Dielectric spectroscopy analysis of CaCu3Ti4O12 polycrystalline systems

Dielectric spectroscopy was used in this study to examine CaCu3Ti4O12 polycrystalline samples. The analysis involved systems presenting low non-Ohmic properties, and the grain's internal domain was evaluated separately from the contribution of barrier-layer capacitances associated with Schottky-type barriers in this type of material. The effect of oxygen-rich atmosphere and high cooling rate was evaluated, revealing a strong increase in the dielectric properties of the CaCu3Ti4O12 system under these conditions. This effect was attributed to a chemical change in the grain's internal domain, which may be considered an internal barrier-layer capacitance of the polycrystalline material. (c) 2006 American Institute of Physics.

Sintering mechanisms of ZrO2 center dot MgO with addition of TiO2 and CuO

Substitutions of Ti and Cu in ZrO2.MgO (Z), cause transformation from monoclinic (m) to cubic (c) and tetragonal (t). According to the vacancy model and solid Solution formation models, neither CuO nor TiO2 cause zirconia stabilization, which derives front other phenomena. Data analysis by TMA using the CRH (constant rate of heating) method shows a solid state reaction of ZrO2.MgO.TiO2 (Z.TiO2) demonstrating a dominant mechanism of volume diffusion (n = 1). However, the sintering of ZrO2.MgO.CuO (Z.CuO) shows a viscous flow mechanism (n = 0), a similar phenomena to that of by sintering of glass. Transformations, such as: CuO to Cu2O at 1000 degreesC, ZrO2 (m) to ZrO2 (t) at 1100 degreesC and Cu2O (s) to Cu2O (l) at 1230 degreesC cause successive rearrangements of microstructure inside of region I (sintering process) and lead to interpretation errors when the Bannister equation is used. (C) 2003 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Evaluation of color removal and degradation of a reactive textile azo dye on nanoporous TiO2 thin-film electrodes

The feasibility of the photobleaching of a textile azo dye, reactive orange 16 (C.I. 17757), in aqueous solution using titanium dioxide thin-film electrodes prepared by the sol-gel method was investigated. The best conditions for maximum photoelectrocatalytic degradation were found to be pH > 10 for Na2SO4 medium and pH < 6 for NaCl. In both situations, an applied potential of +1.0 V and low dye concentration are recommended, when 100% of color removal is obtained after 20 min of photoelectrocatalysis. The effects of side reaction pathway on the degradation rate of dye in sulfate and chloride medium were presented and the best performance are optimized to situations closed to that verified in the textile effluent. The influence of variables as applied potential, pH, supporting electrolyte and dye concentration on the kinetics of photoelectrochemical degradation also were investigated. Oxalic acid is identified by HPLC and UV-Vis spectrophotometric methods as the main degradation product generated after 180 min of photoelectrocatalysis of 4 x 10(-5) mol l(-1) dye in sodium sulphate pH 12 and NaCl pH 4.0 and a maximum reduction of 56 and 62% TOC was obtained, respectively. (C) 2004 Elsevier Ltd. All rights reserved.

A theoretical analysis of the TiO2/Sn doped (110) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO2/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO2 is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sri, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices. (c) 2005 Elsevier B.V. All rights reserved.

Admittance and dielectric spectroscopy of polycrystalline semiconductors

This text discusses about advantageous, powerful and limitations of admittance and dielectric spectroscopy in the characterization of polycrystalline semiconductors. In the context of polycrystalline semiconductors or dielectric materials, the admittance or dielectric frequency response analyses are shown to be sometimes more useful than impedance spectra analysis, mainly because information on the capacitances or deep trap states are possible to be monitored from admittance or dielectric spectra as a function of dopant concentration or annealing effects. The majority of examples of the application of admittance or dielectric analysis approach were here based on SnO2- and ZnO-based polycrystalline semiconductors devices presenting nonohmic properties. Examples of how to perform the characterization of Schottky barrier in such devices are clearly depicted. The approach is based on findings of the true Mott-Schottky pattern of the barrier by extracting the grain boundary capacitance value from complex capacitance diagram analysis. The equivalent circuit of such kind of devices is mainly consistent with the existence of three parallel elements: the high-frequency limit related to grain boundary capacitances, the complex incremental capacitance at intermediate frequency related to the deep trap relaxation and finally at low frequency region the manifestation of the conductance term representing the dc conductance of the multi-junction device. (c) 2007 Elsevier Ltd. All rights reserved.

