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.

Preparation of Pb(Zr,Ti)O-3 thin films by soft chemical route

Lead zirconate titanate, Pb(Zr0.3Ti0.7)O-3 (PZT) thin films were prepared with success by the polymeric precursor method. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FT-IR), Micro-Raman spectroscopy and X-ray diffraction (XRD) were used to investigate the formation of the PZT perovskite phase. X-ray diffraction revealed that the film showed good crystallinity and no presence of secondary phases was identified. This indicates that the PZT thin films were crystallized in a single phase. PZT thin films showed a well-developed dense grain structure with uniform distribution, without the presence of rosette structure. The Raman spectra undoubtedly revealed these thin films in the tetragonal phase. For the thin films annealed at the 500-700 degreesC range, the vibration modes of the oxygen sublattice of the PZT perovskite phase were confirmed by FT-IR. The room temperature dielectric constant and dielectric loss of the PZT films, measured at 1 kHz were 646 and 0.090, respectively, for thin film with 365 nm thickness annealed at 700 degreesC for 2 h. A typical P-E hysteresis loop was observed and the measured values of P-s, P-r and E-c were 68 muC/cm(2), 44 muC/cm(2) and 123 kV/cm, respectively. The leakage current density was about 4.8 x 10(-7) A/cm(2) at 1.5 V. (C) 2003 Elsevier Ltd. All rights reserved.

Ionic medium effects on equilibrium constants .1. Proton, copper(II), cadmium(II), lead(II) and acetate activity coefficients in aqueous solution

The molar single ion activity coefficients associated with hydrogen, copper(II), cadmium(II) and lead(II) ions were determined at 25 degrees C and ionic strengths between 0.100 and 3.00 M (NaClO4), whereas for acetate the ionic strengths were fixed between 0.300 and 2.00 M, held with the same inert electrolyte. The investigation was carried out potentiometrically by using proton-sensitive glass, copper, cadmium and lead ion-selective electrodes and a second-class Hg\Hg-2(CH3COO)(2) electrode. It was found that the activity coefficients of these ions (y(i)) can be assessed through the following empirical equations:log y(H) = -0.542I(0.5) + 0.451I; log y(Cu) = -1.249I(0.5) + 0.912I; log y(Cd) = -0.829I(0.5) + 0.448I(1.5);log y(Pb) = -0.404I(0.5) + 0.117I(2); and log y(Ac) = 0.0370I .

Lead poisoning in cattle grazing pasture contaminated by industrial waste

Lead poisoning is described in a herd of 120 Nelore cows of which 35 were affected. All affected cows died after a clinical course of 2-7 d with clinical signs related to cortical neurological disturbances. The source of Pb was fumes from a car battery recycling plant which has had a failure in its filtering system. Lead concentrations in liver and kidneys of 2 cows, in soil;and in grass where the cows were held were respective 39 to 431 ppm, 147 to 431 ppm,and 245ppm. No significant gross changes were observed. Histopathology revealed of neuronal necrosis, vacuolation of the neuropil and hypertrophy of the vascular endothelium inthecerebral cortices, degeneration of the epithelial cellsofrenal proximal tubules, and hemosiderosis of kidney, spleen and liver.

Synthesis, ferroelectric and optical properties of (Pb,Ca)TiO3 thin films by soft solution processing

Calcium modified lead titanate sol was synthesized using a soft solution processing, the so-called polymeric precursor method. In soft chemistry method, soluble precursors such as lead acetate trihydrate, calcium carbonate and titanium isopropoxide, as starting materials, were mixed in aqueous solution. Pb0.7Ca0.3TiO3 thin films were deposited on platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure, dielectric and optical properties of the thin films were investigated. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) capacitors. The typical measured small signal dielectric constant and dissipation factor at a frequency of 100 kHz were 299 and 0.065, respectively, for a thin film with 230 nm thickness annealed at 600degreesC for 2 h. The remanent polarization (2P(r)) and coercive field (E-c) were 32 muC/cm(2) and 100 kV/cm, respectively. Transmission spectra were recorded and from them, refractive index, extinction coefficient, and band gap energy were calculated. Thin films exhibited good optical transmissivity, and had optical direct transitions. The present study confirms the validity of the DiDomenico model for the interband transition, with a single electronic oscillator at 6.858 eV. The optical dispersion behavior of PCT thin film was found to fit well the Sellmeir dispersion equation. The band gap energy of the thin film, annealed at 600degreesC, was 3.56 eV. The results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of PCT thin films.

Influence of Ca concentration on the electric, morphological, and structural properties of (Pb,Ca)TiO3 thin films

Pb1-xCaxTiO3 (0.10less than or equal toxless than or equal to0.40) thin films on Pt/Ti/SiO2/Si(100) substrates were prepared by the soft solution process and their characteristics were investigated as a function of the calcium content (x). The structural modifications in the films were studied using x-ray diffraction and micro-Raman scattering techniques. Lattice parameters calculated from x-ray data indicate a decrease in lattice tetragonality with the increasing content of calcium in these films. Raman spectra exhibited characteristic features of pure PbTiO3 thin films. Variations in the phonon mode wave numbers, especially those of lower wave numbers, of Pb1-xCaxTiO3 thin films as a function of the composition corroborate the decrease in tetragonality caused by the calcium doping. As the Ca content (x) increases from 0.10 to 0.40, the dielectric constant at room temperature abnormally increased at 1 kHz from 148 to 430. Also calcium substitution decreased the remanent polarization and coercive field from 28.0 to 5.3 muC/cm(2) and 124 to 58 kV/cm, respectively. These properties can be explained in terms of variations of phase transition (ferroelectric-paraelectric), resulting from the substitution the lead site of PbTiO(3)for the nonvolatile calcium. (C) 2002 American Institute of Physics.

