Microwave-assisted selective deoxygenation of layer- and chain-containing oxides

Very rapid (within 5 min), selective, single-step deoxygenation of layer- and chain-containing oxides, MoO3, CrO3, V2O5, alpha-VOPO4 . 2H(2)O and Ag6Mo10O33 has been accomplished using graphitic carbon in a microwave-assisted reaction. The products were found to be MoO2, Cr2O3, VO2, VPO4 and a mixture of (Ag + MoO2), respectively. Products were characterised by X-ray diffraction (XRD), differential scanning calorimetry (DSC), IR and electron paramagnetic resonance (EPR) spectroscopies. Although conventional methods of preparing these materials are tedious, the present method is simple, fast and yields very homogeneous products of good crystallinity. Our results reveal that while layer- and chain-containing oxides undergo rapid microwave-assisted carbothermal reduction, the non-layered materials do not. The high structural selectivity of these reactions is suggestive of the topochemical nature of the fast reduction process.

Temperature-dependent photoluminescence of GaN grown on beta-Si3N4/Si (111) by plasma-assisted MBE

Photoluminescence (PL) of high quality GaN epitaxial layer grown on beta-Si3N4/Si (1 1 1) substrate using nitridation-annealing-nitridation method by plasma-assisted molecular beam epitaxy (PA-MBE) was investigated in the range of 5-300 K. Crystallinity of GaN epilayers was evaluated by high resolution X-ray diffraction (HRXRD) and surface morphology by Atomic Force Microscopy (AFM) and high resolution scanning electron microscopy (HRSEM). The temperature-dependent photoluminescence spectra showed an anomalous behaviour with an `S-like' shape of free exciton (FX) emission peaks. Distant shallow donor-acceptor pair (DAP) line peak at approximately 3.285 eV was also observed at 5 K, followed by LO replica sidebands separated by 91 meV. The activation energy of the free exciton for GaN epilayers was also evaluated to be similar to 27.8 +/- 0.7 meV from the temperature-dependent PL studies. Low carrier concentrations were observed similar to 4.5 +/- 2 x 10(17) Cm-3 by measurements and it indicates the silicon nitride layer, which not only acts as a growth buffer layer, but also effectively prevents Si diffusion from the substrate to GaN epilayers. The absence of yellow band emission at around 2.2 eV signifies the high quality of film. The tensile stress in GaN film calculated by the thermal stress model agrees very well with that derived from Raman spectroscopy. (C) 2010 Elsevier B.V. All rights reserved.

Rapid microwave assisted synthesis of hydroxyapatite

A fast, efficient and novel method of preparation of hydroxyapatite using microwaves has been described.

New Massive Gravity and AdS(4) Counterterms

We show that the recently proposed Dirac-Born-Infeld extension of new massive gravity emerges naturally as a counterterm in four-dimensional anti-de Sitter space (AdS(4)). The resulting on-shell Euclidean action is independent of the cutoff at zero temperature. We also find that the same choice of counterterm gives the usual area law for the AdS(4) Schwarzschild black hole entropy in a cutoff-independent manner. The parameter values of the resulting counterterm action correspond to a c = 0 theory in the context of the duality between AdS(3) gravity and two-dimensional conformal field theory. We rewrite this theory in terms of the gauge field that is used to recast 3D gravity as a Chern-Simons theory.

Structural and optical properties of nonpolar (11-20) a-plane GaN grown on (1-102) r-plane sapphire substrate by plasma-assisted molecular beam epitaxy

We report the structural and optical properties of a-plane GaN film grown on r-plane sapphire substrate by plasma-assisted molecular beam epitaxy. High resolution X-ray diffraction was used to determine the out-of-plane and in-plane epitaxial relation of a-plane GaN to r-plane sapphire. Low-temperature photoluminescence emission was found to be dominated by basal stacking faults along with near-band emission. Raman spectroscopy shows that the a-GaN film is of reasonably good quality and compressively strained. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Microwave assisted preparation and sintering of Al2O3, ZrO2 and their composites from metalorganics

Controlled pyrolysis of Al(OBus)(3), Zr(OPrn)(4) and their mixtures in ethyl acetate induced using microwaves of 2.45 GHz frequency has been carried out. Microwave irradiation yields second-stage precursors for the preparation of respective oxides and their composites. It is observed that the microwave irradiation has a directive influence on the morphology of the ultimate oxide products. Al2O3, ZrO2 and the two composites 90% Al2O3-10% ZrO2 and 90% ZrO2-10% Al2O3 are also found to be sintered to very high densities within 35 min of microwave irradiation by the use of beta-SiC as a secondary susceptor.

