Structural XANES characterization of Ca0.99Sm0.01TiO3 perovskite and correlation with photoluminescence emission

In this work, CaTiO3:Sm (CT:Sm) were prepared by a soft chemical processing at different annealing temperatures starting with a disordered structure and reaching an ordered one, with the propose to understand the relationship between structural order-disorder and photoluminescence emission. The samples were characterized by titanium K-edge, Titanium L-II and L-III-edge XANES, electron paramagnetic resonance (EPR) and photoluminescence (PL) measurements. XANES results clearly point the presence of local distortion in [TiO6] octahedral clusters until the crystallization was completed. The interactions of the network clusters that form the CT:Sm structures provides favorable structural and electronic conditions for the appearance of PL phenomena. (C) 2012 Published by Elsevier B.V.

Hydroxythiazole-Based Fluorescent Probes for Fluoride Ion Detection

This work describes the synthesis of five O-silyloxy-1,3-thiazoles and their use as fast-response turn-on probes for fluoride ion detection in polar aprotic solvents and in aqueous cetyltrimethylammonium bromide micellar medium. The fluoride-triggered deprotection of these silyl ethers results in ca. 180-nm shifts in the fluorescence emission wavelengths. All compounds are suitable for the detection of fluoride ions with a detection limit in DMSO of 107 mol?L1; derivatives containing a 2-pyridyl moiety in the thiazole system are more efficient than those with a 3- or 4-pyridyl moiety. Typical anionic interferents, such as acetate or chloride, are not detected by O-silyloxy-1,3-thiazoles, making these compounds very specific for fluoride.

Titanium surface topography after brushing with fluoride and fluoride-free toothpaste simulating 10 years of use

Objectives: To conduct a controlled study contrasting titanium surface topography after procedures that simulated 10 years of brushing using toothpastes with or without fluoride. Methods: Commercially pure titanium (cp Ti) and Ti-6Al-4V disks (6 mm circle divide x 4 mm) were mirror-polished and treated according to 6 groups (n = 6) as a function of immersion (I) or brushing (B) using deionised water (W), fluoride-free toothpaste (T) and fluoride toothpaste (FT). Surface topography was evaluated at baseline (pretreatment) and post-treatment, using atomic force microscope in order to obtain three-dimensional images and mean roughness. Specimens submitted to immersion were submerged in the vehicles without brushing. For brushed specimens, procedures were conducted using a linear brushing machine with a soft-bristled toothbrush. Immersion and brushing were performed for 244 h. IFT and BFT samples were analysed under scanning electron microscope with Energy-Dispersive X-ray Spectroscopy (EDS). Pre and post-treatment values were compared using the paired Student T-test (alpha = .05). Intergroup comparisons were conducted using one-way ANOVA with Tukey post-test (alpha = .05). Results: cp Ti mean roughness (in nanometers) comparing pre and post-treatment were: IW, 2.29 +/- 0.55/2.33 +/- 0.17; IT, 2.24 +/- 0.46/2.02 +/- 0.38; IFT, 2.22 +/- 0.53/1.95 +/- 0.36; BW, 2.22 +/- 0.42/3.76 +/- 0.45; BT, 2.27 +/- 0.55/16.05 +/- 3.25; BFT, 2.27 +/- 0.51/22.39 +/- 5.07. Mean roughness (in nanometers) measured in Ti-6Al-4V disks (pre/post-treatment) were: IW, 1.79 +/- 0.25/2.01 +/- 0.25; IT, 1.61 +/- 0.13/1.74 +/- 0.19; IFT, 1.92 +/- 0.39/2.29 +/- 0.51; BW, 2.00 +/- 0.71/2.05 +/- 0.43; BT, 2.37 +/- 0.86/11.17 +/- 2.29; BFT, 1.83 +/- 0.50/15.73 +/- 1.78. No significant differences were seen after immersions (p > .05). Brushing increased the roughness of cp Ti and of Ti-6Al-4V (p < .01); cp Ti had topographic changes after BW, BT and BFT treatments whilst Ti-6Al-4V was significantly different only after BT and BTF. EDS has not detected fluoride or sodium ions on metal surfaces. Conclusions: Exposure to toothpastes (immersion) does not affect titanium per se; their use during brushing affects titanium topography and roughness. The associated effects of toothpaste abrasives and fluorides seem to increase roughness on titanium brushed surfaces. (C) 2012 Elsevier Ltd. All rights reserved.