Speciation of lead in seawater and river water by using Saccharomyces cerevisiae immobilized in agarose gel as a binding agent in the diffusive gradients in thin films technique

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

Characterization of dense lead lanthanum titanate ceramics prepared from powders synthesized by the oxidant peroxo method

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

Evaluation of different rhodium modifiers and coatings on the simultaneous determination of As, Bi, Pb, Sb, Se and of Co, Cr, Cu, Fe, Mn in milk by electrothermal atomic absorption spectrometry

Different kinds of modifiers and coatings on the integrated platform of transversely heated graphite atomizer (THGA) have been tested for the simultaneous determination of two group of elements: the first, the more volatile, formed by arsenic, bismuth, lead, antimony and selenium; the second, the less volatile, formed by cobalt, chromium, cupper, iron and manganese in milk by electrothermal atomic absorption spectrometry. Different Rh-modifiers were studied, such as Rh-coated platforms (Rh), carbide plus rhodium coated platforms (W-Rh, Zr-Rh), carbide-coated platforms (W and Zr) with co-injection of RhCl3, solutions and uncoated platforms with injection of solutions of Pd(NO3)(2), Mg(NO3)(2), and RhCl3. Milk samples were diluted 1:10 in 1.0% HNO3 and injected into the tube. The mass of modifier deposited and co-injected in the tube and the use of end capped tubes were also evaluated in order to improve the electrothermal behavior of analytes. Integrated platform pretreated with W plus co-injection RhCl3 for first group and pretreated with W-Rh for second group were elected. For 20 mu L injected samples the analytical curves in the 5.0-20.0 mu g L-1 concentration range have good linear correlation coefficients (r > 0.998). Relative standard deviations (n = 12) are < 6% and the calculated characteristic masses are between 5 pg and 62 pg.

Mechanochemical synthesis of lead magnesium niobate ceramics in iron media

The possibility of mechanochemical synthesis of the lead magnesium niobate (PMN) powders of the composition Pb(Mg(1/3)Nb(2/3))O(3) in iron vials was investigated. According to X-ray and energy-dispersive spectroscopy (EDS) analysis of the obtained powder mixtures, milling in iron vials resulted in incorporation of Fe and formation of PFN of composition Pb(Fe(1/2)Nb(1/2))O(3) simultaneously with formation of PMN. Relative amounts of PMN and PFN were determined based on values of Curie temperature and lattice constant of perovskite phase. Although only 1 wt pct of Fe was incorporated, a stoichiometry of the system was significantly changed, resulting in formation of pyrochlore phase and excess MgO. Single-phase perovskite was obtained when the excess of PbO and Nb(2)O(5) was added during mechanochemical synthesis. Because the dielectric properties were worse than expected, the alternative ways for improvement of dielectric properties were tried and discussed.

The determination of iron, lead, copper and zinc in the hair of children between 22 and 85 months old

In this study the levels of Cu, Fe, Pb and Zn, determined in hair of healthy children (25-85 months), living at Araraquara (São Paulo, Brasil) are reported. Analytical determinations were carried out by using atomic absorption spectrometry employing an air acetylene flame. The results obtained are discussed with regard to effect of sex and age, as well compared with others analogous studies.

Adsorption of Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) from aqueous solutions on a 2-mercaptobenzimidazole-modified silica gel

The chemically modified silica, obtained by reacting 2-mercaptobenz-imidazole with 3-chloropropyl silica gel, was used to adsorb Cu(II), Zn(II), Cd(II) and Pb(II) from aqueous solutions at various pH. Between pH 3-5, the order of selectivity was Hg(II) > Cd(II) ≫ Cu(II) ∼ Zn(II) ∼ Pb(II). Under batch conditions retentions of 100% were achieved for all metals except for Pb(II) where 93% was attained. Under column conditions recoveries of 100% were obtained for all metals. © 1990 Springer-Verlag.

Structural studies in lead germanate glasses: EXAFS and vibrational spectroscopy

The Raman, IR absorption and EXAFS spectra at the Ge K-edge and Pb LIII-edge of eight lead germanate glasses, with general formula xPbO(1-x)GeO2 with x = 0.20, 0.25, 0.33, 0.40, 0.50, 0.53, 0.56 and 0.60, have been measured. The occurrence of [GeO6] units besides [GeO4] could not be deduced unambiguously from the data. The vibrational and EXAFS data agree with a progressive depolymerization of the network. Starting from all Ge atoms linked to four bridging oxygens in GeO2 (x = 0), the number of tetrahedral units with one or two non-bridging oxygens increases with x. At low content, Pb2+ ions act as modifiers in the germanate structure, but to a lesser extent than an equivalent number of alkaline ions. © 1993.

