Photoluminescence property of Ba(Zr0.25Ti0.75)O-3 powders prepared by solid state reaction and polymeric precursor method

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Investigation of Ferroelectric Layered Perovskite Barium Bismuth Tantalate Prepared by Solid-State Reaction

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

Thermal and electrochemical study of solid-state reaction of mercury with Pt-20% Rh alloy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Contribution to the study of the solid-state reaction of mercury with pure rhodium

Thermogravimetry (TG) and other analysis techniques (EDX, SEM, Mapping surface, X-ray diffraction, inductively coupled argon plasma emission spectroscopy and atomic spectrometry with cold vapor generation) were used to study the reaction of Hg with Rh. The results permitted the suggestion that, when subjected to heat, an electrodeposited Hg film reacts with Rh to form intermetallic products with different stabilities, as indicated by at least three mass loss steps. In the first step, between room temperature and 160°C, only the bulk Hg is removed. From this temperature up to about 175°C, the mass loss can be attributed to the desorption of a film of metallic Hg. The last step, from 175 to 240°C, can be ascribed to the removal of Hg from a thin dark film of RhHg2.

On the Methyl-Transfer Reaction in Crystalline Methyl 2-(Methylthio)benzenesulfonate: a Thermally Induced Non-Topochemical Solid-State Reaction

The rearrangement of methyl 2-(methylthio)benzenesulfonate (1) to the zwitterionic 2-(dimethyl-sulfonium)benzenesulfonate (2) is known to proceed in solution by intermolecular Me transfers. The same rearrangement has been observed to occur in crystalline 1, but the crystal structure shows that the molecular packing is not conducive to intermolecular Me transfer. The reaction has been carried out with mixed crystals composed of 1 and deuteriomethylated (D6)-l. By fast-atom-bombardment mass spectroscopy, it has been shown that the product consists of a 1:2:1 mixture of the non-, tri-, and hexadeuterated species, the mixture expected, if the solid-state reaction proceeds by intermolecular Me transfers. From this result, together with the slower rates of conversion in the single crystal compared with the melt, it can be concluded that the reaction must occur not topochemically but rather at defects such as microcavities, surfaces, and other irregularities in the ordered crystal arrangement.

Thermal study of the solid-state reactions on Pt-15%Rh/Hg system

Thermogravimetry (TG), energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), mapping surface and X-ray diffraction (XRD) were used for the study of solid-state reaction on Pt-15%Rh with electrodeposited mercury. The results suggest when heated the mercury film react with the Pt-15%Rh alloy to form intermetallics having different thermal stabilities indicated by three mass loss steps. The first mass loss step occurs between room temperature and 184 degrees C only the bulk Hg is removed and PtHg4, PtHg2 and RhHg2 were characterized by XRD. The second step, between 184 and 271 degrees C, was attributed to PtHg4 decomposition with formation of PtHg2 stabilized by RhHg2. The third step, between 271 and 340 degrees C, was attributed to decomposition of a solid-solution of PtHg2/RhHg2. The fourth step, between 340 and 600 degrees C, was ascribed to: (1) a thermal decomposition of PtHg2, formed by a PtHg eutectoid reaction (similar to 340 degrees C) on the surface and (2) Hg removal from a solid solution of Pt-15%Rh(Hg). (C) 2013 Elsevier B.V. All rights reserved.

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.

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.

Enhanced stability in CO2 of Ta doped BaCe0.9Y 0.1O3-δ electrolyte for intermediate temperature SOFCs

The influence of Ta concentration on the stability of BaCe 0.9-xTaxY0.1O3-δ (where x=0.01, 0.03 and 0.05) powders and sintered samples in CO2, their microstructure and electrical properties were investigated. The ceramic powders were synthesized by the method of solid state reaction, uniaxially pressed and sintered at 1550 °C to form dense electrolyte pellets. A significant stability in CO2 indicated by the X-ray analysis performed was observed for the samples with x≥0.03. The electrical conductivities determined by impedance measurements in the temperature range of 550-750 °C and in various atmospheres (dry argon, wet argon and wet hydrogen) increased with temperature but decreased with Ta concentration. The highest conductivities were observed in the wet hydrogen atmosphere, followed by those in wet argon, while the lowest were obtained in the dry argon atmosphere for each dopant concentration. The composition with Ta content of 3 mol% showed satisfactory characteristics: good resistance to CO2 in extreme testing conditions, while a somewhat reduced electrical conductivity is still comparable with that of BaCe0.9Y0.1O3-δ. © 2012 Elsevier Ltd and Techna Group S.r.l.

