Electronic structure and optical properties of BaMoO(4) powders

Barium molybdate (BaMoO(4)) powders were synthesized by the co-precipitation method and processed in microwave-hydrothermal at 140 degrees C for different times. These powders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis) absorption spectroscopies and photoluminescence (PL) measurements. XRD patterns and FT-Raman spectra showed that these powders present a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 850.4 cm(-1), which is associated to the Mo-O antisymmetric stretching vibrations into the [MoO(4)] clusters. UV-vis absorption spectra indicated a reduction in the intermediary energy levels within band gap with the processing time evolution. First-principles quantum mechanical calculations based on the density functional theory were employed in order to understand the electronic structure (band structure and density of states) of this material. The powders when excited with different wavelengths (350 nm and 488 nm) presented variations. This phenomenon was explained through a model based in the presence of intermediary energy levels (deep and shallow holes) within the band gap. (C) 2009 Elsevier B.V. All rights reserved.

A new processing method of CaZn(2)(OH)(6)center dot 2H(2)O powders: Photoluminescence and growth mechanism

In this communication, we report on the formation of calcium hexahydroxodizincate dehydrate, CaZn(2)(OH)(6)center dot 2H(2)O (CZO) powders under microwave-hydrothermal (MH) conditions. These powders were analyzed by X-ray diffraction (XRD), Field-emission gum scanning electron microscopy (FEG-SEM), ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns confirmed that the pure CZO phase was obtained after MH processing performed at 130 degrees C for 2 h. FEG-SEM micrographs indicated that the morphological modifications as well as the growth of CZO microparticles are governed by Ostwald-ripening and coalescence mechanisms. UV-vis spectra showed that this material have an indirect optical band gap. The pure CZO powders exhibited an yellow PL emission when excited by 350 nm wavelength at room temperature. (C) 2009 Elsevier Masson SAS. All rights reserved.

Formation of beta-nickel hydroxide plate-like structures under mild conditions and their optical properties

Nanostructural beta-nickel hydroxide (beta-Ni(OH)(2)) plates were prepared using the microwave hydrothermal (MH) method at a low temperature and short reaction times. An ammonia solution was employed as the coordinating agent, which reacts with [Ni(H(2)O)(6)](2+) to control the growth of beta-Ni(OH)(2) nuclei. A trigonal beta-Ni(OH)(2) single phase was observed by X-ray diffraction (XRD) analyses, and the crystal cell was constructed with structural parameters and atomic coordinates obtained from Rietveld refinement. Field emission scanning electron microscopy (FE-SEM) images revealed that the samples consisted of hexagonal-shaped nanoplates with a different particle size distribution. Broad absorption bands assigned as transitions of Ni(2+) in oxygen octahedral sites were revealed by UV-vis spectra. Photoluminescence (PL) properties observed with a maximum peak centered in the blue-green region were attributed to different defects, which were produced during the nucleation process. We present a growth process scheme of the beta-Ni(OH)(2) nanoplates. (C) 2011 Elsevier Inc. All rights reserved.

Effect of Different Solvent Ratios (Water/Ethylene Glycol) on the Growth Process of CaMoO(4) Crystals and Their Optical Properties

In this paper, calcium molybdate (CaMoO(4)) crystals (meso- and nanoscale) were synthesized by the coprecipitation method using different solvent volume ratios (water/ethylene glycol). Subsequently, the obtained suspensions were processed in microwave-assisted hydrothermal/solvothermal systems at 140 degrees C for 1 h. These meso- and nanocrystals processed were characterized by X-ray diffraction (X R I)), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR). ultraviolet visible (UV-vis) absorption spectroscopies, held-emission gun scanning electron microscopy (FEG-SEM). transmission electron microscopy (TEM). and photoluminescence (PL) measurements. X RI) patterns and FT-Raman spectra showed that these meso- and nanocrystals have a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 827 cm(-1), which is associated with the Mo-O anti-symmetric stretching vibrations into the [MoO(4)] clusters. FEG-SEM micrographs indicated that the ethylene glycol concentration in the aqueous solution plays an important role in the morphological evolution of CaMoO(4) crystals. High-resolution TEM micrographs demonstrated that the mesocrystals consist of several aggregated nanoparticles with electron diffraction patterns of monocrystal. In addition, the differences observed in the selected area electron diffraction patterns of CaMoO(4) crystals proved the coexistence of both nano- and mesostructures, First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were employed in order to understand the band structure find density of states For the CaMoO(4). UV-vis absorption measurements evidenced a variation in optical band gap values (from 3.42 to 3.72 cV) for the distinct morphologies. The blue and green PI. emissions observed in these crystals were ascribed to the intermediary energy levels arising from the distortions on the [MoO(4)] clusters clue to intrinsic defects in the lattice of anisotropic/isotropic crystals.

