Synthesis of nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) solid solution exhibiting high CO oxidation and water gas shift activity

Nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) has been synthesized using a low temperature sonication method and characterized using XRD, TEM, XPS and H-2-TPR. The potential application of both the solid solutions has been explored as exhaust catalysts by performing CO oxidation. The addition of Si- and Fe-in Ce0.95Ru0.05O2-delta greatly enhanced the reducibility of Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe), as indicated by the H-2-TPR study. The oxygen storage capacity has been used to correlate surface oxygen reactivity to the CO oxidation activity. Both the compounds reversibly release lattice oxygen and exhibit excellent CO oxidation activity with 99% conversion below 200 degrees C. A bifunctional reaction mechanism involving CO oxidation by the extraction of lattice oxygen and rejuvenation of oxide vacancy with gas feed O-2 has been used to correlate experimental data. The performance of both the solid solutions has also been investigated for energy application by performing the water gas shift reaction. The present catalysts are highly active and selective towards the hydrogen production and a lack of methanation activity is an important finding of present study.

Determination of favorable inter-particle interactions for formation of substitutionally ordered solid phases from a binary mixture of oppositely charged colloidal suspensions

The solid phase formed by a binary mixture of oppositely charged colloidal particles can be either substitutionally ordered or substitutionally disordered depending on the nature and strength of interactions among the particles. In this work, we use Monte Carlo molecular simulations along with the Gibbs-Duhem integration technique to map out the favorable inter-particle interactions for the formation of substitutionally ordered crystalline phases from a fluid phase. The inter-particle interactions are modeled using the hard core Yukawa potential but the method can be easily extended to other systems of interest. The study obtains a map of interactions depicting regions indicating the type of the crystalline aggregate that forms upon phase transition.

A multichannel sampling method for 2-D finite-rate-of-innovation signals

We address the problem of sampling and reconstruction of two-dimensional (2-D) finite-rate-of-innovation (FRI) signals. We propose a three-channel sampling method for efficiently solving the problem. We consider the sampling of a stream of 2-D Dirac impulses and a sum of 2-D unit-step functions. We propose a 2-D causal exponential function as the sampling kernel. By causality in 2-D, we mean that the function has its support restricted to the first quadrant. The advantage of using a multichannel sampling method with causal exponential sampling kernel is that standard annihilating filter or root-finding algorithms are not required. Further, the proposed method has inexpensive hardware implementation and is numerically stable as the number of Dirac impulses increases.

Wave propagation in stiffened structures using spectrally formulated finite element

In this work, the wave propagation analysis of built-up composite structures is performed using frequency domain spectral finite elements, to study the high frequency wave responses. The paper discusses basically two methods for modeling stiffened structures. In the first method, the concept of assembly of 2D spectral plate elements is used to model a built-up structure. In the second approach, spectral finite element method (SFEM) model is developed to model skin-stiffener structures, where the skin is considered as plate element and the stiffener as beam element. The SFEM model developed using the plate-beam coupling approach is then used to model wave propagation in a multiple stiffened structure and also extended to model the stiffened structures with different cross sections such as T-section, I-section and hat section. A number of parametric studies are performed to capture the mode coupling, that is, the flexural-axial coupling present in the wave responses.

On the zeta function of a periodic-finite-type shift

Periodic-finite-type shifts (PFT's) are sofic shifts which forbid the appearance of finitely many pre-specified words in a periodic manner. The class of PFT's strictly includes the class of shifts of finite type (SFT's). The zeta function of a PET is a generating function for the number of periodic sequences in the shift. For a general sofic shift, there exists a formula, attributed to Manning and Bowen, which computes the zeta function of the shift from certain auxiliary graphs constructed from a presentation of the shift. In this paper, we derive an interesting alternative formula computable from certain ``word-based graphs'' constructed from the periodically-forbidden word description of the PET. The advantages of our formula over the Manning-Bowen formula are discussed.

Revisiting borylanilines: unique solid-state structures and insight into photophysical properties

The structure and photophysical properties of two known borylanilines, 4-(dimesitylboryl)aniline (1) and 4-(dimesitylboryl)-3,5-dimethylaniline (2), have been investigated. 1 and 2 have similar donor and acceptor centers but differ in their molecular conformations. Compounds 1 and 2 have been structurally characterized, and they exhibit a rare form of intermolecular N-H - - -pi electrostatic interactions. The structure and photophysical properties of 1 and 2 are discussed in the context of computational results.

