Structural and spectroscopic study of oxyfluoride glasses and glass-ceramics using europium ion as a structural probe

Transparent oxyfluoride glasses and beta-PbF(2) nanocrystals containing glass-ceramics were prepared with varying Eu(3+) content (0.3, 0.4, 0.5 and 0.6%). The effect of Eu(3+) content on the preparation of glass-ceramics was investigated. From differential scanning calorimetry, the T(x)-T(g)(T(x)-temperature of the onset of crystallization; T(g)-glass transition temperature) parameter for glasses has shown slight variation, and an exothermic peak near T(g) called the ceramization temperature (T(c)) has been observed. Heat treatments were performed at this temperature to obtain transparent glass-ceramics containing beta-PbF(2) nanocrystals, identified by x-ray diffraction. Heat treatments for different periods of time were performed and were observed to be very important in the control of the crystal size and of the crystallization rate. Based upon the absorption spectra, the scattering level due to the presence of beta-PbF(2) nanocrystals in the glass-ceramics was observed to be similar to that for the mother glasses. Detailed analysis of emission spectra and decay time measurements led to the identification of Eu(3+) ions as the beta-PbF(2) crystalline phase. Excitation spectra at 70 K show the interaction of Eu(3+) ions with the fluorogermanate network.

Density functional theory study on the structural and electronic properties of low index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems

The present study is concerned with the structural and electronic properties of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory at the B3LYP level has been carried out. Relaxed surface energies, structural characteristics and electronic properties of the (I 10), (0 10), (10 1) and (00) low-index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 models are studied. For, comparison purposes, the bare rutile TiO2 and SnO2 structures are also analyzed and compared with previous theoretical and experimental data. The calculated surface energy for both rutile TiO2 and SnO2 surfaces follows the sequence (110) < (010) < (101) < (001) and the energy increases as (010) < (101) < (110) < (001) and (010) approximate to (110) < (101) < (001) for SnO2/TiO2/SnO2 and TiO2/SnO2/TiO2 composite systems, respectively. SnO2/TiO2/SnO2 presents larger values of surface energy than the individual SnO2 and TiO2 metal oxides and the TiO2/SnO2/TiO2 system renders surface energy values of the same order that the TiO2 and lower than the SnO2. An analysis of the electronic structure of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 systems shows that the main characteristics of the upper part of the valence bands for all the studied surfaces are dominated by the external layers, i.e., by the TiO2 and the SnO2, respectively, and the topology of the lower part of the conduction bands looks like the core layers. There is an energy stabilization of both valence band top and conduction band bottom for (110) and (010) surfaces of the SnO2/TiO2/SnO2 composite system in relation to their core TiO2, whereas an opposite trend is found for the same surfaces of the TiO2/SnO2/TiO2 composite system in relation to the bare SnO2. The present theoretical results may explain the growth of TiO2@SnO2 bimorph composite nanotape.

Structural and Electronic Properties of Lithiated SnO2. A Periodic DFT Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural and vibrational study of cubic Sb2O3 under high pressure

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Small angle X-ray scattering study of structural changes in silica gel modified with organofunctional groups

Silica gel surfaces, organofunctionalized with 2-mercaptobenzimidazole, iminosalicylaldehyde and imidazole groups were examined using the small angle X-ray scattering technique (SAXS). From the scattering intensity data it was concluded that particles have a uniform size after the coupling reaction. The chemical treatment of the silica gel leads to an attachment of the organofunctional groups on the solid-pore interface of the silica with an increase of the mean size of the solid phase and some coalescence of the pores. © 1989.

EXAFS and XRD Study of the Structural Evolution during Isothermal Sintering of SnO2 Xerogels

The formation of an ordered (crystalline) phase during isothermal sintering of SnO2 monolithic xerogels, at 200, 250, 300, 400, 500, 600 and 700°C, has been analyzed by the combined use of EXAFS and XRD techniques. For the desiccated gel (110°C), EXAFS results show the formation of small microcrystallites with the incipient cassiterite structure. Between 110 and 250°C, the dehydratation reaction leads to an amorphization evidenced by a decrease of the long and short range crystallographic order. It is due to fissure formation in the xerogel network. For higher temperatures, a continuous coagulation of the crystallites occurs, leading to grain growth. Grain and pore growth obeys the same kinetic relation, so that the microstructure grows by simple enlargement while its morphology is static.