Factorial design to optimize microwave-assisted synthesis of FDU-1 silica with a new triblock copolymer

The synthesis of FDU-1 silica with large cage-like mesopores prepared with a new triblock copolymer Vorasurf 504 (R) (Eo)(38)(BO)(46)(EO)(38) was developed. The hydrothermal treatment temperature, the dissolution of the copolymer in ethanol, the HCl concentration, the solution stirring time and the hydrothermal treatment time in a microwave oven were evaluated with factorial design procedures. The dissolution in ethanol is important to produce a material with better porous morphology. Increases in the hydrothermal temperature (100 degrees C) and HCl concentration (2 M) improved structural, textural and chemical properties of the cubic ordered mesoporous silica. Also, longer times induced better physical and chemical property characteristics. (C) 2010 Elsevier Inc. All rights reserved.

Morphology and Blue Photoluminescence Emission of PbMoO(4) Processed in Conventional Hydrothermal

PbMoO(4) micro-octahedrons were prepared by the coprecipitation method at room temperature without the presence of surfactants and processed in a conventional hydrothermal at different temperatures (from 60 to 120 degrees C) for 10 min. These micro-octahedrons were structurally characterized by X-ray diffraction (XRD) and micro-Raman (MR) spectroscopy, and its morphology was investigated by field-emission gun scanning electron microscopy (FEG-SEM). The optical properties were analyzed by ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns and MR spectra confirmed that the PbMoO(4) micro-octahedrons are characterized by a scheelite-type tetragonal structure. FEG-SEM micrographs points, out that these structures present a polydisperse particle size distribution in consequence of a predominant growth mechanism via aggregation of particles. In addition, it was observed that the hydrothermal conditions favored a spontaneous formation of micro-octahedrons interconnected along a common crystallographic orientation (oriented-attachment), resulting in self-organized structures. An intense blue PL emission at room temperature was observed in these micro-octahedrons when they were excited with a 350 nm wavelength. The origin of the PL emissions as well as its intensity variations are explained by means of a model based on both distorted [MoO(4)] and [PbO(8)] clusters into the lattice.

Investigation of some dielectric properties of phosphate glasses doped with iron oxides, by a microwave technique

The effects of iron ions on dielectric properties of lithium sodium phosphate glasses were studied by non-usual, fast and non-destructive microwave techniques. The dielectric constant (epsilon`). insertion loss (L) and microwave absorption spectra (microwave response) of the selected glass system xFe(2)O(3)center dot(1 - x)(50P(2)O5 center dot 25Li(2)O center dot 25Na(2)O), being x = 0, 3, 6, ....,15 expressed in mol.%, were investigated. The dielectric constant of the samples was investigated at 9.00 GHz using the shorted-line method (SLM) giving the minimum value of epsilon` = 2.10 +/- 0.02 at room temperature, and increasing further with x, following a given law. It was observed a gradual increasing slope Of E in the temperature range of 25 <= t <= 330 degrees C, at the frequency of 9.00 GHz. Insertion loss (measured at 9.00 GHz) and measurements of microwave energy attenuation, at frequencies ranging from 8.00 to 12.00 GHz were also studied as a function of iron content in the glass samples. (C) 2009 Elsevier Ltd. All rights reserved.

Magnetoresistance oscillations in triple quantum wells under microwave irradiation

The interference of magneto-intersubband oscillations and microwave-induced resistance oscillations is studied in high-density triple quantum wells. We give an introduction into magnetotransport in trilayer systems and focus on photoresistance measurements. The power and frequency dependence of the observed magnetoresistance oscillations can be described by the inelastic mechanism of photoresistance, generalized to the three-subband case. (C) 2009 Elsevier B.V. All rights reserved.

Microwave induced magnetoresistance oscillations and inelastic scattering time in double quantum wells

The interference of microwave-induced resistance oscillations and magneto-intersubband oscillations in double quantum wells exposed to a continuous microwave irradiation is under study. By comparing experimental and theoretical magnetoresistance traces at different temperatures, we confirm that the inelastic mechanism of photoresistance explains our observations up to T similar or equal to 4 K. For higher temperatures, our results suggest a deviation of the inelastic scattering time tau(in) from the predicted T(-2) dependence. (C) 2009 Elsevier B.V. All rights reserved.

Integer and fractional microwave induced resistance oscillations in a 2D system with moderate mobility

We report on integer and fractional microwave-induced resistance oscillations in a 2D electron system with high density and moderate mobility, and present results of measurements at high microwave intensity and temperature. Fractional microwave-induced resistance oscillations occur up to fractional denominator 8 and are quenched independently of their fractional order. We discuss our results and compare them with existing theoretical models. (C) 2009 Elsevier B.V. All rights reserved.

MAGNETORESISTANCE OSCILLATIONS IN DOUBLE QUANTUM WELLS UNDER MICROWAVE IRRADIATION

We report in detail oscillatory magnetoresistance in double quantum wells under microwave irradiation. The experimental investigation contains measurements of frequency, power and temperature dependence. In theory, the observed interference oscillations are explained in terms of the influence of subband coupling on the frequency-dependent photoinduced part of the electron distribution function. Thus, the magnetoresistance shows the interference of magneto-intersubband and conventional microwave induced resistance oscillations.

