Physicochemical properties and morphology of spongolite from Mato Grosso do Sul (Brazil)

The physicochemical properties and morphology of spongolite, a fibrous hollow material from Mato Grosso do Sul State (Brazil) have been studied. The results of thermal analysis, scanning electron microscopy (SEM), X-ray diffraction and NMR spectroscopy indicated that external and internal surfaces of silica spicules are covered by silica gel layers. The water evolved in the range 120-350degreesC is the result of silanol groups condensation to siloxane bonds. Total homogenization of the needles is achieved by heating spongolite over 900degreesC. This mineral may be considered as a natural composite material containing surface-immobilized reactive species. The presence of active silica gel layers opens the possibilities of attaching functional groups to spongolite surface. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Synthesis and characterization of Li2ZnTi3O8 spinel using the modified polymeric precursor method

In this work we report the synthesis procedure, crystallographic, structural and magnetic properties of the Li2ZnTi3O8 spinel obtained using a modified polymeric precursor method. This synthesis method generates very reactive and property-controlled nanoparticles. The samples were characterized using X-ray powder diffraction (XRD) associated to the Rietveld refinement method, thermogravimetric analysis (TG), specific surface area, scanning electron microscopy (SEM) and magnetic susceptibility measurements.The phase formation temperature of the lithium zinc titanate spinel was observed to decrease due to the homogeneity and highly controlled nanometric particle size. (C) 2003 Elsevier B.V. All rights reserved.

The influence of crystallization route on the properties of lanthanum-doped Bi4Ti3O12 thin films prepared from polymeric precursors

Pure and lanthanum-doped Bi4Ti3O12 thin films were deposited on Pt/Ti/SiO2/Si substrate using a polymeric precursor solution. The spin-coated films were specular and crack-free and crystalline after annealing at 700 degreesC for 2 h. Crystallinity and morphological evaluation were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Multilayered films obtained using the intermediate-crystalline layer route present a dense microstructure with spherical grains. Films obtained using the intermediate-amorphous layer, present elongated grains around 250 nm in size. The dielectric and ferroelectric properties of the lanthanum-doped Bi4Ti3O12 films are strongly affected by the crystallization route. The hysteresis loops are fully saturated with a remnant polarization and drive voltage of the films, heat-treated by the intermediate-crystalline (P-r = 20.2 muC/cm(2) and V = 1.35 V) and for the film heat-treated by amorphous route (P-r = 22.4 muC/cm(2) and V = 2.99 V). (C) 2004 Elsevier B.V. All rights reserved.

Optical properties of potassium niobate thin films prepared by the polymeric precursor method

Thin films of potassium niobate were deposited on MgO (100) substrates by the polymeric precursor method and annealing in static air at 600 degreesC for 20 h. The obtained films were characterized by X-ray diffraction, atomic force microscopy (AFM) and the prism coupling method. The phi-scan diffraction evidenced the growth of the films with fourfold symmetry. AFM study shows that the films are homogeneous, dense and present a smooth surface. The refractive index and optical losses were strongly influenced by the degree of crystallinity. (C) 2004 Elsevier B.V. All rights reserved.

Influence of the solution pH on the morphological, structural and electrical properties of Bi3.50La0.50Ti3O12 thin films obtained by the polymeric precursor method

Lanthanum-doped Bi4Ti3O12 thin films (BLT) were deposited on Pt/Ti/SiO2/Si substrates using a polymeric precursor solution. The spin-coated films were specular, crack-free and crystalline after annealing at 700 degrees C for 2 h. Crystallinity and morphological evaluation were examined by X ray diffraction (YRD) and atomic force microscopy (AFM). The stability of the formed complex is of extreme importance for the formation of the perovskite phase. Films obtained from acid pH solution present elongated grains around 200 ran in size, whereas films obtained from basic solution present a dense microstructure with spherical grains (100 nm). The dielectric and ferroelectric properties of the BLT films are strongly affected by the solution pH. The hysteresis loops are fully saturated with a remnant polarization and coercive voltage of P-r=20.2 mu C/cm(2) and V-c = 1.35 V and P-r= 15 mu C/cm(2) and V-c = 1.69 V for the films obtained from basic and acid solutions, respectively. (C) 2005 Elsevier B.V. All rights reserved.