Structural refinement, optical and microwave dielectric properties of BaZrO3

In this work, barium zirconate (BaZrO3) ceramics synthesized by solid state reaction method and sintered at 1670 degrees C for 4 h were characterized by X-ray diffraction (XRD), Rietveld refinement, and Fourier transform infrared (FT-IR) spectroscopy. XRD patterns, Rietveld refinement data and FT-IR spectra which confirmed that BaZrO3 ceramics have a perovskite-type cubic structure. Optical properties were investigated by ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) measurements. UV-vis absorption spectra suggested an indirect allowed transition with the existence of intermediary energy levels within the band gap. Intense visible green PL emission was observed in BaZrO3 ceramics upon excitation with a 350 nm wavelength. This behavior is due to a majority of deep defects within the band gap caused by symmetry breaking in octahedral [ZrO6] clusters in the lattice. The microwave dielectric constant and quality factor were measured using the method proposed by Hakki-Coleman. The dielectric resonator antenna (DRA) was investigated experimentally and numerically using a monopole antenna through an infinite ground plane and Ansoft's high frequency structure simulator software, respectively. The required resonance frequency and bandwidth of DRA were investigated by adjusting the dimension of the same material. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Size-induced diffuse behavior in Pb0.89La0.11Zr0.40Ti0.60O3 nanocrystalline ferroelectric ceramics

The Pb1-xLaxZryTi1-yO3 system is a perovskite ABO(3) structured material which presents ferroelectric properties and has been used as capacitors, actuators, transducers and electro-optic devices. In this paper, we describe the synthesis and the characterization of Pb0.89La0.11Zr0.40Ti0.60O3 (PLZT11) nanostructured material. The precursor polymeric method and the spark plasma sintering technique were respectively used to prepare ceramic samples. In order to compare the effect of grain size, microcrystalline PLZT11 ceramic samples were also prepared. PLZT11 samples were characterized by X-ray diffraction technique which results show a reduction on the degree of tetragonality as the average grain size decreases. Moreover, the grain size decrease to a nanometer range induces a diffuse behavior on the dielectric permittivity curves as a function of the temperature and a reduction on the dielectric permittivity magnitude. Furthermore, the large number of grain boundaries due to the nanometer size gives rise to a dielectric anomaly. (C) 2012 Elsevier Masson SAS. All rights reserved.

Novel SrTi1-xFexO3 nanocubes synthesized by microwave-assisted hydrothermal method

We report herein for the first time a facile synthesis method to obtain SrTi1-xFexO3 nanocubes by means by a microwave-assisted hydrothermal (MAH) method at 140 degrees C. The effect of iron addition on the structural and morphological properties of SrTiO3 was investigated. X-ray diffraction measurements show that all STFO samples present a cubic perovskite structure. X-ray absorption spectroscopy at Fe absorption K-edge measurements revealed that iron ions are in a mixed Fe2+/Fe3+ oxidation state and preferentially occupy the Ti4+-site. UV-visible spectra reveal a reduction in the optical gap (E-gap) of STFO samples as the amount of iron is increased. An analysis of the data obtained by field emission scanning electron microscopy points out that the nanoparticles present a cubic morphology independently of iron content. According to high-resolution transmission electron microscopy results, these nanocubes are formed by a self-assembly process of small primary nanocrystals.

Strontium zirconate heterogeneous catalyst for biodiesel production: Synthesis, characterization and catalytic activity evaluation

Strontium zirconate oxide was synthesized by co-precipitation and the citrate route and was evaluated as a heterogeneous catalyst for biodiesel production. The catalyst samples were characterized by XRD, FTIR, and TG, and catalytic activity was measured based on the ester content of the biodiesel produced that was quantified by GC. The co-precipitate samples were obtained in alkaline pH and had a mixture of the perovskite and pure strontium and zirconium oxide phases. Ester conversion using these samples was approximately 1.6%, indicating no catalytic activity. The citrate route was more efficient in producing perovskite when carried out at pH 7-8; excess SrCO3 was found on the catalyst surface due to CO2 adsorption, thus demonstrating no catalytic activity. The same synthesis carried out at pH 2 resulted in free OH- groups, with a small amount of the carbonate species that produced ester yield values of 98%. Therefore, matrices based on strontium zirconate produced via the citrate route in acidic media are potential heterogeneous catalysts for transesterification. (C) 2012 Elsevier B.V. All rights reserved.

