Structure and optical properties of [Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders

[Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders with different yttrium concentrations (x = 0, 0.025 and 0.05) were prepared by solid state reaction. These powders were analyzed by X-ray diffraction (XRD). Fourier transform Raman scattering (FT-RS), Fourier transform infrared (FT-IR) and X-ray absorption near-edge (XANES) spectroscopies. The optical properties were investigated by means of ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. Even with the addition of yttrium, the XRD patterns revealed that all powders crystallize in a perovskite-type cubic structure. FT-RS and FT-IR spectra indicated that the presence of [YO(6)] clusters is able to change the interaction forces between the O-Ti-O and O-Zr-O bonds. XANES spectra were used to obtain information on the off-center Ti displacements or distortion effects on the [TiO(6)] clusters. The different optical band gap values estimated from UV-vis spectra suggested the existence of intermediary energy levels (shallow or deep holes) within the band gap. The PL measurements carried out with a 350 nm wavelength at room temperature showed that all powders present typical broad band emissions in the blue region. (C) 2010 Elsevier Masson SAS. All rights reserved.

Temperature Dependence of the Intergranular Critical Current Density in Uniaxially Pressed Bi(1.65)Pb(0.35)Sr(2)Ca(2)Cu(3)O(10+delta) Samples

We have studied the normal and superconducting transport properties of Bi(1.65)Pb(0.35)Sr(2)Ca(2)Cu(3)O(10+delta) (Bi-2223) ceramic samples. Four samples, from the same batch, were prepared by the solid-state reaction method and pressed uniaxially at different compacting pressures, ranging from 90 to 250 MPa before the last heat treatment. From the temperature dependence of the electrical resistivity, combined with current conduction models for cuprates, we were able to separate contributions arising from both the grain misalignment and microstructural defects. The behavior of the critical current density as a function of temperature at zero applied magnetic field, J (c) (T), was fitted to the relationship J (c) (T)ae(1-T/T (c) ) (n) , with na parts per thousand 2 in all samples. We have also investigated the behavior of the product J (c) rho (sr) , where rho (sr) is the specific resistance of the grain-boundary. The results were interpreted by considering the relation between these parameters and the grain-boundary angle, theta, with increasing the uniaxial compacting pressure. We have found that the above type of mechanical deformation improves the alignment of the grains. Consequently the samples exhibit an enhance in the intergranular properties, resulting in a decrease of the specific resistance of the grain-boundary and an increase in the critical current density.

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.

Relaxation of the electrical resistivity in Cr-doped Nd(0.5)Ca(0.5)MnO(3) single crystals

We have performed a systematic study of the time and temperature dependencies of the electrical resistivity (rho(T, t)) inNd(0.5)Ca(0.5)Mn(1-x)Cr(x)O(3) single crystals with x = 0.02 and 0.07 in order to examine the dynamics of the phase separation. The relaxation effects can be described by the combination of a rapid exponential increase/decrease with a slower logarithmic contribution at longer times. The experimental results suggest the existence of a large temperature window in which huge relaxation effects occur, and the relative fraction of the coexisting phases rapidly changes as a function of time, depending on the initial magnetic state of the sample. The rho(T, t) relaxation measurements were shown to be a suitable tool for probing the dynamical nature of the phase separation, in which magnetically distinct phases compete against each other in a wide temperature range. In addition, the features observed in the rho(T, t) curves were found to be in excellent agreement with both the magnetic properties and the structural transitions observed in these manganites.

Optical and dielectric relaxor behaviour of Ba(Zr(0.25)Ti(0.75))O(3) ceramic explained by means of distorted clusters

In this work, Ba(Zr(0.25)Ti(0.75))O(3) ceramic was prepared by solid-state reaction. This material was characterized by x-ray diffraction and Fourier transform Raman spectroscopy. The temperature dependent dielectric properties were investigated in the frequency range from 1 kHz to 1 MHz. The dielectric measurements indicated a diffuse phase transition. The broadening of the dielectric permittivity in the frequency range as well as its shifting at higher temperatures indicated a relaxor-like behaviour for this material. The diffusivity and the relaxation strength were estimated using the modified Curie-Weiss law. The optical properties were analysed by ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements at room temperature. The UV-vis spectrum indicated that the Ba(Zr(0.25)Ti(0.75))O(3) ceramic has an optical band gap of 2.98 eV. A blue PL emission was observed for this compound when excited with 350 nm wavelength. The polarity as well as the PL property of this material was attributed to the presence of polar [TiO(6)] distorted clusters into a globally cubic matrix.

