New Insights into Selective Heterogeneous Nucleation of Metal Nanoparticles on Oxides by Microwave-Assisted Reduction: Rapid Synthesis of High-Activity Supported Catalysts

Microwave-based methods are widely employed to synthesize metal nanoparticles on various substrates. However, the detailed mechanism of formation of such hybrids has not been addressed. In this paper, we describe the thermodynamic and kinetic aspects of reduction of metal salts by ethylene glycol under microwave heating conditions. On the basis of this analysis, we identify the temperatures above which the reduction of the metal salt is thermodynamically favorable and temperatures above which the rates of homogeneous nucleation of the metal and the heterogeneous nucleation of the metal on supports are favored. We delineate different conditions which favor the heterogeneous nucleation of the metal on the supports over homogeneous nucleation in the solvent medium based on the dielectric loss parameters of the solvent and the support and the metal/solvent and metal/support interfacial energies. Contrary to current understanding, we show that metal particles can be selectively formed on the substrate even under situations where the temperature of the substrate Is lower than that of the surrounding medium. The catalytic activity of the Pt/CeO(2) and Pt/TiO(2) hybrids synthesized by this method for H(2) combustion reaction shows that complete conversion is achieved at temperatures as low as 100 degrees C with Pt-CeO(2) catalyst and at 50 degrees C with Pt-TiO(2) catalyst. Our method thus opens up possibilities for rational synthesis of high-activity supported catalysts using a fast microwave-based reduction method.

Fracture analysis of concrete using singular fractal functions with lattice beam network and confirmation with acoustic emission study

In the present study singular fractal functions (SFF) were used to generate stress-strain plots for quasibrittle material like concrete and cement mortar and subsequently stress-strain plot of cement mortar obtained using SFF was used for modeling fracture process in concrete. The fracture surface of concrete is rough and irregular. The fracture surface of concrete is affected by the concrete's microstructure that is influenced by water cement ratio, grade of cement and type of aggregate 11-41. Also the macrostructural properties such as the size and shape of the specimen, the initial notch length and the rate of loading contribute to the shape of the fracture surface of concrete. It is known that concrete is a heterogeneous and quasi-brittle material containing micro-defects and its mechanical properties strongly relate to the presence of micro-pores and micro-cracks in concrete 11-41. The damage in concrete is believed to be mainly due to initiation and development of micro-defects with irregularity and fractal characteristics. However, repeated observations at various magnifications also reveal a variety of additional structures that fall between the `micro' and the `macro' and have not yet been described satisfactorily in a systematic manner [1-11,15-17]. The concept of singular fractal functions by Mosolov was used to generate stress-strain plot of cement concrete, cement mortar and subsequently the stress-strain plot of cement mortar was used in two-dimensional lattice model [28]. A two-dimensional lattice model was used to study concrete fracture by considering softening of matrix (cement mortar). The results obtained from simulations with lattice model show softening behavior of concrete and fairly agrees with the experimental results. The number of fractured elements are compared with the acoustic emission (AE) hits. The trend in the cumulative fractured beam elements in the lattice fracture simulation reasonably reflected the trend in the recorded AE measurements. In other words, the pattern in which AE hits were distributed around the notch has the same trend as that of the fractured elements around the notch which is in support of lattice model. (C) 2011 Elsevier Ltd. All rights reserved.

Atomic Scale Fluctuations Govern Brittle Fracture and Cavitation Behavior in Metallic Glasses

We perform atomistic simulations on the fracture behavior of two typical metallic glasses, one brittle (FeP) and the other ductile (CuZr), and show that brittle fracture in the FeP glass is governed by an intrinsic cavitation mechanism near crack tips in contrast to extensive shear banding in the ductile CuZr glass. We show that a high degree of atomic scale spatial fluctuations in the local properties is the main reason for the observed cavitation behavior in the brittle metallic glass. Our study corroborates with recent experimental observations of nanoscale cavity nucleation found on the brittle fracture surfaces of metallic glasses and provides important insights into the root cause of the ductile versus brittle behavior in such materials.