Microwave Assisted Synthesis and Antimicrobial Study of Schiff Base Vanadium(IV) Complexes of Phenyl Esters of Amino Acids

Schiff base vanadium(IV) complexes of phenyl esters of the two acidic amino acids, i.e., aspartic and glutamic acid, were synthesized. The phenyl esters of these amino acids were synthesized by conventional method whereas the Schiff base vanadium(IV) complexes were synthesized using microwave irradiation. The complexes were characterized by spectroscopic tools such as IR, 1H NMR, mass (ES), ESR, and UV visible spectroscopy. All the complexes were studied for antibacterial and antifungal activity and found to be moderately active.

Synthesis of Ti, Ga, and V nitrides: Microwave-assisted carbothermal reduction and nitridation

A simple, novel, and fast method of preparation of metal nitride powders (GaN, TiN, and VN) using microwave-assisted carbothermal reduction and nitridation has been demonstrated. The procedure uses the respective oxides and amorphous carbon powder as the starting materials. Ammonia gas is found to be more effective in nitridation than high-purity N-2 gas. Complete nitridation is achieved by the use of a slight excess of amorphous carbon. Metals themselves are not found to be effectively nitrided. The products were characterized using XRD, TEM, and SAED and found to possess good crystallinity and phase purity. The method can be of general applicability for the preparation of metal nitrides.

Guest-Assisted Self-assembly of Organostannoxane Nanotubules on a Mica Surface

The reaction of n-BuSn(O)OH](n), and 9-hydroxy-9-fluorenecarboxylic acid in the presence of p-X-C6H4-OH (X = F, Br) afforded hydroxyl-rich hexameric organostannoxane prismanes. The crystal structures of these prismanes reveal guest-assisted supramolecular structures. Self-assembly of these compounds on a mica surface affords organooxotin nanotubules.

Ultrafast Microwave-Assisted Route to Surfactant-Free Ultrafine Pt Nanoparticles on Graphene: Synergistic Co-reduction Mechanism and High Catalytic Activity

We demonstrate an ultrafast method for the formation of, graphene supported Pt catalysts by the co-reduction of graphene oxide and Pt salt using ethylene glycol under microwave irradiation conditions. Detailed analysis of the mechanism of formation of the hybrids indicates a synergistic co-reduction mechanism whereby the presence of the Pt ions leads to a faster reduction of GO and the presence of the defect sites on the reduced GO serves as anchor points for the heterogeneous nucleation of Pt. The resulting hybrid consists of ultrafine nanoparticles of Pt uniformly distributed on the reduced GO susbtrate. We have shown that the hybrid exhibits good catalytic activity for methanol oxidation and hydrogen conversion reactions. The mechanism is general and applicable for the synthesis of other multifunctional hybrids based on graphene.

Effect of Zr4+-ion substitution in CeO2 on H2O2-assisted degradation of orange G

A series of Pd ion-substituted CeO2-ZrO2 solid solutions were synthesized using the solution combustion technique. H2O2-assisted degradation of orange G was carried out in the presence of the catalysts. The activity of the catalysts was found to increase with the introduction of the second component in the solid solution, as signified by an increase in the rate constants and lowering of activation energy. The study showed the involvement of lattice oxygen and the importance of reducibility of the compound for the reaction. (C) 2011 Elsevier B.V. All rights reserved.