U Pb and Sm Nd geochronologic studies of the eastern Borborema Province, Northeastern Brazil: initial conclusions

The Borborema Province of NE Brasil comprises the central part of a wide Pan-African-Brasiliano orogenetic belt that formed as a consequence of late Neoproterozoic convergence and collision of the São Luis-West Africa craton and the São Francisco-Congo-Kasai cratons. New Sm Nd and U Pb results from the eastern part of this province help to define the basic internal architecture and pre-collisional history of this province, with particular emphasis on delineating older cratonic terranes, their fragmentation during the Mesoproterozoic, and their assembly into West Gondwana during the Pan African-Brasiliano orogeny at ca. 600 Ma. The region can be divided into three major geotectonic domains: a) Rio Piranhas-Caldas Brandão massif, with overlying Paleoproterozoic to Neoproterozoic supracrustal rocks, north of the Patos Lineament; b) the Archean to Paleoproterozoic São Francisco craton (SFC) to the south; and c) a complex domain of Paleoproterozoic to Archean basement blocks with several intervening Mesoproterozoic to Neoproterozoic fold belts in the center (south of Patos Lineament and north of SFC). The northern and central domains comprise the Borborema Province. Archean basement gneiss and Transamazonian granulite of northern SFC are exposed in the southern part of the central domain, underlying southern parts of the Sergipano fold belt. Basement in the Rio Piranhas massif appears to consist mostly of Transamazonian (2.1 to 2.2 Ga) gneissic rocks; Nd model ages (TDM) of ca. 2.6 Ga for 2.15 Ga gneisses indicate a substantial Archean component in the protoliths to these gneisses. The Caldas Brandão massif to the east yields both Transamazonian and Archean U Pb zircon and Nd (TDM) ages, indicating a complex architecture. Metasedimentary rocks of the Jucurutu Formation yield detrital zircons with original crystallization ages as young as 1.8 Ga, indicating that these rocks may be late Paleoproterozoic and correlate with other ca. 1.8 Ga cratonic supracrustal rocks in Brazil such as the Roraima Group and Espinhaço Group. Most metavolcanic and pre-Brasiliano granitic units of the Sergipano (SDS), Pajeú-Paraíba (SPP), Riacho Pontal (SRP), and Piancó-Alto Brígida (SPAB) fold belts in the central domain formed ~ 1.0 ± 0.1 Ga, based on U Pb ages of zircons. Nd model ages (TDM) for these same rocks, as well as Brasiliano granites intruded into them and large parts of the Pernambuco-Alagoas massif, are commonly 1.3-1.7 Ga, indicating that rocks of the fold belts were not wholly derived from either older (> 2.1 Ga) or juvenile (ca. 1.0 Ga) crust, but include mixtures of both components. A simple interpretation of Brasiliano granite genesis and the Nd data implies that there is no Transamazonian or Archean basement underlying large parts of these fold belts or of the Pernambuco-Alagoas massif. An exception is a belt of syenitic Brasiliano plutons (Syenitoid Line) and host gneisses between SPAB and SPP that clearly has a Transamazonian (or older) source. In addition, there are several smaller blocks of Archean to Transamazonian gneiss that can be defined within and among these fold belts. These blocks do not appear to constitute a continuous basement complex, but appear to be isolated older crustal fragments. Our data support a model in which ca. 1.0 Ga rifting was an important tectonic and crust-forming event along the northern edge of the São Francisco craton. Our data also show that significant parts of the Borborema Province are not remobilized Transamazonian to Archean crust, but that Mesoproterozoic crust is a major feature of the Province. There are several small remnants of older crust within the area dominated by Mesoproterozoic crust, suggesting that the rifting event created several small continental fragments that were later incorporated into the Brasiliano collisional orogen. We cannot at present determine if the Rio Piranhas-Caldas Brandão massifs and the older crustal blocks of the central domain were originally part of the São Francisco craton or whether some (or all) of them came from more exotic parts of the Proterozoic Earth. Finally, our data have not yet revealed any juvenile terranes of either Transamazonian or Brasiliano age. © 1995.

Mechanism of phase formation in Pb(ZrxTi1-x)O3 synthesized by a partial oxalate method

The phase formation mechanism, as well as the morphotropic phase boundary, of lead zirconate titanate (PZT) processed by a partial oxalate method was investigated by simultaneous thermal analysis (TG-DTA) and by qualitative and quantitative X-ray diffraction (XRD). The results show that the ZrxTi1-xO2 (ZT) phase reacts with PbO forming the PZT phase without intermediate phases. XRD analysis showed the coexistence of rhombohedral and tetragonal phases for 0.47 ≤ x ≤ 0.55 with the phase boundary composition for x = 0.51. For low calcination temperatures, preferential formation of the PZT rhombohedral phase was observed. A model for phase formation of PZT by the partial oxalate method is proposed based on the existence of two interfaces of reaction (PbO-PZT and PZT-ZT) and diffusion of cations.