Decode-and-forward relay beamforming for secrecy with finite-alphabet input

In this letter, we compute the secrecy rate of decode-and-forward (DF) relay beamforming with finite input alphabet of size M. Source and relays operate under a total power constraint. First, we observe that the secrecy rate with finite-alphabet input can go to zero as the total power increases, when we use the source power and the relay weights obtained assuming Gaussian input. This is because the capacity of an eavesdropper can approach the finite-alphabet capacity of 1/2 log(2) M with increasing total power, due to the inability to completely null in the direction of the eavesdropper. We then propose a transmit power control scheme where the optimum source power and relay weights are obtained by carrying out transmit power (source power plus relay power) control on DF with Gaussian input using semi-definite programming, and then obtaining the corresponding source power and relay weights which maximize the secrecy rate for DF with finite-alphabet input. The proposed power control scheme is shown to achieve increasing secrecy rates with increasing total power with a saturation behavior at high total powers.

Interdiffusion and solid solution strengthening in Ni-Co-Pt and Ni-Co-Fe ternary systems

Diffusion couple experiments are conducted in Co-Ni-Pt system at 1200 degrees C and in Co-Ni-Fe system at 1150 degrees C, by coupling binary alloys with the third element. Uphill diffusion is observed for both Co and Ni in Pt rich corner of the Co-Ni-Pt system, whereas in the Co-Ni-Fe system, it is observed for Co. Main and cross interdiffusion coefficients are calculated at the composition of intersection of two independent diffusion profiles. In both the systems, the main interdiffusion coefficients are positive over the whole composition range and the cross interdiffusion coefficients show both positive and negative values at different regions. Hardness measured by performing the nanoindentations on diffusion couples of both the systems shows the higher values at intermediate compositions.

Out of equilibrium plasticity dynamics and the annealing of supersolidity in solid He-4

We present a numerical study of a continuum plasticity field coupled to a Ginzburg-Landau model for superfluidity. The results suggest that a supersolid fraction may appear as a long-lived transient during the time evolution of the plasticity field at higher temperatures where both dislocation climb and glide are allowed. Supersolidity, however, vanishes with annealing. As the temperature is decreased, dislocation climb is arrested and any residual supersolidity due to incomplete annealing remains frozen. Our results may provide a resolution of many perplexing issues concerning a variety of experiments on bulk solid He-4.

Lead-free piezoelectric system (Na0.5Bi0.5)TiO3-BaTiO3: Equilibrium structures and irreversible structural transformations driven by electric field and mechanical impact

The structure-property correlation in the lead-free piezoelectric (1 - x)(Na0.5Bi0.5)TiO3-(x)BaTiO3 has been systematically investigated in detail as a function of composition (0 < x <= 0.11), temperature, electric field, and mechanical impact by Raman scattering, ferroelectric, piezoelectric measurement, x-ray, and neutron powder diffraction methods. Although x-ray diffraction study revealed three distinct composition ranges characterizing different structural features in the equilibrium state at room temperature: (i) monoclinic (Cc) + rhombohedral (R3c) for the precritical compositions, 0 <= x <= 0.05, (ii) cubiclike for 0.06 <= x <= 0.0675, and (iii) morphotropic phase boundary (MPB) like for 0.07 <= x < 0.10, Raman and neutron powder diffraction studies revealed identical symmetry for the cubiclike and the MPB compositions. The cubiclike structure undergoes irreversible phase separation by electric poling as well as by pure mechanical impact. This cubiclike phase exhibits relaxor ferroelectricity in its equilibrium state. The short coherence length (similar to 50A degrees) of the out-of-phase octahedral tilts does not allow the normal ferroelectric state to develop below the dipolar freezing temperature, forcing the system to remain in a dipolar glass state at room temperature. Electric poling helps the dipolar glass state to transform to a normal ferroelectric state with a concomitant enhancement in the correlation length of the out-of-phase octahedral tilt.

Effect of Ti concentration on the growth of Nb3Sn between solid Nb(Ti) and liquid Sn

The change in the growth rate of the Nb3Sn product phase because of Ti addition is studied for solid Nb(Ti)-liquid Sn interactions. The growth rate increased from no Ti to 1 at.% and 2 at.% of Ti in Nb, and the activation energy decreased from 221 kJ/mol to 146 kJ/mol. Based on the estimated values, the role of grain boundary and lattice diffusion is discussed in light of the possibility of increased grain boundary area and point defects such as antisites and vacancies.