Characterization of ZnO-degraded varistors used in high-tension devices

The effects of the degradation process on the structural, microstructural and electrical properties of ZnO-based varistors were analyzed. Rietveld refinement showed that the BiO2-x phase is affected by the degradation process. Besides the changes in the spinel phase, the degradation process also affects the lattice microstrain in the ZnO phase. Scanning electron microscopy analysis showed electrode-melting failure, while wavelength dispersive X-ray spectroscopy qualitative analysis showed deficiency of oxygen species at the grain boundaries in the degraded samples. Atomic force microscopy using electrostatic mode force illustrated a decrease in the charge density at the grain boundaries of the degraded sample. Transmission electron microscopy showed submicrometric spinel grains embedded in a ZnO matrix, but their average grain size is smaller in the degraded sample than in the standard one. Long pulses appeared to be more harmful for the varistors' properties than short ones, causing higher leakage current values. The electrical characteristics of the degraded sample are partially restored after heat treatment in an oxygen-rich atmosphere. (C) 2006 Elsevier Ltd. All rights reserved.

Ferroelectric and piezoelectric properties of bismuth titanate thin films grown on different bottom electrodes by soft chemical solution and microwave annealing

Bismuth titanate (Bi4Ti3O12, BIT) films were evaluated for use as lead-free piezoelectric thin films in micro-electromechanical systems. The films were grown by the polymeric precursor method on LaNiO3/SiO2/Si (1 0 0) (LNO), RuO2/SiO2/Si (1 0 0) (RuO2) and Pt/Ti/SiO2/Si (1 0 0) (Pt) bottom electrodes in a microwave furnace at 700 degrees C for 10 min. The domain structure was investigated by piezoresponse force microscopy (PFM). Although the converse piezoelectric coefficient, d(33), regardless of bottom electrode is around (similar to 40 pm/V), those over RuO2 and LNO exhibit better ferroelectric properties, higher remanent polarization (15 and 10 mu C/cm(2)), lower drive voltages (2.6 and 1.3 V) and are fatigue-free. The experimental results demonstrated that the combination of the polymeric precursor method assisted with a microwave furnace is a promising technique to obtain films with good qualities for applications in ferroelectric and piezoelectric devices. (c) 2006 Elsevier Ltd. All rights reserved.

Color and structural analysis of CoxZn7-xSb2O12 pigments

The polymeric precursor method was successfully used to synthesize CoxZn7-xSbO12 (x = 0-7) powders. Pigments were evaluated using colorimetry, X-ray diffraction, UV-vis and infrared spectroscopy. The optical band gap values vary with the Co2+ substitution. These results suggest that the concomitant presence of Co and Zn in the spinel lattice leads to the rupture of the Vegard law, as well as other properties of the studied system, such as unit cell volume. The Co-richer samples display a higher absorbance than the Co-lean samples. The high absorption of the Co7Sb2O12 sample at most of the visible region makes this compound a candidate for a black pigment. It was shown that color depends on the site where the chromophore ion is located, in agreement with the ligand field theory. (c) 2006 Elsevier Ltd. All rights reserved.

Luminescence in semi-crystalline zirconium titanate doped with lanthanum

This paper aims to describe the synthesis of the semi-crystalline and crystalline powder of lanthanum doped with zirconium titanate (65/35), LZT through Pechini method. The analysis done by Raman demonstrated that semi-crystalline phase at 550 degrees C and crystalline phase after 600 degrees C were formed. The XRD pattern shows the ZrTiO4 phase formation demonstrating that La substitutions into the lattice take place. The calcined powder at different temperatures shows a semi-crystalline phase presenting photoluminescence effect when processed at low temperatures. From 300 to 400 degrees C a broadband is observed at 563 nm and 568 nm, respectively. Defects creation such as: Zr3+ center dot Vo(center dot center dot) and Ti3+ - V-O(center dot center dot), Zr and Ti replaced by La with vacancy formation, impurities and imperfections contributed to the photoluminescence effect. However, the main emission is due to a reverse Ti4+ -> O2- or/and Zr4+ -> O2- transition that occur within a regular titanate or zirconate eight-fold coordination [BO8-delta], B = Zr4+, Ti4+. (c) 2006 Elsevier B.V. All rights reserved.

Room temperature co-precipitation of nanocrystalline CeO2 and Ce0.8Gd0.2O1.9-delta powder

This paper describes a simple method to co-precipitate CeO2 and Ce0.8Gd0.2O1.9-delta with ammonium hydroxide from solvents such as: water, ethylene glycol, ethyl alcohol and isopropyl alcohol. Characterization by Raman spectroscopy and XRD evidenced the formation of a solid solution of gadolinium-doped ceria at room temperature. Nanometric particles with crystallite size of 3.1 nm were obtained during synthesis using ethyl alcohol as solvent. This is a promising result compared with those mentioned in the literature, in which the smallest crystallite size reported was, 6.5 nm. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis and photoluminescence study of La1.8Eu0.2O3 coating on nanometric alpha-Al2O3

