An approach to analyzing synthesis, structure and properties of bismuth titanate ceramics

The family of bismuth titanate, Bi(4)Ti(3)O(12) (BIT) layered-structured ferroelectrics materials is attractive from the viewpoint of such as their application as electronic materials dielectrics, piezoelectrics and pyroelectrics, because they are characterized by good stability of piezoelectric properties, a high Curie temperature and a good resistance vs temperature. Bismuth titanate (Bi(4)Ti(3)O(12)) powders can be prepared using different methods, depending if the creation will be film coating or ceramics. The structure and properties of bismuth titanate materials show a significance dependence on the applied synthesis method. In this review paper, we made an attempt to give an approach to analyszing the structure, synthesis methods and properties of bismuth titanate ferroelectrics materials.

Blue cooperative luminescence properties in Yb3+ doped GeO2-PbO-Bi2O3 vitreous system for the production of thin films

Germanate glasses are of interest for optoelectronic applications because they combine high mechanical strength, high chemical durability and temperature stability with a large transmission window (400 to 4500 nm) and high refractive index (2.0). GeO2-PbO-Bi2O3 glasses doped with Y-b(3+) were fabricated by melting powders in a crucible and then pouring them in a brass mold. Energy Dispersive Spectroscopy showed that the glass composition has a high spatial uniformity and that the Yb concentration in the solid sample is proportional to the Yb concentration in the melt, what was confirmed by absorption measurements. Intense blue emission at 507 nm was observed, corresponding to half of the wavelength of the near infrared region (NIR) emission; besides, a decay lifetime of 0.25 ms was measured and this corresponds to half of the decay lifetime in the infrared region; these are very strong indications of the presence of blue cooperative luminescence. Larger targets have been produced to be sputtered, resulting in thin films for three dimensional (3D) display and waveguide applications. (c) 2006 Elsevier B.V. All rights reserved.

Study of Ti-modified columbite route and the effect of lithium doping in 0.9PMN-0.1PT ceramics

The influence of lithium on the structural characteristics of PMN-PT ceramic was studied. The synthesis of PMN-PT powders using this precursor leads to the formation of high amount of perovskite phase. The insertion of Li(+) ions in B-site affects the microstructure because the rise in mass transport changes the mechanical characteristics of sintered ceramic. Higher values of K(m) and T(m) were gotten when lithium is inserted into perovskite phase. Secondary phase was found when lithium content increase beyond 1 mol%, besides the occurrence of transgranular fractures in sintered ceramic. Also, the additive acts increasing the relaxor behavior.

Influence of Ta2O5 on the electrical properties of ZnO- and CoO-doped SnO2 varistors

SnO2-based varistors doped with 0.5% cobalt, 0.5% zinc and various tantalum amounts were prepared by the solid-state route. Experimental evidence shows that small quantities of Ta2O5 improve the nonlinear properties of the samples significantly. It was found that samples doped with 0.05 mol% Ta2O5 exhibit the highest density (98.5%), the lowest electric breakdown field (E-b = 1050 V/cm) and the highest coefficient of nonlinearity (alpha = 11.5). The effect of Ta2O5 dopant could be explained by the substitution of Ta5+ by Sn4+. (C) 2004 Elsevier Ltd and Techna S.r.l. All rights reserved.

Densification and electrical conductivity of fast fired manganese-doped ceria ceramics

Reactive pure and manganese-doped (5% and 10 at.%) ceria nanosized powders were prepared by the polymeric precursor technique. Physical properties of powder materials were studied by X-ray diffraction, nitrogen adsorption, and diffuse reflectance infrared Fourier transform spectroscopy. Characterization of powder compacts after fast firing at 1200 degrees C for 5 min was carried out by scanning electron microscopy and impedance spectroscopy measurements. The bulk apparent density of sintered pellets was determined for pellets of different compositions sintered at 1200 degrees C. A gradual decrease of the particle size occurs with increasing doping content. Relatively high values of apparent density were obtained after fast firing doped specimens at 1200 degrees C. DRIFT spectra evidence that a fraction of Mn ions was segregated onto particles surface. The electrical resistivity of sintered pellets reveals different mechanisms of conduction depending on the Mn content. (C) 2005 Elsevier B.V All rights reserved.

Room-temperature photoluminescence of BaTiO3: Joint experimental and theoretical study

Strong photoluminescent emission has been measured at room temperature for noncrystalline BaT'O-3 (BT) perovskite powders. A joint experimental and theoretical study has been carried out to rationalize this phenomenon. From the experimental side, BT powder samples have been synthesized following a soft chemical processing, their crystal structure has been confirmed by x-ray data and the corresponding photoluminescence (PL) properties have been measured. Only the structurally disordered samples present PL at room temperature. From the theoretical side, first-principles quantum-mechanical techniques, based on density-functional theory at the B3LYP level, have been employed to study the electronic structure of crystalline (BT-c) and asymmetric (BT-a) models. Theoretical and experimental results are found to be consistent and their confrontation leads to an interpretation of the PL apparition at room temperature in the structurally disordered powders.

