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.

A low cost approach for the fabrication of microwave phase shifter on laminates

This paper presents a simple and low cost fabrication approach using extended printed circuit board processing techniques for an electrostatically actuated phase shifter on a common microwave laminate. This approach uses 15 mu m thin copper foils for realizing the bridge structures as well as for a spacer. A polymeric thin film deposited by spin coating and patterned using lithographic process is used as a dielectric layer to improve the reliability of the device. The prototype of the phase shifter for X-band operation is fabricated and tested for electrical and electromechanical performance parameters. The realized devices have a figure of merit of 70 degrees/dB for a maximum applied bias potential of 85 V. Since these phase shifters can be conveniently fabricated directly on microwave substrates used for feed distribution networks of phased arrays, the overall addition in cost, dimensions and processing for including these phase shifters in these arrays is minimal.

Dielectric response of BaZrO3/BaTiO3 and SrTiO3/BaZrO3 superlattices

Dielectric materials with high tunability, low loss, and desired range of permittivity are an attractive class of materials for a variety of applications in microwave components such as tunable filters, phase shifters, antennas, etc. In this article, we have investigated the low frequency dielectric properties of BaZrO3/BaTiO3 and SrTiO3/BaZrO3 superlattices of varying modulation periods for the potential application toward electrically tunable devices. The dielectric response of the superlattices as a function of temperature revealed remarkable stability for both types of superlattices, with no observed dielectric anomalies within that range. Dielectric losses were also nominally low with minimal variation within the measured temperature range. Sufficiently high tunability of ∼ 40% was observed for the BaZrO3/BaTiO3 superlattices at the lowest individual layer thicknesses. In comparison, the SrTiO3/BaZrO3 superlattices showed a minimum tunability for lowest period structures. It showed maximum tunability of ∼ 20% at 10 kHz and room temperature at an intermediate dimension of 3.85 nm periodicity superlattice. The tunability value degraded with increasing as well as decreasing periodicities for the SrTiO3/BaZrO3 superlattices. The dielectric response has been explained on the basis of size effects, interlayer coupling between dissimilar materials, domain contribution, and depolarizing electric fields.

Improved microwave dielectric properties of (Mg1-(x+y)CaxLay)(Ti1-yAly)O3 ceramics

Phase-singular solids of the composition, (Mg1−(x+y) Cax Lay)(Ti1−yAly)O3 (x = 0 to 0.88; y = 0.05 to 0.35) having the cubic perovskite-type structure were prepared by the substitution of La3+ and Al3+ in equivalent quantities which brought about complete miscibility between MgTiO3 and CaTiO3. These ceramics showed relative permittivities of 16.5 to 50 (at 6 GHz) with increasing Ca content, high Q values of 10 000 to 30 000 and retained near-zero temperature coefficients in permittivity at optimum y values. Their dielectric characteristics are better accountable in terms of the positional disorder rather than the tolerance factor of perovskite structure.

Microwave cavity resonators. Some perturbation effects and their applications

Lagrange's equation is utilized to show the analogy of a lossless microwave cavity resonator with the conventional LC network. A brief discussion on the resonant frequencies of a microwave cavity resonator and the two degenerate companion modes H01 and E11 appearing in a cavity is given. The first order perturbation theory of a small deformation of the wall of a cavity is discussed. The effects of perturbation, such as the change in the resonant frequency and the Q of a cavity, the change in the electromagnetic field configurations and hence mixing of modes are also discussed. An expression for the coupling coefficient between the two degenerate modes H01 and E11 is derived with the help of the field equations. Results indicate that in the absence of perturbation the above two degenerate modes can co-exist without losing their individual identities. Several applications of the perturbation theory, such as the measurement of the dielectric properties of matter, study of ferromagnetic resonance, etc., are described.

