Study of structural evolution and photoluminescent properties at room temperature of Ca(Zr, Ti)O-3 powders

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural evolution of aerogels prepared from TEOS sono-hydrolysis upon heat treatment up to 1100 degrees C

The structural evolution of aerogels prepared from TEOS sono-hydrolysis was studied as a function of the temperature of heat treatment up to 1100 degreesC by means of small angle X-ray scattering (SAXS) and density measurements. The mass fractal structure of the original wet sonogel (with scattering exponent alpha similar to 2.2) apparently transforms to a surface fractal structure in a length scale lesser than similar to1.5 nm, upon the process resulting in aerogel. Such a structural transformation is interpreted by the formation of new particles with characteristic dimension of similar to1.5 nm, with rough boundaries or electronic density fluctuations (or ultra-micropores) in their interior. The structural arrangement of these particles seem to preserve part of mass fractal characteristics of the original wet sonogel, now in a length scale greater than similar to1.5 nm. The electronic density heterogeneities in the particles start to be eliminated at around 800 degreesC and, at 900 degreesC, the particles become perfectly homogeneous, so the structure can be described as a porous structure with a porosity of similar to68% with similar to9.0 nm mean size pores and similar to4.3 nm mean size solid particles. Above 900 degreesC, a vigorous viscous flux sintering process sets in, eliminating most of the porosity and increasing rapidly the bulk density in an aerogel-glass transformation. (C) 2003 Elsevier B.V. All rights reserved.

Isothermal structural evolution of SnO2 monolithic porous xerogels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural evolution up to 1100 degrees C of xerogels prepared from TEOS sonohydrolysis and liquid phase exchanged by acetone

Silica xerogels were prepared from sonohydrolysis of tetraethoxysilane and exchange of the liquid phase of the wet gel by acetone. Monolithic xerogels were obtained by slow evaporation of acetone. The structural characteristics of the xerogels were studied as a function of temperature up to 1100 degrees C by means of bulk and skeletal density measurements, linear shrinkage measurements and thermal analyses (DTA, TG and DL). The results were correlated with the evolution in the UV-Vis absorption. Particularly, the initial pore structure of the dried acetone-exchanged xerogel was studied by small-angle X-ray scattering and nitrogen adsorption. The acetone-exchanged xerogels exhibit greater porosity in the mesopore region presenting greater mean pore size (similar to 4 nm) when compared to non-exchanged xerogels. The porosity of the xerogels is practically stable in the temperature range between 200 degrees C and 800 degrees C. Evolution in the structure of the solid particles (silica network) is the predominant process upon heating up to about 400 degrees C and pore elimination is the predominant process above 900 degrees C. At 1000 degrees C the xerogels are still monolithic and retain about 5 vol.% pores. The xerogels exhibited foaming phenomenon after hold for 10 h at 1100 degrees C. This temperature is even higher than that found for foaming of non-exchanged xerogels. (c) 2005 Elsevier B.V. All rights reserved.

Structural evolution of Eu-doped hydroxyapatite nanorods monitored by photoluminescence emission

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

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.

Structural and spectroscopic characterization of Al2-xCrxO3 powders obtained by polymeric precursor method

Al2O3 and Al2-x Cr (x) O-3 (x = 0.01, 0.02 and 0.04) powders have been synthesized by the polymeric precursors method. A study of the structural evolution of crystalline phases corresponding to the obtained powders was accomplished through X-Ray Diffraction and UV-vis spectroscopy (reflectance spectra and CIEL* a*b* color data). The obtained results allow to identify the gamma-Al2O3 to alpha-Al2O3 phase transition. The single-phase alpha-Al2O3 powder was obtained after heat treatment at 1050 degrees C for 2 h. The results show that the green to red color transition and ruby luminescence lines observed for the powders of Al2-x Cr (x) O-3 are related to the gamma to alpha-Al2O3 phase transition and the temperature and time range for such transition depends on the chromium content.

Structural investigations of tungsten silver phosphate glasses by solid state NMR, vibrational and X-ray absorption near edge spectroscopies

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

Structural studies of AgPO3-MoO3 glasses using solid state NMR and vibrational spectroscopies

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

Visible and near-infrared luminescent Eu3+ or Er3+ doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

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

Synthesis and structural investigations on TeO2-PbF2-CdF2 glasses and transparent glass-ceramics

New glasses have been prepared in the oxifluoride mixed system TeO2-PbF2-CdF2. Starting from pure TeO2 the addition of the fluorides leads to a decrease in the glasses characteristic temperatures. Also from Raman scattering results a structural evolution was observed where the number of structural units described as [TeO3] trigonal pyramids and [TeO3+1] polyhedra increases at the expense of the [TeO4] trigonal bipyramids supposed to exist in the TeO2, rich samples. Transparent glass ceramics were obtained from the glass with composition 80TeO(2)-10PbF(2)-10CdF(2), (mol%) with the PbTe3O7 crystalline phase being identified by X-ray diffraction and EXAFS measurements performed at the Te K, Cd K and Pb L-III edges. Also from Exafs measurements it is proposed that cadmium ions are preferentially surrounded by oxygen atoms although they were in a fluoride anion environment in the starting material. (C) 2002 Published by Elsevier B.V. Ltd.

