Optical and Thermal Characterization of Dye Intercalated Montmorillonites and Rare Earth Doped Materials

Nondestructive photothermal methods as well as optical absorption and fluorescence spectroscopy are utilized to characterise three different materials, both thermally and optically. The possibility of using montmorillonite clay minerals, after textile waste-water treatment, is investigated for further applications. The laser induced luminescence studies and thermal characterisation of certain rare earth titanates prepared by self propagating high temperature synthesis method are also presented. Moreover, effort is made to characterise rare earth doped sol gel silica glasses with the help of these nondestructive techniques.

Microstructural, structural and dielectric properties of Er(3+)-modified BaTi(0.85)Zr(0.15)O(3) ceramics

The (micro)structural and electrical properties of undoped and Er(3+)-doped BaTi(0.85)Zr(0.15)O(3) ceramics were studied in this work for both nominal Ba(2+) and Ti(4+) substitution formulations. The ceramics were produced from solid-state reaction and sintered at 1400 degrees C for 3 h. For those materials prepared following the donor-type nominal Ba(1-x)Er(x)(Ti(0.85)Zr(0.15))O(3) composition, especially, Er(3+) however showed a preferential substitution for the (Ti,Zr)(4+) lattice sites. This allowed synthesis of a finally acceptor-like, highly resistive Ba(Ti,Zr,Er)O(3-delta)-like system, with a solubility limit below but close to 3 cat.% Er(3+). The overall phase development is discussed in terms of the amphoteric nature of Er(3+), and appears to mainly or, at least, partially also involve a minimization of stress effects from the ion size mismatch between the dopant and host cations. Further results presented here include a comparative analysis of the behavior of the materials` grain size, electrical properties and nature of the ferroelectric-to-paraelectric phase transition upon variation of the formulation and Er(3+) content. (C) 2008 Elsevier Ltd. All rights reserved.

Phase-transition studies of Ba(0.90)Ca(0.10)(Ti(1-x)Zr(x))O(3) ferroelectric ceramic compounds

Perovskite-structured Ba(0.90)Ca(0.10)(Ti(1-x)Zr(x))O(3) ceramics were prepared in this work and subsequently studied in terms of composition-dependent dielectric and high-resolution long-range order structural properties from 30 to 450 K. The dielectric response of these materials was measured at several frequencies in the range from 1 kHz to 1 MHz. Combining both techniques, including Rietveld refinement of the X-ray diffraction data, allowed observing that, when increasing Zr(4+) content, the materials change from conventional to diffuse and relaxor ferroelectric compounds, the transition occurring spontaneously at the x = 0.18 composition. Interestingly, this spontaneous transition turned out to be prevented for a further increase of Zr(4+). On the basis of all the dielectric and structural results processed, a phase diagram of this system is presented. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Morphological and Structural changes of CaxSr1-xTiO3 Powders Obtained by the Microwave-Assisted Hydrothermal Method

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

Estudo de titanatos nanoestruturados obtidos por tratamento hidrotérmico de óxido de titânio em meio alcalino

TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase

Síntese e Caracterização de Titanatos de Cobalto e Níquel, dopados com Praseodímio, obtidos a partir da decomposição de Nitrilotriacetatos

In recent years, studies about the physicochemical properties of mixed oxides, call attention of the scientific community, properties like as piezoelectricity, photoluminescence, or applications as catalysts, arise in these compounds, when their chemical compositions are modified, in this context some routes are employed in the synthesis of these materials, among which can be cited these methods: ceramic, combustion, co-precipitation, Pechini or polymeric precursor method, hydrothermal, sol-gel; these routes are divided into traditional routes or chemical routes. In this work were synthesized oxides with variable composition, from the thermal decomposition of titanium, cobalt, nickel and praseodymium nitrilotriacetates. The nitrilotriacetates were characterized by IR Spectroscopy (FTIR), Thermogravimetric (TG/ DTG) and Differential Scanning Calorimetry (DSC), while oxides have been characterized by X-ray diffraction (XRD), Spectrofluorimetry and IR Spectroscopy (FTIR). From FTIR data, it was demonstrated that the displacement of the band corresponding to the carboxylate group (νCOOH) at 1712 cm-1, present in nitrilotriacetic acid (H3NTA), for 1680-1545 cm-1, these stretches are characteristics of coordinated nitrilotriacetates, By thermal analysis (TG/DTG /DSC), it was suggested, that in an oxidizing atmosphere (air) oxides are obtained at lower temperatures than in an inert atmosphere N2(g). By results from X-ray Diffraction (XRD), it was determinated that the oxides are crystalline and the predominant phases obtained are summarized titanate phases rutile and ilmenite. By fluorimetry was observed that the intensity of emission bands are directly proportional to the concentration of ions Ni2+, Co2+ and Pr3+, and IR spectroscopy (FTIR) from oxides, demonstrated the disappearance of characteristic bands by nitrilotriacetates, determining the complete decomposition of the nitrilotriacetates in oxides

Síntese hidrotérmica e caracterização estrutural de titanatos nanotubulares para aplicação na captura do dióxido de carbono

