Short-range structure of Pb(1-x)Ba(x)Zr(0.65)Ti(0.35)O(3) ceramic compounds probed by XAS and Raman scattering techniques

Ti K-edge x-ray absorption near-edge spectroscopy (XANES) and Raman scattering were used to study the solid solution effects on the structural and vibrational properties of Pb(1-x)Ba(x)Zr(0.65)Ti(0.35)O(3) with 0.0 < x < 0.40. Compared with x-ray diffraction techniques, which indicates that the average crystal symmetry changes with the substitution of Pb by Ba ions or with temperature variations for samples with x=0.00, 0.10, and 0.20, local structural probes such as XANES and Raman scattering results demonstrate that at local level, the symmetry changes are much less prominent. Theoretical XANES spectra calculation corroborate with the interpretation of the XANES experimental data.

Upconversion luminescence in Er3+ doped and Er3+/Yb3+ codoped zirconia and hafnia nanocrystals excited at 980 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Corrosion protection of fluorzirconate glasses coated by a layer of surface modified tin oxide nanoparticles

The protection efficiency against water corrosion of fluorozirconate glass, ZBLAN, dip-coated by nanocrystalline tin oxide film containing the organic molecule Tiron® was investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The chemical bonding structure of the surface region and morphology were studied before and after two water exposure periods of 5 and 30 min. The results of the analysis for the as-grown sample revealed a SnO1.6 phase containing carbon and sulfur, related to Tiron®, and traces of elements related to ZBLAN (Zr, F, Ba). This fact and the clear evidence of the presence of tin oxifluoride specie (SnOxF y) indicates a diffusion of the glass components into the porous coating. After water exposure, the increase of the oxygen concentration accompanied by a strong increase of Zr, F, Ba and Na content is interpreted as filling of the nanopores of the film by glass compounds. The formation of a compact protective layer is supported by the morphological changes observed by AFM. © 2005 Elsevier B.V. All rights reserved.

Efficiency evaluation of ZrB2 incorporation in the MgB 2 matrix phase using high-energy milling

The present study suggests the use of high energy ball milling to mix (to dope) the phase MgB2 with the AlB2 crystalline structure compound, ZrB2, with the same C32 hexagonal structure than MgB 2, in different concentrations, enabling the maintenance of the crystalline phase structures practically unaffected and the efficient mixture with the dopant. The high energy ball milling was performed with different ball-to-powder ratios. The analysis of the transformation and formation of phases was accomplished by X-ray diffractometry (XRD), using the Rietveld method, and scanning electron microscopy. As the high energy ball milling reduced the crystallinity of the milled compounds, also reducing the size of the particles, the XRD analysis were influenced, and they could be used as comparative and control method of the milling. Aiming the recovery of crystallinity, homogenization and final phase formation, heat treatments were performed, enabling that crystalline phases, changed during milling, could be obtained again in the final product. © (2010) Trans Tech Publications.

Amorphous ZrF4-a molecular dynamics study

Using an effective two-body interaction potential, a molecular dynamics study of the structural properties of amorphous ZrF4 phase is presented. The effective pair potential includes steric repulsion, Coulomb interaction due to charge transfer, and charge-dipole interaction due to the large electronic polarizability of anions. The results for structural correlations, such as pair distribution functions, coordination numbers, and bond angle distributions are presented. Excellent agreement is obtained by comparing experimental X-ray diffraction and the simulated static X-ray structure factor. © 1993.

Solid-state metallurgy studies of pure columbium and Cb-1 Zr alloy /

"Contract AT(11-1)-229."

Pi*-pi* bonding interactions generated by halogen oxidation of zirconium(IV) redox-active ligand complexes.

The new complex, [Zr(pda)2]n (1, pda2- = N,N'-bis(neo-pentyl)-ortho-phenylenediamide, n = 1 or 2), prepared by the reaction of 2 equiv of pdaLi2 with ZrCl4, reacts rapidly with halogen oxidants to afford the new product ZrX2(disq)2 (3, X = Cl, Br, I; disq- = N,N'-bis(neo-pentyl)-ortho-diiminosemiquinonate) in which each redox-active ligand has been oxidized by one electron. The oxidation products 3a-c have been structurally characterized and display an unusual parallel stacked arrangement of the disq- ligands in the solid state, with a separation of approximately 3 A. Density functional calculations show a bonding-type interaction between the SOMOs of the disq- ligands to form a unique HOMO while the antibonding linear combination forms a unique LUMO. This orbital configuration leads to a closed-shell-singlet ground-state electron configuration (S = 0). Temperature-dependent magnetism measurements indicate a low-lying triplet excited state at approximately 750 cm-1. In solution, 3a-c show strong disq--based absorption bands that are invariant across the halide series. Taken together these spectroscopic measurements provide experimental values for the one- and two-electron energies that characterize the pi-stacked bonding interaction between the two disq- ligands.