In this work the La1.8Eu0.2O3 coating on nanometric alpha-alumina, alpha-Al2O3@La1.8Eu0.2O3, was prepared for the first time by a soft chemical method. The powder was heat-treated at 100, 400, 800 and 1200 degrees C for 2 h. X-ray powder diffraction patterns (XRD), transmission electronic microscopy (TEM), emission and excitation spectra, as well as Eu3+, lifetime were used to characterize the material and to follow the changes in structure as the heating temperature increases. The Eu3+ luminescence data revealed the characteristic transitions D-5(0) --> F-7(J) (J = 0, 1 and 3) of Eu3+ at around 580, 591 and 613 nm, respectively, when the powders were excited by 393 nm. The red color of the samples changed to yellow when the powder was annealed at 1200 degrees C. The decrease in the (D-5(0) --> F-7(2))/(D-5(0) --> F-7(1)) ratio from around 5.0 for samples heated at lower temperatures to 3.1 for samples annealed at 1200 degrees C is consistent with a higher symmetry of the Eu3+ at higher temperature. The excitation spectra of the samples also confirms this change by the presence of a more intense and broad band at around 317 nm, instead of the presence of the characteristic peak at 393 mn, which corresponds to the F-7(0) --> L-5(6) transition of the Eu3+. The lifetimes of the D-5(0) --> F-7(2) transition of Eu3+ for the samples heat-treated at 100, 400, 800 and 1200 degrees C was evaluated as 0.57, 0.72, 0.43 and 0.31 ms, respectively. (C) 2006 Elsevier Ltd. All fights reserved.

Microstructural and ferroelectric properties of PbZr1-xTi(x)O(3) thin films prepared by the polymeric precursor method

The polymeric precursor method was employed in the preparation of PZT thin films on Pt(111)Ti/SiO2/Si(100) substrates. X-ray diffraction patterns revealed the polycrystalline nature of the PZT (53:47) thin films, which had a granular structure and a grain size of approximately 70 nm. A 350-nm thick film was obtained by running three cycles of the dip-coating/heating process. Atomic force microscopy (AFM) analyses showed the surface of these thin films to be smooth, dense and crack-free with low surface roughness (= 2.0 nm). The PZT (53:47) thin films annealed at 700 degreesC showed a well-saturated hysteresis loop. The C-V curves of perovskite thin film displayed normal ferroelectric behavior, while the remanent polarization (2P(r)) and coercive field (E-e) of the film deposited and measured at room temperature were 40 muC/cm(2) and 110 kV/cm, respectively. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Phosphate functionalization of spongiolite surface

Spongiolite from Mato Grosso do Sul (Brazil), natural inorganic composite constituted of silica needles, was treated with concentrated phosphoric acid at high temperatures. Superficial coating of the needles was proved to be constituted of silicon diphosphate, a compound offering six-coordinated silicon sites. Owing to the affinity of three charged ions to phosphate groups, this coating acts as specific adsorbent for the rare earth elements which prefer octahedral coordination (starting from samarium, yttrium included). The uptake of lanthanum and neodymium are significantly lower due to different coordination tendencies. Lanthanide fixation upon silica with PO4 groups anchored on its surface may be useful in the manufacturing of special phosphate-silicate glasses. (C) 2003 Elsevier B.V. All rights reserved.

Structural effects of Li and K additives on the columbite precursor and 0.9PMN-0.1PT powders

Single-phase perovskite 0.9Pb(Mg1/3Nb2/3)O-3-0.1PbTiO(3) (PMN-PT) powders were prepared by using a Ti-modified columbite precursor (MNT) obtained by the polymeric precursor method. The innovation consists in the preparation of Ti-modified columbite in order to react directly with a stoichiometric amount of PbO to obtain pyrochlore-free PMN-PT powders. It has been shown that titanium oxide forms a solid solution with columbite (MN) and does not affect the obtaining of a single-phase columbite precursor. Thus, a high amount of perovskite phase can be obtained by reaction with PbO at 800 degreesC for 2 h. Effects of K and Li additives on the structure of MNT and PMN-PT were studied. X-ray diffraction studies were carried out to verify the phase formation at each processing step and these data were used for structural refinement by the Rietveld method. Both K and Li additives increase the crystallinity of MNT powders, being this effect more intense for the Li-doped samples. For PMN-PT samples the additives cause an insignificant decrease in the amount of perovskite phase. The morphology of the PMN-PT powder depends on the type of the additive. (C) 2003 Elsevier B.V All rights reserved.

Thermal conductivity features of ZnO-based varistors using the laser-pulse method

The thermal conductivity of several commercial ZnO-based varistor systems was determined based on the laser-pulse method, a technique that proved extremely useful and easy to apply. Using this technique, the thermal conductivity was found to be dependent on the microstructural features of the devices, involving the mean grain size and phase composition. Among the phases existing in commercial ZnO-based varistors, ZniSb2O12 and Bi2O3 were found to contribute strongly to the thermal conductivity of the devices. (C) 2003 Elsevier B.V. All rights reserved.