Small-angle x-ray scattering study of the structural evolution of the drying of sonogels with the liquid phase exchanged by acetone

The structural evolution on the drying of wet sonogels of silica with the liquid phase exchanged by acetone, obtained from tetraethoxisilane sonohydrolysis, was studied in situ by small-angle x-ray scattering (SAXS). The periods associated to the structural evolution as determined by SAXS are in agreement with those classical ones established on basis of the features of the evaporation rate of the liquid phase in the obtaining of xerogels. The wet gel can be described as formed by primary particles (microclusters), with characteristic length a ∼ 0.67 nm and surface which is fractal, linking together to form mass fractal structures with mass fractal dimension D=2.24 in a length scale ξ∼6.7 nm. As the network collapses while the liquid/vapor meniscus is kept out of the gel volume, the mass fractal structure becomes more compacted by increasing D and decreasing ξ, with smoothing of the fractal surface of the microclusters. The time evolution of the density of the wet gels was evaluated exclusively from the SAXS parameters ξ, D, and a. The final dried acetone-exchanged gel presents Porod's inhomogeneity length of about 2.8 nm and apparently exhibits an interesting singularity D →3, as determined by the mass fractal modeling used to fit the SAXS intensity data for the obtaining of the parameters ξ and D.

A structural conformation study of aquatic humic acid

In the present work, aquatic humic substances (HS) were extracted by use of adsorbent XAD 8 and the acid humic fraction (AH) was separated throught acidification. After being purified by Hyphan resin and dialyze, the aquatic AH was characterized using Fourier-transform infrared spectroscopy and elemental analysis. The influence of the aquatic HA and electrolyte concentrations, pH and aquatic AH-metal complexation time on the conformation was investigated using UV/Vis spectroscopic studies, employing the equation suggested by Doty and Steiner. The results indicated that the acid humic flexible macromolecule assumes a condensed form at acid and alkaline pH. Other factors favoring condensed conformations are longer metal complexation time (ageing) and higher aquatic AH and electrolyte concentrations. Thus considering the strong influence of the investigated parameters in the structural conformation of the humic macromolecule, we conclude that studies using UV/Vis spectroscopy to estimate the concentration, aromaticity, humification degree of the aquatic AH and so on, require rigorous control over the experimental conditions employed to provide a correct interpretation of the analytical results. ©2006 Sociedade Brasileira de Química.

A theoretical and experimental study to unequivocal structural assignment of tetrahydroquinoline derivatives

The tetrahydroquinoline derivatives can be easily synthesized through Povarov reaction and have several important biological activities. This work describes a comparative study for the unequivocal assignment of molecular structure of different tetrahydroquinoline derivatives, through a complete analysis of NMR 1D and 2D NMR spectra (1H, 13C, COSY, HSQC, and HMBC), and the correlation this data with theoretical calculations of energy-minimization and chemical shift (δ), employing the theory level of DFT/B3LYP with set of the cc-pVDZ basis. For these derivatives the experimental analyses and the theoretical model adopted were sufficient to obtain a good description of its structures, and these results can be used to assign the structure of various others tetrahydroquinoline derivatives. © 2013 Springer Science+Business Media New York.

Effect of yttrium doping in barium zirconium titanate ceramics: A structural, impedance, modulus spectroscopy study

In the current article, we studied the effect of yttrium [Y3+] ions' substitution on the structure and electric behavior of barium zirconate titanate (BZT) ceramics with a general formula [Ba1-x Y 2x/3](Zr0.25Ti0.75)O3 (BYZT) with [x = 0, 0.025, 0.05] which were prepared by the solid-state reaction method. X-ray diffraction patterns indicate that these ceramics have a single phase with a perovskite-type cubic structure. Rietveld refinement data confirmed [BaO 12], [ZrO6], [TiO6], [YO6] clusters in the cubic lattice. The Y3+ ions' effects on the electric conductivity behavior of BZT ceramics as a function of temperature and frequency are described, which are based on impedance spectroscopy analyses. The complex impedance plots display a double semicircle which highlights the influences of grain and grain boundary on the ceramics. Impedance analyses showed that the resistance decreased with the increasing temperature and resulted in a negative temperature coefficient of the resistance property in all compositions. Modulus plots represent a non-Debye-type dielectric relaxation which is related to the grain and grain boundary as well as temperature-dependent electric relaxation phenomenon and an enhancement in the mobility barrier by Y3+ ions. Moreover, the electric conductivity increases with the replacement of Ba 2+ by Y3+ ions may be due to the rise in oxygen vacancies. © 2013 The Minerals, Metals & Materials Society and ASM International.

Structural, electronic and optical properties of Fe(III) complex with pyridine-2,6-dicarboxylic acid: A combined experimental and theoretical study

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

An Experimental Study on the Effect of Temperature on Piezoelectric Sensors for Impedance-Based Structural Health Monitoring

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Unusual broadening of the NIR luminescence of Er3+-doped Nb2O5 nanocrystals embedded in silica host: Preparation and their structural and spectroscopic study for photonics applications

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A DFT Study of Structural and Electronic Properties of ZnS Polymorphs and its Pressure-Induced Phase Transitions

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis, structural characterization, luminescent properties and theoretical study of three novel lanthanide metal-organic frameworks of Ho(III), Gd(III) and Eu(III) with 2,5-thiophenedicarboxylate anion

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)