Nanostructured materials have been spreading successfully over past years due its size and unusual properties, resulting in an exponential growth of research activities devoted to nanoscience and nanotechnology, which has stimulated the search for different methods to control main properties of nanomaterials and make them suitable for applications with high added value. In the late 90 s an alternative and low cost method was proposed from alkaline hydrothermal synthesis of nanotubes. Based on this context, the objective of this work was to prepare different materials based on TiO2 anatase using hydrothermal synthesis method proposed by Kasuga and submit them to an acid wash treatment, in order to check the structural behavior of final samples. They were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), adsorption/desorption of N2, thermal analysis (TG/DTA) and various spectroscopic methods such as absorption spectroscopy in the infrared (FT-IR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). All the information of characterizations confirmed the complete conversion of anatase TiO2 in nanotubes titanates (TTNT). Observing the influence of acid washing treatment in titanates structure, it was concluded that the nanotubes are formed during heat treatment, the sample which was not subjected to this process also achieved a complete phase transformation, as showed in crystallography and morphology results, however the surface area of them practically doubled after the acid washing. By spectroscopy was performed a discussion about chemical composition of these titanates, obtaining relevant results. Finally, it was observed that the products obtained in this work are potential materials for various applications in adsorption, catalysis and photocatalysis, showing great promise in CO2 capture

Effect of processing route on the phase formation and properties of Bi4Ti3O12 ceramics

Our efforts were directed to the preparation of bismuth titanate-Bi4Ti3O12 (BIT) by two procedures: mechanically assisted synthesis and polymeric precursor method to display a variety of their advantages. To follow the nucleation and phase formation of BIT, XRD and Rietveld refinement analysis were used and it was shown that Bi4Ti3O12 ceramic can been successfully prepared from nano-sized powders obtained by both methods. The ferroelectric properties were determined and the loops from BIT obtained by polymeric precursor method were not fully saturated with a remnant polarization of 20 mu C/cm(2) and coercitive field of 1500 kV/cm. BIT obtained from powders prepared by mechanically assisted synthesis shows a remnant polarization of 0.65 mu C/cm(2) and coercitive field of 1050 kV/cm. The grain morphology may be the factor causing the observed differences. (C) 2005 Published by Elsevier Ltd and Techna Group S.r.l.

SYNTHESIS OF ULTRA-FINE CRYSTALLINE ZRXTI1-XO4 POWDER BY POLYMERIC PRECURSOR METHOD

Reactive ZrxTi1-xO4 (x=0.65, 0.50 and 0.35) powder was prepared by the polymeric precursor method. Studies by X-ray diffraction (XRD), nitrogen adsorption/desorption, and thermogravimetric analysis (TG) showed that powders with high crystallinity (>90%) and high surface areas (>40 m(2)/g) are obtained after calcination at 700 degrees C for 3 h. Infrared spectroscopy and XRD results showed that these titanates nucleate from the amorphous phase with no intermediate phases, at low temperature (450 degrees C).

Electrical properties of screen printed BaTiO3 thick films

The deposition of thick film pastes by screen-printing is a relatively simple and convenient method to produce thicker layers with thickness up to 100 mum. In the present work, the barium titanate thick films were prepared from mechanically activated powders based on BaC03 and TiO2. After mixing, the powders were calcined at low temperature by slow heating and cooling rates. The thick films were deposited on to Al2O3 substrates through hybrid technology. The obtained films were fired at 850 degreesC together with electrode material (silver/palladium). The electrical properties of thick films: dielectric permittivity, dielectric losses, Curie temperature, hysteresis loop were reported. The obtained BT thick films can be applied in as multilayer capacitors or in gas sensor application. (C) 2003 Elsevier Ltd. All rights reserved.

Secondary phases in Nb-doped BaTiO3 ceramics

In this work, the effect of Nb2O5 addition on the microstructure of BaTiO3 was studied. From XRD diagrams, a diminution in tetragonality parameters with an increase in dopant concentration was observed. In order to determine morphology and composition of secondary phases in niobium-doped barium titanate, EDAX and SEM analyses were carried out. It was found that a concentration of dopant higher than 0.15 mol% leads to fine-grained BaTiO3 without abnormal grain growth. Otherwise, compositions of secondary phases correspond to the titanium-rich region in the BaO-TiO2 phase diagram. Besides, the titanium content in the precipitate increases with the Nb2O5 addition. (C) 2002 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Theoretical and experimental study of the relation between photoluminescence and structural disorder in barium and strontium titanate thin films

Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.

Improvement of the ferroelectric properties of ABO(3) (A= Pb, Ca, Ba; B=Ti, Zr) films

High-quality ABO(3)/LaNiO3 (A = Ph, Ca, Ba; B = Ti, Zr) hetero structures have been grown on LaAlO3 (1 0 0) substrate by the chemical solution deposition method and crystallized by a microwave oven technique. The structural, morphological and electric properties were characterized by means of X-ray diffraction (XRD), atomic force microscope (AFM), and dielectric and ferroelectric measurements. XRD patterns revealed single-phase polycrystalline and oriented thin films whose feature depends on the composition of the films. The AFM surface morphologies showed a smooth and crack-free surface with the average grain size ranging from 116 to 300 nm for both LaNiO3 electrode and the ferroelectric films. Dielectric measurements on these samples revealed dielectric constants as high as 1800 at frequency of 100 KHz. Such results showed that the combination of the chemical solution method with the microwave process provides a promising technique to grow high-quality thin films with good dielectric and ferroelectric properties. (c) 2005 Elsevier Ltd. All rights reserved.

Barium titanate screen-printed thick films

Barium titanate (BT) thick films were prepared from mechanically activated powders based on BaCO(3) and TiO(2). After homogenization and milling in a high-energy vibro mill, the powders were calcined at 700 degreesC for 2 h by slow heating and cooling rates. A thick film paste was prepared by mixing BT fine powders with small amount of low temperature sintering aid and organic binder. The thick films were screen-printed on alumina substrates electroded with Ag-Pd. The BT films were sintered at 850 degreesC for 1 h. The thickness was 25-75 mum depending of number of layers. The microstructure of thick films and the compatibility between BT layers and substrate were investigated by SEM Results of dielectric property measurements are also reported. (C) 2002 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Disorder-dependent photoluminescence in Ba0.8Ca0.2TiO3 at room temperature

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