Properties of Al2O3 films prepared by argon ion assisted deposition

Aluminum oxide films have been prepared by ion assisted deposition using argon ions with energy in the range 300 to 1000 eV and current density in the range 50 to 220 μA/cm2. The influence of ion energy and current density on the optical and structural properties has been investigated. The refractive index, packing density, and extinction coefficient are found to be very sensitive to the ion beam parameters and substrate temperatures. The as-deposited films were found to be amorphous and could be transformed into crystalline phase on annealing. However, the crystalline phases were different in films prepared at ambient and elevated substrate temperatures.

Stresses in Ion Assisted Deposited Oxide Thih Films

Thin films of Ceria, Titania and Ziroonia have been prepared using Ion Assisted Deposition(IAD). The energy of ions was varied between 0 and 1 keV and current densities up to 220 μA/cm were used. It was found that the stress behaviour is dependent on ion species, i.e. Argon or Oxygen, ion energy and current density and substrate temperature apart from the material. While oeria files showed tensile stresses under the influence of argon ion bombardment at ambient temperature, they showed a sharp transition from tensile to compressive stress with increase in substrate temperature. When bombarded with oxygen ions they showed a transition from tensile to compressive stress with increase in energy. The titania films deposited with oxygen ions, on the other hand showed purely tensile stresses. Zirconia films deposited with oxygen ions, however, showed a transition from tensile to compressive stress.

Surfactant-mediated Synthesis of Functional Metal Oxide Nanostructures via Microwave Irradiation-assisted Chemical Synthesis

Nanostructured materials have attracted considerable interest in recent years due to their properties which differ strongly from their bulk phase and potential applications in nanoscale electronic and optoelectronic devices. Metal oxide nanostructures can be synthesized by variety of different synthesis techniques developed in recent years such as thermal decomposition, sol-gel technique, chemical coprecipitation, hydrothermal process, solvothermal process, spray pyrolysis, polyol process etc. All the above processes go through a tedious synthesis procedure followed by prolonged heat treatment at elevated temperature and are time consuming. In the present work we describe a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant, without the use of any templates The method is simple, inexpensive, and helps one to prepare nanostructures in a very simple way, and in a very short time, measured in minutes. The synthesis procedure employs high quality metalorganic complexes (typically -diketonates) featuring a direct metal-to-oxygen bond in its molecular structure. The complex is dissolved in a suitable solvent, often with a surfactant added, and the solution then subjected to microwave irradiation in a domestic microwave oven operating at 2.45 GHz frequency with power varying from 160-800 W, from a few seconds to a few minutes, leading to the formation of corresponding metal oxides. This method has been used successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with the change of different parameters such as microwave power, irradiation time, appropriate solvent, surfactant type and concentration. Cationic, anionic, nonionic and polymeric surfactants have been used to generate a variety of nanostructures. Even so, to remove the surfactant, there is either no need of heat treatment or a very brief exposure to heat suffices, to yield highly pure and crystalline oxide materials as prepared. By adducting the metal complexes, the shape of the nanostructures can be controlled further. In this manner, very well formed, single-crystalline, hexagonal nanorods and nanotubes of ZnO have been formed. Adducting the zinc complex leads to the formation of tapered ZnO nanorods with a very fine tip, suitable for electron emission applications. Particle size and their monodispersity can be controlled by a suitable choice of a precursor complex, the surfactant, and its concentration. The resulting metal oxide nanostructures have been characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, photoluminescence, and electron emission measurements.

Indium Nitride Nanometric-Objects on c-Sapphire Grown by Plasma-Assisted Molecular Beam Epitaxy

The indium nitride (InN)-based nanometric-objects were grown directly on a c-sapphire substrate by using plasma-assisted molecular beam epitaxy (PAMBE) at different substrate temperatures. High resolution X-ray diffraction (HRXRD) reveals the InN (0002) reflection and full width at half maximum (FWHM) found to be decreased with increasing the growth temperature. The size, height and density of the grown nanometric-objects studied by scanning electron microscopy (SEM) has remarkable differences, evidencing the decisive role of substrate temperature. Photoluminescence (PL) studies revealed that the emission energy is shifted towards the higher side from the bulk value, i.e., a blue shift in the PL spectra was observed. The temperature dependence of the PL peak position shows an ``S-shaped'' emission energy shift, which can be attributed to the localization of carriers in the nanometric-objects.