Influence of water flow rate on shear bond strength of resin composite to Er : YAG cavity preparation

Purpose: To evaluate in vitro the influence of water flow rate on shear bond strength of a resin composite to enamel and dentin after Er:YAG cavity preparation. Methods: Ten bovine incisors were selected and roots removed. Crowns were sectioned in four pieces, resulting in 40 samples that were individually embedded in polyester resin (n=10), and ground to plane the enamel and expose the dentin. The bonding site was delimited and samples were randomly assigned according to cavity preparation: (1) Er:YAG/1.0 mL/minute; (2) Er:YAG/1.5 mL/minute; (3) Er:YAG/2.0 mL/minute and (4) High speed handpiece/bur (control group). Samples were fixed to a metallic device, where composite resin cylinders were prepared. Subsequently, they were stored for 24 hours and subjected to a shear bond strength test (500N at 0.5 mm/minute). Results: Means (MPa) were: enamel: 1: 12.8; 2: 16.8; 3: 17.5; 4: 36.0 and Dentin: 1: 13.6; 2: 18.7; 3: 12.1; 4: 21.3. Data were submitted to ANOVA and Tukey`s test. Adhesion to enamel was more efficient than for dentin. The cavities prepared with conventional bur (control) presented higher statistically significant bond strength values (P<0.05) than for Er:YAG laser for both enamel and dentin. No significant differences were observed between water flow rates employed during enamel ablation. For dentin, the shear bond strength of 2.0 mL/minute water flow rate was lower than for 1.5 mL/minute and 1.0 mL/minute rates. The Er:YAG laser adversely affected shear bond strength of resin composite to both enamel and dentin, regardless of the water flow rate used.

Study of Water-Gas-Shift Reaction over La((1-y))Sr(y)Ni(x)Co((1-x))O(3) Perovskite as Precursors

The performance of La((1-y))Sr(y)Ni(x)Co((1-x))O(3) perovskites for the water gas shift reaction (WGSR) was investigated. The samples were prepared by the co- precipitation method and were performed by the BET method, XRD, TPR, and XPS. The catalytic tests were performed at 300 and 400 A degrees C and H(2)O(v)/CO = 2.3/1 (molar ratio). The sample with the highest surface area is La(0.70)Sr(0.30)NiO(3). The XRD results showed the formation of perovskite structure for all samples, and the La(0.70)Sr(0.30)NiO(3) sample also presented peaks corresponding to La(2)NiO(4) and NiO, indicating that the solubility limit of Sr in the perovskite lattice was surpassed. The replacement of Co by Ni favored the reduction of the species at lower temperatures, and the sample containing Sr presented the highest amount of reducible species, as identified by TPR results. All samples were active, the Sr containing perovskite appearing the most active due to the highest surface area, presence of the La(2)NiO(4) phase, and higher content of Cu in the surface, as detected by XPS. Among the samples containing Co, the most active one was that with x = 0.70 (60% of CO conversion).

Intergranular properties of uniaxially pressed YBa(2)Cu(3)O(7-delta) ceramic samples

We performed measurements of electrical resistivity as a function of temperature, rho(T), in polycrystalline samples of YBa(2)Cu(3)O(7-delta) (Y-123) subjected to different uniaxial compacting pressures. We observed by using X-ray diffractometry that samples have a very similar composition. Most of the identified peaks are related to the superconducting Y-123 phase. Also, from the X-ray diffraction patterns performed, in powder and pellet samples, we estimated the Lotgering factor along the (00l) direction, F((00l)). The results indicate that F((00l)) increases from 0.13 to 0.16. From electrical resistivity measurements as a function of temperature, we were able to separate contributions arising from both the grain misalignment and microstructural defects. We found appreciable degradation in the normal-state transport properties of samples with an increase in uniaxial compacting pressure. It seems that this type of behavior is associated with an increase in the influence of microstructural defects at the intergranular level. The experimental results are analyzed in the framework of a current conduction model of granular samples.