Study of La2-xCaxCuO4 perovskites for the low temperature water gas shift reaction

The effects of small fractions of calcium (x = 0, 0.05, 0.1, 0.15, and 0.20) on the structure and the catalytic properties of La2-xCaxCuO4 peroviskites have been investigated. The samples have been synthesized using the co-precipitation method. Perovskite-type oxides were characterized by XRD, TPR, XPS, XANES, SEM, and TEM. Catalytic tests for the water gas shift reaction (WGSR) were carried out in a tubular reactor at 290 degrees C. All samples showed a well-defined perovskite structure with surface areas between 6 and 18 m(2) g(-1). The partial substitution of La by Ca enhanced the stability of the perovskites and increased their reduction temperature. All catalysts were actives for WGSR, and the best catalytic performance was obtained for the La1.85Ca0.15CuO4 catalyst, but the samples with 5 and 10% of Ca had the best TOF values for reaction. These results can be associated to promoter effect of calcium, the high surface area, and the reducible species Cu-0 and Cu1+. (C) 2011 Elsevier B.V. All rights reserved.

Local order and electronic structure of Pb1-xLaxZr0.40Ti0.60O3 materials and its relation with ferroelectric properties

The knowledge of electronic and local structures is a fundamental step towards understanding the properties of ferroelectric ceramics. X-ray absorption near-edge structure (XANES) of Pb1-xLaxZr0.40Ti0.60O3 ferroelectric samples was measured in order to know how the local order and electronic structure are related to their ferroelectric property, which was tailored by the substitution of lead by lanthanum atoms. The analysis of XANES spectra collected at Ti K- and L-edges XANES showed that the substitution of Pb by La leads to a decrement of local distortion around Ti atoms on the TiO6 octahedron. The analysis of O K-edge XANES spectra showed that the hybridization between O 2p and Pb 6sp states is related to the displacement of Ti atoms in the TiO6 octahedra. Based on these results, it is possible to determine that the degree of ferroelectricity in these samples and the manifestation of relaxor behavior are directly related to the weakening of O 2p and Pb 6sp hybridization. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720472]

The Banhado Alkaline Complex, Southeastern Brazil: source and evolution of potassic SiO2-undersaturated high-Ca and low-Ca magmatic series

The Cretaceous Banhado alkaline complex in southeastern Brazil presents two potassic SiO2-undersaturated series. The high-Ca magmatic series consist of initially fractionated olivine (Fo(92-91)) + diopside (Wo(48-43)En(49-35)Ae(0-7)), as evidenced by the presence of xenocrysts and xenoliths. In that sequence, diopside (Wo(47-38)En(46-37)Ae(0-8)) + phlogopite + apatite + perovskite (Prv(> 92)) crystallized to form the phlogopite melteigite and led to the Ca enrichment of the magma. Diopside (Wo(47-41)En(32-24) Ae(3-14)) continued to crystallize as an early mafic mineral, followed by nepheline (Ne(74.8-70.1)Ks(26.3-21.2)Qz(7.6-0.9)) and leucite (Lc(65-56)) and subsequently by melanite and potassic feldspar (Or(85-99)Ab(1-7)) to form melanite ijolites, wollastonite-melanite urtites and melanite-nepheline syenites. Melanite-pseudoleucite-nepheline syenites are interpreted to be a leucite accumulation. Melanite nephelinite dykes are believed to represent some of the magmatic differentiation steps. The low-Ca magmatic series is representative of a typical fractionation of aegirine-augite (Wo(36-29)En(25-4)Ae(39-18)) + alkali feldspar (Or(57-96)Ab(3-43)) + nepheline (Ne(76.5-69.0)Ks(19.9-14.4)Qz(15.1-7.7)) + titanite from phonolite magma. The evolution of this series from potassic nepheline syenites to sodic sodalite syenites and sodalitolites is attributed to an extensive fractionation of potassic feldspar, which led to an increase of the NaCl activity in the melt during the final stages forming sodalite-rich rocks. Phonolite dykes followed a similar evolutionary process and also registered some crustal assimilation. The mesocratic nepheline syenites showed interactions with phlogopite melteigites, such as compatible trace element enrichments and the presence of diopside xenocrysts, which were interpreted to be due to a mixing/mingling process of phonolite and nephelinite magmas. The geochemical data show higher TiO2 and P2O5 contents and lower SiO2 contents for the high-Ca series and different LILE evolution trends and REE chondrite-normalized patterns as compared to the low-Ca series. The Sr-87/Sr-86, Nd-143/Nd-144, Pb-206/Pb-204 and Pb-208/Pb-204 initial ratios for the high-Ca series (0.70407-0.70526, 0.51242-0.51251, 17.782-19.266 and 38.051-39.521, respectively) were slightly different from those of the low-Ca series (0.70542-0.70583, 0.51232-0.51240, 17.758-17.772 and 38.021-38.061, respectively). For both series, a CO2-rich potassic metasomatized lithospheric mantle enriched the source with rutile-bearing phlogopite clinopyroxenite veins. Kamafugite-like parental magma is attributed to the high-Ca series with major contributions from the melting of the veins. Potassic nephelinite-like parental magma is assigned to the low-Ca series, where the metasomatized wall-rock played a more significant role in the melting process.