Remoulded shear strength at plastic and semi-solid states

The undrained shear strength of remoulded soils is of great concern in geotechnical engineering applications. This study aims to develop a reliable approach for determining the undrained shear strength of remoulded fine-grained soils, through the use of index test results, at both the plastic and semi-solid states of consistency. Experimental investigation and subsequent analysis involving a number of fine-grained soils of widely varying plasticity and geological origin have led to a two-parameter linear model of the relationship between logarithm of remoulded undrained shear strength and liquidity index. The numerical values of the parameters are found to be dependent to a lesser extent on the soil group and to a greater extent on the soil state. Based on the values of regression coefficient, ranking index and ranking distance, it seems that the relationship represents the experimental results well. It may be pointed out that the possibility of such a relationship in the semi-solid state of a soil has not been explored in the past. It is also shown that the shear strength at the plastic limit is about 32-34 times that at the liquid limit.

Polymorphic phase boundaries and enhanced piezoelectric response in extended composition range in the lead free ferroelectric BaTi1-xZrxO3

Neutron powder diffraction study of Ba(Ti1-xZrx)O-3 at close composition intervals has revealed coexistence of ferroelectric phases: orthorhombic (Amm2) + tetragonal (P4mm) for 0.02 <= x <= 0.05 and rhombohedral (R3m) + orthorhombic (Amm2) for 0.07 <= x < 0.09. These compositions exhibit relatively enhanced piezoelectric properties as compared to their single phase counterparts outside this composition region, confirming the polymorphic phase boundary nature of the phase coexistence regions. (C) 2013 AIP Publishing LLC.

Solid-liquid transition in polydisperse Lennard-Jones systems

We study melting of a face-centered crystalline solid consisting of polydisperse Lennard-Jones spheres with Gaussian polydispersity in size. The phase diagram reproduces the existence of a nearly temperature invariant terminal polydispersity (delta(t) similar or equal to 0.11), with no signature of reentrant melting. The absence of reentrant melting can be attributed to the influence of the attractive part of the potential upon melting. We find that at terminal polydispersity the fractional density change approaches zero, which seems to arise from vanishingly small compressibility of the disordered phase. At constant temperature and volume fraction the system undergoes a sharp transition from crystalline solid to the disordered amorphous or fluid state with increasing polydispersity. This has been quantified by second- and third-order rotational invariant bond orientational order, as well as by the average inherent structure energy. The translational order parameter also indicates a similar sharp structural change at delta similar or equal to 0.09 in case of T* = 1.0, phi = 0.58. The free energy calculation further supports the sharp nature of the transition. The third-order rotationally invariant bond order shows that with increasing polydispersity, the local cluster favors a more icosahedral arrangement and the system loses its local crystalline symmetry. Interestingly, the value of structure factor S(k) of the amorphous phase at delta similar or equal to 0.10 (just beyond the solid-liquid transition density at T* = 1) becomes 2.75, which is below the value of 2.85 required for freezing given by the empirical Hansen-Verlet rule of crystallization, well known in the theory of freezing.

Novel piezoelectric thin film impact sensor: application in non-destructive material discrimination

We report on the design, development, and performance study of a packaged piezoelectric thin film impact sensor, and its potential application in non-destructive material discrimination. The impact sensing element employed was a thin circular diaphragm of flexible Phynox alloy. Piezoelectric ZnO thin film as an impact sensing layer was deposited on to the Phynox alloy diaphragm by RF reactive magnetron sputtering. Deposited ZnO thin film was characterized by X-ray diffraction (XRD), Atomic Force Microscopy (AFM), and Scanning Electron Microscopy (SEM) techniques. The d(31) piezoelectric coefficient value of ZnO thin film was 4.7 pm V-1, as measured by 4-point bending method. ZnO film deposited diaphragm based sensing element was properly packaged in a suitable housing made of High Density Polyethylene (HDPE) material. Packaged impact sensor was used in an experimental set-up, which was designed and developed in-house for non-destructive material discrimination studies. Materials of different densities (iron, glass, wood, and plastic) were used as test specimens for material discrimination studies. The analysis of output voltage waveforms obtained reveals lots of valuable information about the impacted material. Impact sensor was able to discriminate the test materials on the basis of the difference in their densities. The output response of packaged impact sensor shows high linearity and repeatability. The packaged impact sensor discussed in this paper is highly sensitive, reliable, and cost-effective.