Footemineite, the Mn-analog of atencioite, from the Foote mine, Kings Mountain, Cleveland County, North Carolina, USA, and its relationship with other roscherite-group minerals

Footemineite, ideally Ca2Mn2+square Mn22+Be4(PO4)(6)(OH)(4)-6H(2)O, triclinic, is a new member of the roscherite group. It occurs on thin fractures crossing quartz-microcline-spodumene pegmatite at the Foote mine, Kings Mountain, Cleveland County, North Carolina, U.S.A. Associated minerals are albite, analcime, eosphorite, siderite/rhodochrosite, fairfieldite, fluorapatite, quartz, milarite, and pyrite. Footemineite forms prismatic to bladed generally rough to barrel-shaped crystals up to about 1.5 mm long and I mm in diameter. Its color is yellow, the streak is white, and the luster is vitreous to slightly pearly. Footemineite is transparent and non-fluorescent. Twinning is simple, by reflection, with twin boundaries across the length of the crystals. Cleavage is good on {0 (1) over bar1}) and {100}. Density (calc.) is 2.873 g/cm(3). Footemineite is biaxial (-), n(alpha) = 1.620(2), n(beta) = 1.627(2), n(gamma) = 1.634(2) (white light). 2V(obs) = 80 degrees, 2V(calc) = 89.6 degrees. Orientation: X boolean AND b similar to 12 degrees, Y boolean AND c similar to 15 degrees, Z boolean AND a similar to 15 degrees. Elongation direction is c, dispersion: r > v or r < v, weak. Pleochroism: beta (brownish yellow) > alpha = gamma (yellow). Mossbauer and IR spectra are given. The chemical composition is (EDS mode electron microprobe, Li and Be by ICP-OES, Fe3+:Fe2+ y Mossbauer, H2O by TG data, wt%): Li2O 0.23, BeO 9.54, CaO 9.43, SrO 0.23, BaO 0.24, MgO 0.18, MnO 26.16, FeO 2.77, Fe2O3 0.62, Al2O3 0.14, P2O5 36.58, SiO2 0.42, H2O 13.1, total 99.64. The empirical formula is (Ca1.89Sr0.03Ba0.02)Sigma(1.94)(Mn-0.90(2+)square(0.10))Sigma(1.00)(square 0.78Li0.17Mg0.05) Sigma(1.00)(Mn3.252+Fe0.432+ Fe0.093+Al0.03)Sigma(3.80) Be-4.30(P5.81Si0.08O24)[(OH)3.64(H2O)0.36]Sigma(4.00)center dot 6.00H(2)O . The strongest reflection peaks of the powder diffraction pattern [d, angstrom (1, %) (hkl)] are 9.575 (53) (010), 5.998 (100) (0 (1) over bar1), 4.848 (26) (021), 3.192 (44) (210), 3.003 (14) (0 (2) over bar2), 2.803 (38) ((1) over bar 03), 2.650 (29) ((2) over bar 02), 2.424 (14) (231). Single-crystal unit-cell parameters are a = 6.788(2), b = 9.972(3), c = 10.014(2) A, (x = 73.84(2), beta = 85.34(2), gamma = 87.44(2)degrees,V = 648.74 angstrom(3), Z = 1. The space group is P (1) over bar. Crystal structure was refined to R = 0.0347 with 1273 independent reflections (F > 2(5). Footemineite is dimorphous with roscherite, and isostructural with atencioite. It is identical with the mineral from Foote mine described as ""triclinic roscherite."" The name is for the Foote mine, type locality for this and several other minerals.