Synthesis and characterization of 9.5/65/35 PLZT prepared from the polymeric precursors

The 9.5/65/35 PLZT was prepared from the polymeric precursors (the Pechini and partial oxalate process) and by sintering in two stages in an oxygen atmosphere. After thermal treatment at 400 degreesC, the powders were calcinated and sintered at 1200 degreesC with slow heating and cooling rates. The second stage of sintering consisted of hot pressing at the same temperature in oxygen atmosphere. After calcination of PLZT powders obtained by both methods, as well as after sintering of PLZT obtained by Pechini process, the paraelectric cubic phase was formed. After sintering of PLZT obtained by partial oxalate procedure, small tetragonality of crystal structure was observed. After hot pressing PLZT was pseudocubic. SEM microstructural analyses were carried out of the sintering and hot pressed samples and indicated the small grain size less than 2 mum. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Structure of SnO2 alcosols and films prepared by sol-gel dip coating

To obtain SnO2 films to be used for surface protection of fluoride glasses, a non-aqueous sol-gel route for the preparation was developed. An ethanolic SnO2 colloidal suspension was prepared by thermohydrolysis of SnCl4 solution at 70 degreesC. By using this procedure, redispersable powders with nanometer sized particles were obtained. Films were obtained by dip coating on glass and mica substrates. The structures of the ethanolic precursor suspension and films were compared to those of similar samples prepared by the classical aqueous sol-gel route. Comparative analyses performed by photon correlation spectroscopy demonstrated that the powders obtained by freeze-drying are fully redispersable either in aqueous or in alcoholic solutions at pH greater than or equal to 8. As prepared sols and redispersed colloidal suspensions have hydrodynamic radius distribution (2-14 nm) with an average size close to 7 nm. The variations in film structures with firing temperature were investigated by small-angle X-ray scattering and X-ray reflectometry. The experimental results show that the films have a two level porous structure composed of agglomerates of primary colloidal particles. The sintering of the primary particles leads to the densification of agglomerates and to the formation of inter-agglomerate spatially correlated pores. The volume fraction of intra-agglomerate pores is reduced from approximate to 50% to approximate to 30% by the precipitation of precursor salts partially hydrolyzed in ethanolic solution. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Effect of PbO excess on the formation of lead magnesium niobate perovskite by the columbite method

The effect of lead excess on the pyrochlore-type formation in Pb(Mg1/3Nb2/3)O-3 (PMN) powders has been investigated. The polymeric precursor method was used in the synthesis of the columbite in association to the partial oxalate method to synthesize the PMN powder samples. Structure refinement of the columbite precursor and PMN powders was carried out using the Rietveld method. The quantitative phase analysis showed that the amount of perovskite phase is not affected by PbO excess, but a great excess drives the pyrochlore-type formation so that 3 wt.% of PbO causes the predominance of Mg-containing pyrochlore phase. Using the refined data obtained from the Rietveld refinement, the compositional fluctuation in the perovskite phase was calculated from Nb/Mg ratio values and Pb occupation factor. Mg inclusion occurs concomitant with Ph one into PMN perovskite phase and this effect is directed by PbO excess during powder synthesis. (C) 2003 Elsevier B.V. All rights reserved.

Role of the surface state and structural feature in the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The sols produced by admixture of ZrOCl2 acidified solutions to hot H2SO4 aqueous solutions were studied to clarify the effects of Cl- and SO42- ions on the kinetic stability of nanoparticles and to obtain some new evidence concerning the mechanism of a thermoreversible sol-gel transition observed in this system. The study of suspensions prepared with different molar ratios R-S = [Zr]/[SO42-] and R-Cl = [Zr]/[Cl-] revealed domains of composition of formation of thermoreversible gels, thermostable sols, and powder precipitation. The effects of R-S and R-Cl on the structural features of nanoparticles and on the particle solution interface were systematically analyzed for samples of thermoreversible and thermostable sol domains. Small-angle X-ray scattering measurements revealed the presence of small fractal aggregates in all samples of thermoreversible domains, while compact packing aggregates of primary particles are present in the thermostable sol. Extended X-ray absorption fine structure and elemental chemical analysis revealed that irrespective of the nominal value of R-S and R-Cl all studied samples of the thermoreversible domain are constituted by a well-defined compound possessing an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded on the surface by complexing sulfate ligands. zeta potentials of powders extracted by freeze-drying from the thermoreversible gel revealed a point of surface charge inversion attributed to the specific adsorption of SO42- ion. Thermoreversible gel formation is rationalized by considering the effect of the specific adsorption on the electrical double-layer repulsion together with the temperature dependency of the physical chemical properties of ions in solution.

