the synthesis of air stable nZVI has been developed without any capping agents and characterized by powder X-Ray Diffraction (XRD), Scanning Electron Microscopy Energy-dispersive X-Ray (SEM-EDS), Transmission Electron Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS). The results of the present study suggest that the synthetic nZVI are air-stable over a period of one year and consists of particles of 30-40 nm in diameter. Although a layer of less than 3 am thick oxide/hydroxide is observed by TEM and XPS, it appears to be due to oxidation of outer surface during analysis. Adsorption study has shown that the synthetic nZVI are more effective adsorbent than the commercial nZVI and can remove simultaneously arsenite As-III] and arsenate As-V] from water without prior reduction of As-V to As-III. The removal process is adsorptive rather than precipitative and the removal of As-III is greater than that of As-V.

An approximately H-1-optimal Petrov-Galerkin meshfree method: application to computation of scattered light for optical tomography

Nearly pollution-free solutions of the Helmholtz equation for k-values corresponding to visible light are demonstrated and verified through experimentally measured forward scattered intensity from an optical fiber. Numerically accurate solutions are, in particular, obtained through a novel reformulation of the H-1 optimal Petrov-Galerkin weak form of the Helmholtz equation. Specifically, within a globally smooth polynomial reproducing framework, the compact and smooth test functions are so designed that their normal derivatives are zero everywhere on the local boundaries of their compact supports. This circumvents the need for a priori knowledge of the true solution on the support boundary and relieves the weak form of any jump boundary terms. For numerical demonstration of the above formulation, we used a multimode optical fiber in an index matching liquid as the object. The scattered intensity and its normal derivative are computed from the scattered field obtained by solving the Helmholtz equation, using the new formulation and the conventional finite element method. By comparing the results with the experimentally measured scattered intensity, the stability of the solution through the new formulation is demonstrated and its closeness to the experimental measurements verified.

Anomalous piezoelectric response due to stabilization of two ferroelectric phases in Zr-modified BaTiO3

The lead-free Ba (Ti1-xZrx)O-3 ceramic has shown enhanced piezo-response (d(33)) in a narrow composition interval (0.01 <= x <= 0.03) exhibiting the coexistence of two ferroelectric phases. The system presents two electric-field-dependent-property regimes: (i) a low field regime (E < 1.7 kV mm(-1)) where d(33) is nearly independent of the poling field, and (ii) (E > 1.7 kV mm(-1)) for which d(33) drops sharply. X-ray diffraction studies revealed that the later phenomenon is related to field driven irreversible structural transformation, which tends to drive the system away from an equilibrium two phase state to a nearly single phase metastable state.