Improvement of the Mo/TiO2-Al2O3 catalyst by the control of the sol-gel synthesis

Traditional hydrotreating catalysts are constituted by molybdenum deposited on Al2O3 promoted by nickel and phosphorous. Several studies have shown that TiO2-Al2O3 mixed oxides are excellent supports for the active phases. Results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, the titanium one chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal molar ratio [Ti]/[Ti+Al] on the microstructural features of nanometric particles was analyzed by X-Ray Diffraction, N-2 Adsorption Isotherms and Transmission Electron Microscopy. The catalytic activity of Mo impregnated supports was evaluated using the thiophene hydrodesulfurization at different temperatures and atmospheric pressure. The pores size distribution curve moves from the micropores to the mesopores by increasing the Ti contents, allowing the fine tuning of average size from 2.5 to 6 nm. Maximal (367 m(2).g(-1)) and minimal (127 m(2).g(-1)) surface area were found for support containing [Ti]/[Ti+Al] ratio equal to 0.1 and 1, respectively. The good mesopore texture of alumina-titania support with [Ti]/[Ti+Al] molar ratio between 0.3 and 0.5 was found particularly valuable for the preparation of well dispersed MoS2 active phase, leading to HDS catalyst with somewhat higher activity than that prepared using a commercial alumina support.

Tailoring of heterostructures in a SnO2/TiO2 system by the oriented attachment mechanism

In order to verify the possibility of forming a heterostructure-i.e., a nanoparticle tailored by the junction of two or more different materials-through the oriented attachment (OA) mechanism, experiments with rutile TiO2 and cassiterite SnO2 as candidate materials were done, since they have similar crystallographic parameters. The experiments were carried out in hydrothermal conditions and in an in situ observation at the high resolution transmission electron microscopy. The results showed the formation of TiO2/SnO2 heterostructures, confirming the coexistence of rotation-alignment and oriented collision mechanisms, hypothesis of OA behavior proposed in previous theoretical works.

Anisotropic growth of oxide nanocrystals: Insights into the rutile TiO2 phase

In this work, we report the synthesis of titanium oxide nanocrystals, especially the rutile TiO2 phase with nanorod morphology, by a method based on peroxotitanium complex decomposition. The results indicate that the anisotropic morphology reported for rutile TiO2 nanocrystals is related to the oriented attachment process. Despite the predominance of rutile nanocrystals at longer treatment times, the nanocrystals were obtained also in the anatase type, according to the degradation time adopted. XANES results evidenced the absence of structural correlation between the peroxytitanium complex and phase evolution, and the coexistence of the two phases strongly suggests a correlation of the oriented attachment mechanism and the rutile phase stabilization.

Crystallographic and magnetic structure of polycrystalline Zn7-xNixSb2O12 spinels

The crystallographic and magnetic structure of sintered, polycrystalline samples of zinc-antimony spinel, Zn7-xNixSb2O12, have been investigated. The samples were prepared by the modified polymeric precursors method. The magnetic contributions of the Ni2+ ions distributed in three non-equivalent crystallographic sites were investigated, revealing the occurrence of different magnetic regimes. A hysteresis response in the magnetic susceptibility indicates a spin-glasslike behavior at low temperatures. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Photoluminescence in amorphous TiO2-PbO systems

Photoluminescence (PL) at room temperature has been achieved in amorphous thin films and powders of the TiO2-PbO system. They were prepared by the polymeric precursor method with [PbO]/[TiO2] molar ratios ranging from 0.0 to 1.0. The energy position of maximum PL emission and the PL intensity showed dependence on Pb concentration. The Pb addition suggests an increase in the number of nonbridging oxygens (NBO) in the amorphous TiO2 network. These results support the relationship between photoluminescence and structure in TiO2-based amorphous materials.