Fulvalene cyclopentadienyl titanium and zirconium(III) and -(IV) complexes. X-Ray crystal structure of [{Ti(η5-C5H5) Cl}2 (μ-O)(μ-η5-η5-C10H8)]

The reaction of the fulvalene titanium(III) hydride [{Ti(η5-C5H5)(μ-H)}2(μ-η5-η5-C10H8)] (1) with chlorine leads to [{Ti(η5-C5H5)(μ-Cl)}2(μ-η5-η5-C10H8)] (3) and [{Ti(η5-C5H5)Cl2}2(μ-η5-η5-C10H8)] (4). The reaction of 3 with azobenzene, in wet toluene, gives [{Ti(η5-C5H5)Cl}2(μ-O)(μ-η5-η5-C10H8)] (5) and 1,2-diphenyl hydrazine. The alkylation of 4 and the analogous zirconium complex [{Zr(η5-C5H55)Cl2}2(μ-η5-η5-C10H8)] (2) with LiCH2SiMe3 or LiCH3 permits isolation of the tetraalkyl derivatives [{M(η5-C5H5)(CH2SiMe3)2}2(μ-η5-η5-C10H8)] (M  Ti (6); Zr (8)) and [{Ti(η5-C5H5)(CH3)2}2(μ-η5-η5C10H8)] (7). All the new fulvalene compounds were characterized by IR, and 1H and 13C NMR spectroscope, and mass spectra and 5 by X-ray diffraction. The structure of 5 is very similar to that of the comparable TiIV compound [{Ti(η5-C5H5)2Cl}2(μ-O)] except for the smaller TiOTi angle (159.4° against 173.81°) and a significant deviation from linearity.

X-ray photoelectron spectroscopy analysis of zirconium nitride-like films prepared on Si(100) substrates by ion beam assisted deposition

Thin zirconium nitride films were prepared on Si(l 00) substrates at room temperature by ion beam assisted deposition with a 2 keV nitrogen ion beam. Arrival rate ratios ARR(N/Zr) used were 0.19, 0.39, 0.92, and 1.86. The chemical composition and bonding structure of the films were analyzed with X-ray photoelectron spectroscopy (XPS). Deconvolution results for Zr 3d, Zr 3p(3/2), N 1s, O 1s, and C 1s XPS spectra indicated self-consistently the presence of metal Zr-0, nitride ZrN, oxide ZrO2, oxymnide Zr2N2O, and carbide ZrC phases, and the amounts of these compounds were influenced by ARR(N/Zr). The chemical composition ratio N/Zr in the film increased with increasing ARR(N/Zr) until ARR(N/Zr) reached 0.92, reflecting the high reactivity of nitrogen in the ion beam, and stayed almost constant for ARR(N/Zr) >= 1, the excess nitrogen being rejected from the growing film. A considerable incorporation of contaminant oxygen and carbon into the depositing film was attributed to the getter effect of zirconium. (C) 2007 Elsevier B.V. All rights reserved.

Protection of short-time enamel erosion by different tetrafluoride compounds

objective: This in vitro study aimed to analyse the protective effect of differently concentrated titanium (TiF4), zirconium (ZrF4) and hafnium (HfF4) tetrafluoride on enamel erosion. Methods: Polished enamel surfaces of 36 bovine crowns were covered with tape leaving 4 enamel windows each 3 mm in diameter exposed. The crowns were randomly assigned to six groups (each n = 6) and pretreated with 4% TiF4, 10% TiF4, 4% ZrF4, 10% ZrF4, 4% HfF4 or 10% HfF4 for 4 min (first window), 10 min (second window) or 15 min (third window). The fourth window of each crown was not pretreated and served as control. Erosion was performed stepwise with 1% HCl (pH 2) in five consecutive intervals of each 15 s (total 75 s). Enamel dissolution was quantified by colorimetric determination of phosphate release into the acid. For each tooth, cumulative phosphate loss of enamel pretreated with one of the tetrafluoride compounds was calculated as percentage of the respective control and statistically analysed using two-way ANOVA.Results: Enamel erosion was significantly reduced by TiF4, ZrF4 and HfF4 application. Cumulative phosphate loss (mean % of control, 75 s erosion) after 4-15 min application was significantly lower for 4% ZrF4 (7-11%), 10% ZrF4 (2-6%), 4% HfF4 (11-9%) and 10% HfF4 (12-16%) compared to 4% TiF4 (42-27%) and 10% TiF4 (54-33%). Only for 4% and 10% TiF4, phosphate loss decreased with increasing duration of application, but also increased with increasing acid intervals.Conclusion: TiF4, ZrF4 and HfF4 might protect enamel against short-time erosion, but protection was more enhanced by ZrF4 and HfF4 compared to TiF4 application overtime. (C) 2008 Elsevier Ltd. All rights reserved.