Nanocrystalline TiO(2) preparation by microwave route and nature of anatase-rutile phase transition in nano TiO(2)

Nanopowders of TiO(2) has been prepared using a microwave irradiation-assisted route, starting from a metalorganic precursor, bis(ethyl-3-oxo-butanoato)oxotitanium (IV), [TiO(etob)(2)](2). Polyvinylpyrrolidone (PVP) was used as a capping agent. The as-prepared amorphous powders crystallize into anatase phase, when calcined. At higher calcination temperature, the rutile phase is observed to form in increasing quantities as the calcination temperature is raised. The structural and physicochemical properties were measured using XRD, FT-IR, SEM, TEM and thermal analyses. The mechanisms of formation of nano-TiO(2) from the metal-organic precursor and the irreversible phase transformation of nano TiO(2) from anatase to rutile structure at higher temperatures have been discussed. It is suggested that a unique step of initiation of transformation takes place in Ti(1/2)O layers in anatase which propagates. This mechanism rationalizes several key observations associated with the anatase rutile transformation.

Towards a broadband chirped pulse Fourier transform microwave spectrometer

This article gives a brief review of microwave spectroscopy and the experimental techniques used for obtaining microwave spectrum of molecules and complexes since 1950s. It presents a brief summary of the pulsed nozzle Fourier transform microwave (PNFTMW) spectrometer, fabricated in our laboratory, and discusses some of the important results obtained using the spectrometer. The most significant among the results from this spectrometer is the direct structural determination of weakly bound complexes involving H2O/H2S. These have challenged the conventional wisdom on hydrogen bonding leading us to propose a modern definition for the same through IUPAC. The limitations of the PNFTMW spectrometer and the need for the new chirped pulse Fourier transform microwave spectrometer are discussed as well. Moreover, preliminary results from our laboratory on generating a 1 A mu s chirped pulse of 1 GHz bandwidth are given.

Low temperature charge transport and microwave absorption of carbon coated iron nanoparticles-polymer composite films

In this paper, the low temperature electrical conductivity and microwave absorption properties of carbon coated iron nanoparticles-polyvinyl chloride composite films are investigated for different filler fractions. The filler particles are prepared by the pyrolysis of ferrocene at 980 degrees C and embedded in polyvinyl chloride matrix. The high resolution transmission electron micrographs of the filler material have shown a 5 nm thin layer graphitic carbon covering over iron particles. The room temperature electrical conductivity of the composite film changes by 10 orders of magnitude with the increase of filler concentration. A percolation threshold of 2.2 and an electromagnetic interference shielding efficiency (EMI SE) of similar to 18.6 dB in 26.5-40 GHz range are observed for 50 wt% loading. The charge transport follows three dimensional variable range hopping conduction. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis and characterization of nano silicon and titanium nitride powders using atmospheric microwave plasma technique

We have demonstrated a simple, scalable and inexpensive method based on microwave plasma for synthesizing 5 to 10 g/h of nanomaterials. Luminescent nano silicon particles were synthesized by homogenous nucleation of silicon vapour produced by the radial injection of silicon tetrachloride vapour and nano titanium nitride was synthesized by using liquid titanium tetrachloride as the precursor. The synthesized nano silicon and titanium nitride powders were characterized by XRD, XPS, TEM, SEM and BET. The characterization techniques indicated that the synthesized powders were indeed crystalline nanomaterials.

ZnO-Au nanohybrids by rapid microwave-assisted synthesis for CO oxidation

We present a green method for the synthesis of ZnO-Au hybrids using an ultrafast microwave-based technique. This method provides good control over the nucleation of the metal nanoparticles on the oxide support, which governs the morphology and microstructure of the hybrids. The hybrids exhibit good catalytic activity for CO oxidation compared to similar hybrids reported in the literature. Detailed XPS investigation reveals the presence of Au-Zn and Au-O bonds at the interface. This surface doping leads to the formation of anionic and cationic Au sites that contribute to the enhanced activity. Our method is general and can be applied for designing other supported catalysts with controlled interfaces.