Influence of substrate temperature on the properties of oxygen‐ion‐assisted deposited CeO2 films

Substrate temperature and ion bombardment during deposition have been observed to modify significantly the optical and structural properties of dielectric thin films. Single‐layer films of CeO2 have been deposited by electron beam evaporation with simultaneous oxygen‐ion bombardment using a Kaufman broad beam ion source and maintaining the substrates at elevated temperature. A systematic study has been made on the influence of (a) substrate temperature in the range ambient to 300 °C, (b) ion energy in the range 300–700 eV, and (c) ion current density 100–220 μA/cm2 on optical properties such as refractive index, extinction coefficient, inhomogeneity, packing density, and structural properties. The refractive index increased with in increase in substrate temperature: ion energy up to 600 eV and ion current density. Homogeneous, absorption free and high index (2.48) films have been obtained at 600 eV, 220 μA/cm2 and at substrate temperature of 300 °C. The packing density of the films was observed to be unity for the same deposition conditions. Substrate temperature with simultaneous ion bombardment modified the structure of the films from highly ordered to fine grain structure.

Indium flux, growth temperature and RF power induced effects in InN layers grown on GaN/Si substrate by plasma-assisted MBE

In the present work, we report the growth of wurtzite InN epilayers on GaN/Si (1 1 1) substrate by plasma-assisted molecular beam epitaxy (PAMBE). The growth parameters such as indium flux, substrate temperature and RF power affect the crystallographic and morphological properties of InN layers, which were evaluated using high resolution X-ray diffraction (HRXRD) analysis and atomic force microscopy (AFM). It is found that excess indium (In) concentrations and surface roughness were increased with increase in In flux and growth temperature. The intensity of HRXRD (0 0 0 2) peak, corresponding to c-axis orientation has been increased and full width at half maxima (FWHM) has decreased with increase in RF power. It was found that highly c-axis oriented InN epilayers can be grown at 450 degrees C growth temperature, 450 W RF power and 1.30 x 10(-7) mbar In beam equivalent pressure (BEP). The energy gap of InN layers grown by optimizing growth conditions was determined by photoluminescence and optical absorption measurement. (C) 2011 Elsevier B.V. All rights reserved.

The influence of Zr layer thickness on contact deformation and fracture in a ZrN-Zr multilayer coating

In order to understand the influence of ductile metal interlayer on the overall deformation behavior of metal/nitride multilayer, different configurations of metal and nitride layers were deposited and tested under indentation loading. To provide insight into the trends in deformation with multilayer spacings, an FEM model with elastic-perfect plastic metal layers alternate with an elastic nitride on top of an elastic-plastic substrate. The strong strain mismatch between the metal and nitride layers significantly alters the stress field under contact loading leading to micro-cracking in the nitride, large tensile stresses immediately below the contact, and a transition from columnar sliding in thin metal films to a more uniform bending and microcracking in thicker coatings.

Fracture analysis of cracked plate panels using NI-MVCCI technique

The objective of this paper is to propose a numerically integrated modified virtual crack closure integral (NI-MVCCI) technique for fracture analysis of cracked plate panels. NI-MVCCI technique is generalized one and the expressions for computing the strain energy release rate (SERR) are independent of the finite element employed. NI-MVCCI technique has been demonstrated for 4-noded, 8-noded (regular and quarter-point) and 9-noded isoparametric finite elements. Numerical studies on fracture analysis of 2-D crack (mode-I and mode-II) problems have been conducted employing these elements. SERR and stress intensity factors (SIF) have been computed for these problems and found to be in good agreement with the respective analytical solutions available in the literature. The appropriate Gauss numerical integration order to be employed for each of these elements for accurate computation of SERR and SIF has been recommended based on the studies.

Removal of Nitrogen Oxides in Diesel Engine Exhaust by Plasma Assisted Molecular Sieves

This paper reports the studies conducted on removal of oxides of nitrogen (NOx) from diesel engine exhaust using electrical discharge plasma combined with adsorbing materials such as molecular sieves. This study is being reported for the first time. The exhaust is taken from a diesel engine of 6 kW under no load conditions. The characteristic behavior of a pulse energized dielectric barrier discharge reactor in the diesel exhaust treatment is reported. The NOx removal was not significant (36%) when the reactor without any packing was used. However, when the reactor was packed with molecular sieves (MS -3A, -4A & -13X), the NOx removal efficiency was increased to 78% particularly at a temperature of 200 °C. The studies were conducted at different temperatures and the results were discussed.