Lead-free BaBi4Ti4O15 ceramics: Effect of synthesis methods on phase formation and electrical properties

The processing of ferroelectric BaBi4Ti4O15 (BBT) ceramics from powders prepared by conventional solid state reaction (SSR) and mechanochemical activation (MA) has been investigated. It was shown that MA synthesis reduces the synthesis temperature of BBT powders, leading to smaller particles with reduced anisotropy and consequently to smaller grain size of ceramics. Dielectric properties were investigated in a wide range of temperatures (20-800 degrees C) and frequencies (1.21 kHz to 1 MHz). The relative dielectric permittivity at Curie temperature was higher for solid state obtained ceramics than for the mechanically treated ones. The conductivity of sintered samples was studied, suggesting decreasing of conductivity of BBT-MA in comparison with BBT-SS ceramics. The influence of the grain and the grain boundaries contribution to the dielectric behavior in both ceramics was analyzed through impedance spectroscopy. A well-defined ferroelectric hysteresis loop was obtained for both samples. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

In situ solid state oxidation reaction for La1-xSrxMnO3 (x=0, 0.1, 0.2 and 0.3) formation

In situ solid state oxidation reaction for an alternative La1-xSrxMnO3 (x = 0, 0.1, 0.2 and 0.3) formation is reported. Samples have been obtained by using strontium peroxide, lanthanum and manganese (III) oxide reagents. Strontium peroxide has induced the oxidation of Mn+3 to Mn+4. Lanthanum strontium-doped manganite was obtained without secondary phase formation. La0.825Sr0.175MnO3 showed two structural transitions. The first from 88 to 373 K and the second at 1073 K. which are explained by Jahn-Teller effect at low temperature and cation displacement at high temperature. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Thermal and crystalographic studies of mixture La2O3-SrO prepared via reaction in the solid state

The compound obtained via state solid reaction of the La2O3 and SrO oxides and expose the room atmosphere shows the crystallographic data of the compound reported as La2SrOx. However, thermogravimetric, differential thermal analysis and XRD with controlled temperature indicated that the stoichiometry of the compound is 2La(OH)(3)-SrCO3, which structural parameters were determined by using the Rietveld method. It was verified that when the compound exposed at room atmosphere, the mixture oxide absorbs H2O and CO2 producing hydroxide and carbonate of lanthanum and strontium, respectively, which thermal decomposition occurs by the same steps, producing the La2O3-SrO.

Reaction pathways in the solid state synthesis of multiferroic BiFeO 3

The obtaining of multiferroicBiFeO3 as a pure single-phase product is particularly complex since the formation of secondary phases seems to be unavoidable. The process by which these secondary impurities are formed is studied by analyzing the diffusion and solidstate reactivity of the Bi2O3–Fe2O3 system. Experimental evidence is reported which indicates that the progressive diffusion of Bi3+ ions into the Fe2O3 particles governs the solidstatesynthesis of the perovskite BiFeO3 phase. However a competition is established between the diffusion process which tends to complete the formation of BiFeO3, and the crystallization of stable Bi2Fe4O9 mullite crystals, which tend to block that formation reaction.

Reaction pathways in the solid state synthesis of multiferroic BiFeO3

The obtaining of multiferroic BiFeO3 as a pure single-phase product is particularly complex since the formation of secondary phases seems to be unavoidable. The process by which these secondary impurities are formed is studied by analyzing the diffusion and solid state reactivity of the Bi2O3?Fe2O3 system. Experimental evidence is reported which indicates that the progressive diffusion of Bi3+ ions into the Fe2O3 particles governs the solid state synthesis of the perovskite BiFeO3 phase. However a competition is established between the diffusion process which tends to complete the formation of BiFeO3, and the crystallization of stable Bi2Fe4O9 mullite crystals, which tend to block that formation reaction.

Photochemically induced nuclear spin polarization in reaction centers of photosystem II observed by 13C-solid-state NMR reveals a strongly asymmetric electronic structure of the P680.+ primary donor chlorophyll

We report 13C magic angle spinning NMR observation of photochemically induced dynamic nuclear spin polarization (photo- CIDNP) in the reaction center (RC) of photosystem II (PS2). The light-enhanced NMR signals of the natural abundance 13C provide information on the electronic structure of the primary electron donor P680 (chlorophyll a molecules absorbing around 680 nm) and on the pz spin density pattern in its oxidized form, P680⨥. Most centerband signals can be attributed to a single chlorophyll a (Chl a) cofactor that has little interaction with other pigments. The chemical shift anisotropy of the most intense signals is characteristic for aromatic carbon atoms. The data reveal a pronounced asymmetry of the electronic spin density distribution within the P680⨥. PS2 shows only a single broad and intense emissive signal, which is assigned to both the C-10 and C-15 methine carbon atoms. The spin density appears shifted toward ring III. This shift is remarkable, because, for monomeric Chl a radical cations in solution, the region of highest spin density is around ring II. It leads to a first hypothesis as to how the planet can provide itself with the chemical potential to split water and generate an oxygen atmosphere using the Chl a macroaromatic cycle. A local electrostatic field close to ring III can polarize the electronic charge and associated spin density and increase the redox potential of P680 by stabilizing the highest occupied molecular orbital, without a major change of color. This field could be produced, e.g., by protonation of the keto group of ring V. Finally, the radical cation electronic structure in PS2 is different from that in the bacterial RC, which shows at least four emissive centerbands, indicating a symmetric spin density distribution over the entire bacteriochlorophyll macrocycle.