Qualitative evaluation of active potential barriers in SnO2-based polycrystalline devices by electrostatic force microscopy

This paper discuss the qualitative use of electrostatic force microscopy to study the grain boundary active potential barrier present in dense SnO2-based polycrystalline semiconductors. The effect of heat treatment under rich- and poor-oxygen atmospheres was evaluated while especially considering the number of active barriers at grain boundary regions. The results show that the number of active barriers decrease after heat treatment in an oxygen-poor atmosphere and increase after heat treatment in oxygen-rich atmospheres. The observed effect was explained by considering the presence of oxidized transition metal elements segregated at grain boundary regions which leads to the p-type character of this region, in agreement with the atomic barrier formation mechanism in metal oxide varistor systems.

a-b axis-oriented lanthanum doped Bi4Ti3O12 thin films grown on a TiO2 buffer layer

a-b axis-oriented, lanthanum doped Bi4Ti3O12 (BLT) thin films with a TiO2 rutile buffer layer deposited on Pt/Ti/SiO2/Si substrates were grown by the soft chemical method. Butterfly dielectric behavior has been achieved and can be ascribed to the ferroelectric domain switching. The remanent polarization and the coercive voltage for the film deposited on TiO2 buffer layer were 22.2 mu C/cm(2) and 1.8 V, respectively. Random-oriented BLT films showed a reduction in switching polarization when compared to the a-b axis-oriented films. Due to the excellent physical properties, these films are a promising candidate for use in lead-free applications in ferroelectric devices. (c) 2006 American Institute of Physics.

Separation of dielectric and space charge polarizations in CaCu3Ti4O12/CaTiO3 composite polycrystalline systems

The complex analysis of dielectric/capacitance is a very useful approach to separate different polarization contributions existing in polycrystalline ceramics. In this letter, the authors use this type of spectroscopic analysis to separate the bulk's dielectric dipolar relaxation contributions from the polarization contribution due to space charge in the grain boundaries of a CaCu3Ti4O12/CaTiO3 polycrystalline composite system. The bulk dielectric dipolar relaxation was attributed to the self-intertwined domain structures from the CaCu3Ti4O12 phase coupled to the dipole relaxation from the CaTiO3 phase, while the space charge relaxation was attributed to the Schottky-type potential barrier responsible for the highly non-Ohmic properties observed in this composite polycrystalline system.

Characterization of an all sol-gel electrochromic device WO3/Ormolyte/CeO2-TiO2

Electrochemical lithium intercalation in thin films of CeO2-TiO2 and WO3, prepared by the sol-gel technique was investigated with cyclic voltammetry and spectroelectrochemical techniques in propylene carbonate solutions. A solid state system having the configuration WO3/Ormolyte/CeO2-TiO2 has been assembled. The solid electrolyte, an organically modified electrolyte (ormolyte), was prepared with different [O]/[Li] ratios. The transmittance variation of this system during a potentiostatic step from -0.7 V to 0.8 V was about 35% at 550 nm.

Nonlinear behavior of TiO2 center dot Ta2O5 center dot MnO2 material doped with BaO and Bi2O3

A study was made on the effect of the addition of BaO (0.025-0.05 mol%) and Bi2O3 (0.025-0.05 mol%) to the TiO2.Ta2O5.MnO2 material. The samples were characterized by X-ray diffraction, and current-voltage measurements were accomplished for determination of the nonlinear coefficient. An analysis was made to evaluate the microstructural characteristics of the materials. The most appropriate sintering conditions for the materials were analyzed with the purpose of obtaining the best nonlinear coefficient associated with the smallest breakdown electric field. After sintering at 1400 degreesC for 2 h, a low-voltage (30 V cm(-1)) varistor was obtained, which, however, presented a low nonlinear coefficient (6). It was found that the sintering conditions must be controlled in order to improve the electrical properties of these materials. (C) 2004 Elsevier B.V. All rights reserved.