Morphological and luminescent studies on nanosized Er, Yb-Yttrium oxide up-converter prepared from different precursors

In this paper, we report luminescent and morphological studies with yttrium oxide samples doped with ytterbium and erbium. The samples were prepared by the combustion method and also from different precursors: oxalate, basic carbonate and polymeric resin. All powders were identified Lis being an yttrium oxide with a C-form structure, independent of the employed precursor. From mean crystallite size measurements, it was verified that oxides prepared through the polymeric precursor and combustion methods lead to the smallest crystallite size. Particle shape and size were investigated by SEM and TEM, and showed that both the oxalate precursor and the combustion methods do not provide oxide materials of suitable shape or size, on the other hand. The basic carbonate and polymeric precursors resulted in spherically shaped particles with an average diameter of 90 and 15 run. respectively, Upon 980 run diode laser excitation, green and red emission lines were detected for all samples and were assigned to the H-2(11/2) S-4(3/2) -> I-4(15/2) and (4)Fg(9/2) -> 4I(15/12) transitions, respectively. Such transitions are characteristic for Er3+ and result from energy transfer from Yb3+ energy levels, F-2(7/2) -> F-2(5/2). A relationship between the decrease in the mean crystallite size and the enhancement in red emission was also established as well as the influence of the presence of a high percentage of Yb-3 Both factors promote ET from Yb3+ (F-2(5/2)) to Er3+ (I-4(11/2)). (c) 2004 Elsevier B.V. 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.

Photoluminescent BaMoO4 nanopowders prepared by complex polymerization method (CPM)

The BaMoO4 nanopowders were prepared by the Complex Polymerization Method (CPM). The structure properties of the BaMoO4 powders were characterized by FTIR transmittance spectra, X-ray diffraction (XRD), Raman spectra, photoluminescence spectra (PL) and high-resolution scanning electron microscopy (HR-SEM). The XRD, FTIR and Raman data showed that BaMoO4 at 300 degrees C was disordered. At 400 degrees C and higher temperature, BaMoO4 crystalline scheelite-type phases could be identified, without the presence of additional phases, according to the XRD, FTIR and Raman data. The calculated average crystallite sizes, calculated by XRD, around 40 nm, showed the tendency to increase with the temperature. The crystallite sizes, obtained by HR-SEM, were around of 40-50 nm. The sample that presented the highest intensity of the red emission band was the one heat treated at 400 degrees C for 2 h, and the sample that displayed the 'highest intensity of the green emission band was the one heat treated at 700 degrees C for 2 h. The CPM was shown to be a low cost route for the production of BaMoO4 nanopowders, with the advantages of lower temperature, smaller time and reduced cost. The optical properties observed for BaMoO4 nanopowders suggested that this material is a highly promising candidate for photoluminescent applications. (C) 2005 Elsevier B.V. All rights reserved.

Effect of boron powder purity on superconducting properties of MgB2

The effect of the properties of starting boron powders on the superconducting properties of MgB2 has been studied. The 92% and 96% pure powders produce lower surface reactivity and larger particle size than the 99% boron powder, as can be seen from Brunauer - Emmett - Teller (BET) and scanning electron microscopy (SEM) results, indicating that the low purity powders cannot be used to archive the same superconducting properties as those of samples made from pure 99% boron powder. However, the purity of 92% and 96% boron powders can be improved by using a simple chemical process, leading to enhanced magnetic critical current densities J(c). From x-ray diffraction (XRD) measurement, oxide impurity has been observed, which might be originated from the B2O3 phase in the boron powders. In order to get high performance MgB2, it is obviously important to control the phase composition and microstructure of amorphous boron starting powders and solid reaction conditions.

Investigation on possibility of mechanochemical synthesis of CaTiO3 from different precursors

Recently, mechanochemical synthesis was widely used in preparation of perovskite type of materials, such as BaTiO3, PbTiO3, PZT, etc. In this work, the possibility of mechanochemical synthesis of CaTiO3 from different precursors, such as CaCO3 or CaO and TiO2 was investigated. Intensive milling of mixture of CaO and TiO2, under optimal milling conditions, resulted in synthesis of single phase CaTiO3. It was also found that intensive milling of powder mixture containing CaCO3 and TiO2 only activate the powders for the sintering process; hence the CaTiO3 could be obtained at lower temperatures of sintering. To complete reaction of CaTiO3 formation during milling it is necessary to reduce CO2 partial pressure, i.e. it is necessary to change the atmosphere inside the vials during milling. In this work, an explanation for difference in milling behavior of different precursors was proposed and discussed. (c) 2006 Elsevier Ltd. All rights reserved.