Estimation of heavy rainfall during cyclonic storms from microwave observations using nonlinear approach over Indian Ocean

In this study, an effort has been made to study heavy rainfall events during cyclonic storms over Indian Ocean. This estimate is based on microwave observations from tropical rainfall measuring mission (TRMM) Microwave Imager (TMI). Regional scattering index (SI) developed for Indian region based on measurements at 19-, 21- and 85-GHz brightness temperature and polarization corrected temperature (PCT) at 85 GHz have been utilized in this study. These PCT and SI are collocated against Precipitation Radar (PR) onboard TRMM to establish a relationship between rainfall rate, PCT and SI. The retrieval technique using both linear and nonlinear regressions has been developed utilizing SI, PCT and the combination of SI and PCT. The results have been compared with the observations from PR. It was found that a nonlinear algorithm using combination of SI and PCT is more accurate than linear algorithm or nonlinear algorithm using either SI or PCT. Statistical comparison with PR exhibits the correlation coefficients (CC) of 0.68, 0.66 and 0.70, and root mean square error (RMSE) of 1.78, 1.96 and 1.68 mm/h from the observations of SI, PCT and combination of SI and PCT respectively using linear regressions. When nonlinear regression is used, the CC of 0.73, 0.71, 0.79 and RMSE of 1.64, 1.95, 1.54 mm/h are observed from the observations of SI, PCT and combination of SI and PCT, respectively. The error statistics for high rain events (above 10 mm/h) shows the CC of 0.58, 0.59, 0.60 and RMSE of 5.07, 5.47, 5.03 mm/h from the observations of SI, PCT and combination of SI and PCT, respectively, using linear regression, and on the other hand, use of nonlinear regression yields the CC of 0.66, 0.64, 0.71 and RMSE of 4.68, 5.78 and 4.02 mm/h from the observations of SI, PCT and combined SI and PCT, respectively.

Microwave-assisted, surfactant-free synthesis of air-stable copper nanostructures and their SERS study

A simple, rapid, and surfactant-free synthesis of crystalline copper nanostructures has been carried out through microwave irradiation of a solution of copper acetylacetonate in benzyl alcohol. The structures are found to be stable against oxidation in ambient air for several months. High-resolution electron microscopy (SEM and TEM) reveals that the copper samples comprise nanospheres measuring about 150 nm in diameter, each made of copper nanocrystals similar to 7 nm in extension. The nanocrystals are densely packed into spherical aggregates, the driving force being minimization of surface area and surface energy, and are thus immune to oxidation in ambient air. Such aggregates can also be adherently supported on SiO2 and Al2O3 when these substrates are immersed in the irradiated solution. The air-stable copper nanostructures exhibit surface enhanced Raman scattering, as evidenced by the detection of 4-mercaptobenzoic acid at 10(-6) M concentrations.

Multi-Port Network Approach for the Analysis of Dual Band Fractal Microstrip Antennas

The multiport network approach is extended to analyze the behavior of microstrip fractal antennas. The capacitively fedmicrostrip square ring antenna has the side opposite to the feed arm replaced with a fractal Minkowski geometry. Dual frequency operation is achieved by suitably choosing the indentation of this fractal geometry. The width of the two sides adjacent to this is increased to further control the resonant characteristics and the ratio of the two resonance frequencies of this antenna. The impedance matrix for the multiport network model of this antenna is simplified exploiting self-similarity of the geometry with greater accuracy and reduced analysis time. Experimentally validated results confirm utility of the approach in analyzing the input characteristics of similar multi-frequency fractal microstrip antennas with other fractal geometries.

Studies on Ultra Wideband Triangular Patch Antennas for Imaging Applications

This paper presents simulation and experimental studies on the characterization of ultra wideband antennas for imaging applications. Various configurations of antennas were simulated for their time and frequency domain characteristics with special emphasis on flat responses for group delay and gain versus frequency. Parametric studies reported here showed that locating the capacitive feed strip near the vertex of the triangle gave better response in these respects. An antenna with operating frequency from 2.9GHz to 4.1GHz was fabricated and measured.