Seven years of external control of fluoride levels in the public water supply in Bauru, São Paulo, Brazil

Fluoridation of the public water supplies is recognized as among the top ten public health achievements of the twentieth century. However, the positive aspects of this measure depend on the maintenance of fluoride concentrations within adequate levels. To report the results of seven years of external control of the fluoride (F) concentrations in the public water supply in Bauru, SP, Brazil in an attempt to verify, on the basis of risk/benefit balance, whether the levels are appropriate. From March 2004 to February 2011, 60 samples were collected every month from the 19 supply sectors of the city, totaling 4,641 samples. F concentrations in water samples were determined in duplicate, using an ion-specific electrode (Orion 9609) coupled to a potentiometer after buffering with TISAB II. After the analysis, the samples were classified according to the best risk-benefit adjustment. Means (±standard deviation) of F concentrations ranged between 0.73±0.06 and 0.81±0.10 mg/L for the different sectors during the seven years. The individual values ranged between 0.03 and 2.63 mg/L. The percentages of the samples considered “low risk” for dental fluorosis development and of “maximum benefit” for dental caries prevention (0.55-0.84 mg F/L) in the first, second, third, fourth, fifth, sixth, and seventh years of the study were 82.0, 58.5, 37.4, 61.0, 89.9, 77.3, and 72.4%, respectively, and 69.0% for the entire period. Fluctuations of F levels were found in the public water supply in Bauru during the seven years of evaluation. These results suggest that external monitoring of water fluoridation by an independent assessor should be implemented in cities where there is adjusted fluoridation. This measure should be continued in order to verify that fluoride levels are suitable and, if not, to provide support for the appropriate adjustments

Effect of fluoride sodium mouthwash solutions on cpTI: evaluation of physicochemical properties

The effects of fluoride, which is present in different oral hygiene products, deserve more investigation because little is known about their impact on the surface of titanium, which is largely used in Implantology. This study evaluated the surface of commercially pure titanium (cpTi) after exposure to different concentrations of sodium fluoride (NaF). The hypothesis tested in this study was that different concentrations of NaF applied at different time intervals can affect the titanium surface in different ways. The treatments resulted in the following groups: GA (control): immersion in distilled water; GB: immersion in 0.05% NaF for 3 min daily; GC: immersion in 0.2% NaF for 3 min daily; GD: immersion in 0.05% NaF for 3 min every 2 weeks; and GE: immersion in 0.2% NaF for 3 min every 2 weeks. The experiment lasted 60 days. Roughness was measured initially and every 15 days subsequently up to 60 days. After 60 days, corrosion analysis and anodic polarization were done. The samples were examined by scanning electron microscopy (SEM). The roughness data were analyzed by ANOVA and there was no significant difference among groups and among time intervals. The corrosion data (i corr) were analyzed by the Mann-Whitney test, and significant differences were found between GA and GC, GB and GC, GC and GD, GC and GE. SEM micrographs showed that the titanium surface exposed to NaF presented corrosion that varied with the different concentrations. This study suggests that the use of 0.05% NaF solution on cpTi is safe, whereas the 0.2% NaF solution should be carefully evaluated with regard to its daily use.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786

Influence of the network modifier on the characteristics of MSnO3 (M=Sr and Ca) thin films synthesized by chemical solution deposition

CaSnO3 and SrSnO3 alkaline earth stannate thin films were prepared by chemical solution deposition using the polymeric precursor method on various single crystal substrates (R- and C-sapphire and 100-SrTiO3) at different temperatures. The films were characterized by X-ray diffraction (θ-2θ, ω- and φ-scans), field emission scanning electron microscopy, atomic force microscopy, micro-Raman spectroscopy and photoluminescence. Epitaxial SrSnO3 and CaSnO3 thin films were obtained on SrTiO3 with a high crystalline quality. The long-range symmetry promoted a short-range disorder which led to photoluminescence in the epitaxial films. In contrast, the films deposited on sapphire exhibited a random polycrystalline growth with no meaningful emission regardless of the substrate orientation. The network modifier (Ca or Sr) and the substrate (sapphire or SrTiO3) influenced the crystallization process and/or the microstructure. Higher is the tilts of the SnO6 octahedra, as in CaSnO3, higher is the crystallization temperature, which changed also the nucleation/grain growth process.