Vanadium Pentoxide Nanostructures: An Effective Control of Morphology and Crystal Structure in Hydrothermal Conditions

A systematic study was made of the synthesis of V(2)O(5)center dot nH(2)O nanostructures, whose morphologies, crystal structure, and amount of water molecules between the layered structures were regulated by strictly controlling the hydrothermal treatment variables. The synthesis involved a direct hydrothermal reaction between V(2)O(5) and H(2)O(2), without the addition of organic surfactant or inorganic ions. The experimental results indicate that high purity nanostructures can be obtained using this simple and clean synthetic route. Oil the basis of a study of hydrothermal treatment variables such as reaction temperature and time, X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) revealed that it was possible to obtain nanoribbons of the V(2)O(5)center dot nH(2)O monoclinic phase and nanowires or nanorods of the V(2)O(5)center dot nH(2)O orthorhombic phase. Thermal gravimetric analysis (TGA) shows also that the water content in the Structure call be controlled at appropriate hydrothermal conditions. Concerning the oxidation state of the vanadium atoms of as-obtained samples, a mixed-valence state composed of V(4+) and V(5+) was observed ill the V(2)O(5)center dot nH(2)O monoclinic phase, while the valence of the vanadium atoms was preferentially 5+ in the V(2)O(5)center dot nH(2)O orthorhombic phase. The X-ray absorption near-edge structure (XANES) results also indicated that the local structure of vanadium possessed a higher degree of symmetry in the V(2)O(5)center dot nH(2)O monoclinic phase.

Hierarchical Assembly of CaMoO(4) Nano-Octahedrons and Their Photoluminescence Properties

Hierarchical assemblies of CaMoO4 (CM) nano-octahedrons were obtained by microwave-assisted hydrothemial synthesis at 120 degrees C for different times. These structures were structurally, morphologically and optically characterized by X-ray diffraction, micro-Raman spectroscopy, field-emission gun scanning electron microscopy, ultraviolet-visible absorption spectroscopy and photoluminescence measurements. First-principle calculations have been carried out to understand the structural and electronic order-disorder effects as a function of the particle/region size. Supercells of different dimensions were constructed to simulate the geometric distortions along both they and z planes of the scheelite structure. Based on these experimental results and with the help of detailed structural simulations, we were able to model the nature of the order-disorder in this important class of materials and discuss the consequent implications on its physical properties, in particular, the photoluminescence properties of CM nanocrystals.

HYDROTHERMAL REE FLUOROCARBONATE MINERALIZATION AT BARRA DO ITAPIRAPUA, A MULTIPLE STOCKWORK CARBONATITE, SOUTHERN BRAZIL

The Barra do Itapirapua ( BIT) carbonatites in southern Brazil belong to the final stages of the Early Cretaceous alkaline rock - carbonatite magmatism of the Ponta Grossa Arch Province. The BIT complex is a dyke and vein stockwork in which four main carbonatitic phases are recognized, mainly magnesiocarbonatites and ferrocarbonatites. These carbonatites are generally overprinted by pervasive hydrothermal events. The C-O stable isotopic data indicate re-equilibration under hydrothermal conditions at temperatures between 375 and 80 degrees C. Significant amounts of REE fluorocarbonate minerals, relatively Sr- and Th-rich, were deposited. Syntaxy between synchysite-(Ce) and parisite-(Ce) is very common owing to the similarity in structures, with alternating (001) layers of (CeF), (CO3) and (Ca). However, bastnasite-(Ce) occurs as individual crystals, overgrown by the synchysite and parisite polycrystals. Textural and chemical reactions between the REE fluorocarbonates provide insights into the mobility of rare-earth elements during fluid-rock interaction. The BIT complex is considered to be of potential economic interest for production of the rare-earth concentrates.

The direct determination of rare earth elements in basaltic and related rocks using ICP-MS: Testing the efficiency of microwave oven sample decomposition procedures

Tests are described showing the results obtained for the determination of REE and the trace elements Rb, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th and U with ICP-MS methodology for nine basaltic reference materials, and thirteen basalts and amphibolites from the mafic-ultramafic Niquelandia Complex, central Brazil. Sample decomposition for the reference materials was performed by microwave oven digestion (HF and HNO(3), 100 mg of sample), and that for the Niquelandia samples also by Parr bomb treatment (5 days at 200 degrees C, 40 mg of sample). Results for the reference materials were similar to published values, thus showing that the microwave technique can be used with confidence for basaltic rocks. No fluoride precipitates were observed in the microwave-digested solutions. Total recovery of elements, including Zr and Hf, was obtained for the Niquelandia samples, with the exception of an amphibolite. For this latter sample, the Parr method achieved a total digestion, but not so the microwave decomposition; losses, however, were observed only for Zr and Hf, indicating difficulty in dissolving Zr-bearing minerals by microwave acid attack.