Dielectric investigations of vanadium modified barium zirconium titanate ceramics obtained from mixed oxide method

Vanadium modified barium zirconium titanate ceramics Ba(Zr(0.10)Ti(0.90))O(3):2V (BZT:2V) were prepared from the mixed oxide method. According to X-ray diffraction analysis, addition of vanadium leads to ceramics free of secondary phases. Electrical characteristics reveal a dielectric permittivity at around 15,000 with low dielectric loss with a remnant polarization (P(r))of 8 mu C/cm(2) at 2 kV/cm. From the obtained results, we assume that vanadium substitution in the BZT lattice affects dielectric characteristics due to the electron-relaxation-mode in which carriers (polarons, protons, and so on) are coupled with existing dielectric modes. (C) 2009 Published by Elsevier B.V.

Titanium and zirconium complexes containing sterically hindered hydrotris(pyrazolyl)borate ligands: synthesis, structural characterization, and ethylene polymerization studies

The synthesis, characterization and ethylene polymerization behavior of a set of Tp'MCl3 complexes (4, M = Ti, Tp' HB(3-neopentyl-pyrazolyl)(3)(-) (Tp(NP)); 5, M = Ti, Tp'= HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu)); 6, M = Ti, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(Ph)); 7, M = Zr, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(ph)); 8, M = Zr, Tp' = HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu))) is described. Treatment of these tris(pyrazolyl)borate Group IV compounds with methylalumoxane (MAO) generates active catalysts for ethylene polymerization. For the polymerization reactions performed in toluene at 60 degreesC and 3 atm of ethylene pressure, the activities varied between 1.3 and 5.1 X 10(3) g of PE/mol[M](.)h. The highest activity is reached using more sterically open catalyst precursor 4. The viscosity-average molecular weights ((M-v) over bar) of the PE's produced with these catalyst precursors varying from 3.57 to 20.23 x 10(5) gmol(-1) with melting temperatures in the range of 127-134 degreesC. Further polymerization studies employing 7 varying Al/Zr molar ratio and temperature of polymerization showed that the activity as well as the polymer properties are dependent on these parameters. In that case, higher activity was attained at 60 degreesC. The viscosity-average molecular weights of the polyethylene's decreases with increasing AI/Zr molar ratio. (C) 2003 Elsevier B.V. All rights reserved.

CONTRIBUTION TO THE STUDY OF ZIRCONIUM AND HAFNIUM ALPHA-HYDROXYCARBOXYLATES

A study of both zirconium and hafnium alpha-hydroxycarboxylates for analytical applications is presented, These compounds are studied by infrared spectroscopy, thermal analysis and X-ray diffractometry. dl-Mandelic, dl-p-bromomandelic and dl-2-naphthylglycolic acids are the more adequate reagents for gravimetric determinations of zirconium and hafnium, the ligands dl-2-hydroxyhexanoic and dl-2-hydroxydodecanoic acids were used for the first time and the results showed that they are also adequate reagents for the same purpose.

Effect of yttrium doping in barium zirconium titanate ceramics: A structural, impedance, modulus spectroscopy study

In the current article, we studied the effect of yttrium [Y3+] ions' substitution on the structure and electric behavior of barium zirconate titanate (BZT) ceramics with a general formula [Ba1-x Y 2x/3](Zr0.25Ti0.75)O3 (BYZT) with [x = 0, 0.025, 0.05] which were prepared by the solid-state reaction method. X-ray diffraction patterns indicate that these ceramics have a single phase with a perovskite-type cubic structure. Rietveld refinement data confirmed [BaO 12], [ZrO6], [TiO6], [YO6] clusters in the cubic lattice. The Y3+ ions' effects on the electric conductivity behavior of BZT ceramics as a function of temperature and frequency are described, which are based on impedance spectroscopy analyses. The complex impedance plots display a double semicircle which highlights the influences of grain and grain boundary on the ceramics. Impedance analyses showed that the resistance decreased with the increasing temperature and resulted in a negative temperature coefficient of the resistance property in all compositions. Modulus plots represent a non-Debye-type dielectric relaxation which is related to the grain and grain boundary as well as temperature-dependent electric relaxation phenomenon and an enhancement in the mobility barrier by Y3+ ions. Moreover, the electric conductivity increases with the replacement of Ba 2+ by Y3+ ions may be due to the rise in oxygen vacancies. © 2013 The Minerals, Metals & Materials Society and ASM International.