Structural studies of NaPO3-WO3 glasses by solid state NMR and Raman spectroscopy

Vitreous samples were prepared in the (100 2 x) NaPO3-x WO3 (0 <= x <= 70) glass forming system using conventional melting-quenching methods. The structural evolution of the vitreous network was monitored as a function of composition by thermal analysis, Raman spectroscopy and high resolution one- and two-dimensional P-31 solid state NMR. Addition of WO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures, suggesting a significant increase in network connectivity. At the same time Raman spectra indicate that up to about 30 mol% WO3 the tungsten atoms are linked to some non-bridging oxygen atoms (W-O- or W=O bonded species), suggesting that the network modifier sodium oxide is shared to some extent between both network formers. W-O- W bond formation occurs only at WO3 contents exceeding 30 mol%. P-31 magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. The possible formation of some anionic tungsten sites suggested from the Raman data implies an average increase in the degree of polymerization for the phosphorus species, which would result in diminished P-31/Na-23 interactions. This prediction is indeed confirmed by P-31{Na-23} and Na-23{P-31} rotational echo double resonance (REDOR) NMR results, which indicate that successive addition of WO3 to NaPO3 glass significantly diminishes the strength of phosphorus-sodium dipole-dipole couplings.

Structural features of phosphate and sulfate modified zirconia prepared by sol-gel route

This paper describes the effect of sulfate, phosphate and nitrate complexing ligands on the structural features of amorphous xerogels and on the crystallization of metastable zirconia phases during the xerogel-ceramic conversion. Powdered samples were prepared by a sol-gel route using zirconyl chloride precursors chemically modified by complexing ligands. The structural evolution of ZrO2 phases as function of firing temperature was analyzed by XRPD, EXAFS and P-13 NMR/MAS. The experimental results show the formation of metastable t-ZrO2 during the low firing temperature of xerogels modified by sulfate or phosphate groups. The martensitic tetragonal-monoclinic transformation occurs during desorption of sulfate groups. The largest temperature interval of stability of metastable tetragonal zirconia was observed for phosphate-modified xerogels.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO3-x% MoO3 (0 <= x <= 70) glass-forming system by a modified melt method that allowed good optical quality samples to be obtained. The structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), Raman scattering, and solid-state nuclear magnetic resonance (NMR) for P-31, Na-23, and Mo-95 nuclei. Addition of MoO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures up to x = 45, suggesting a significant increase in network connectivity. For this same composition range, vibrational spectra suggest that the Mo6+ ions are bonded to some nonbridging oxygen atoms (Mo-O- or Mo=O bonded species). Mo-O-Mo bond formation occurs only at MoO3 contents exceeding x = 45. P-31 magic-angle spinning (MAS) NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. These sites are denoted as Q(2Mo)((2)), Q(1Mo)((2)), and Q(0Mo)((2)), respectively. For x < 0.45, the populations of these sites can be described along the lines of a binary model, according to which each unit of MoO3 converts two Q(nMo)((2)) sites into two Q((n+1)Mo)((2)) sites (n = 0, 1). This structural model is consistent with the presence of tetrahedral Mo(=O)(2)(O-1/2)(2) environments. Indeed, Mo-95 NMR data suggest that the majority of the molybdenum species are four-coordinated. However, the presence of additional six-coordinate molybdenum in the MAS NMR spectra indicates that the structure of these glasses may be more complicated and may additionally involve sharing of network modifier oxide between the network formers phosphorus and molybdenum. This latter hypothesis is further supported by Na-23{P-31} rotational echo double resonance (REDOR) data, which clearly reveal that the magnetic dipole-dipole interactions between P-31 and Na-23 are increasingly diminished with increasing molybdenum content. The partial transfer of modifier from the phosphate to the molybdate network former implies a partial repolymerization of the phosphate species, resulting in the formation of Q(nMo)((3)) species and accounting for the observed increase in the glass transition temperature with increasing MoO3 content that is observed in the composition range 0 <= x <= 45. Glasses with MoO3 contents beyond x = 45 show decreased thermal and crystallization stability. Their structure is characterized by isolated phosphate species [most likely of the P(OMo)(4) type] and molybdenum oxide clusters with a large extent of Mo-O-Mo connectivity.