Synthesis and reactivity in salt metathesis reactions of trivalent [La(Tp(Me2))(2)X] (X = Cl, I) complexes: crystal structures of [La(Tp(Me2))(2)Cl] and [La(Tp(Me2))(2)(kappa(2)-pz(Me2))]

Reaction of LaX3(THF)(n) (X = Cl, 1) with two equiv. of K(Tp(Me2)) gave good yields of the bis-Tp complexes [La(Tp(Me2))(2)X] (X = Cl (1); I (3)). However, the formation of 1 and 3 is always accompanied by significant amounts of La(Tp(Me2))(2)(kappa(2)-pz(Me2)) ([pz(Me2)](-) = 3,5-dimethyl-pyrazolato) (2). The pyrazolato complex 2, which presumably arises from decomposition of the [Tp(Me2)](-) moiety during salt metathesis, was independently prepared in good yield from 1 and in situ generated [pz(Me2)](-). The solid-state structures of 1 and 2 were determined by single-crystal X-ray diffraction studies. Subsequent reactions of halogeno-Tp(Me2) complexes 1 and 3 with various alkali metal salts MR (M = Li, R = CH2SiMe3, Ph, N(SiMe3)(2); M = K, R = OAr) gave M(Tp(Me2)) as the major product. Alternatively, the mono-Tp bis(aryloxide) derivatives [Ln(Tp(Me2))(OC6H2-2,6-'Bu-4-Me)(2)] (Ln = La (4); Nd (5)) were obtained in high yields by salt metathesis of [Ln(OC6H2-2,6-'Bu-4-Me)(3)] with one equiv. of K(Tp(Me2)). (C) 2004 Elsevier Ltd. All rights reserved.

Optical properties and energy transfer processes in (Tm3+, Nd3+) doped tungstate fluorophosphate glass

We investigate the linear optical properties and energy transfer processes in tungstate fluorophosphate glass doped with thulium (Tm3+) and neodymium (Nd3+) ions. The linear absorption spectra from 370 to 3000 nm were obtained. Transitions probabilities, radiative lifetimes, and transition branching ratios were determined using the Judd-Ofelt [Phys. Rev. 127, 750 (1962); J. Chem. Phys. 37, 511 (1962)] theory. Frequency up-conversion to the blue region and fluorescence in the infrared were observed upon pulsed excitation in the range of 630-700 nm. The excitation spectra of the luminescence were obtained to understand the origin of the signals. The temporal decay of the fluorescence was measured for different concentrations of the doping ions. Energy transfer rates among the Tm3+ and Nd3+ ions were also determined.

Phosphate functionalization of spongiolite surface

Spongiolite from Mato Grosso do Sul (Brazil), natural inorganic composite constituted of silica needles, was treated with concentrated phosphoric acid at high temperatures. Superficial coating of the needles was proved to be constituted of silicon diphosphate, a compound offering six-coordinated silicon sites. Owing to the affinity of three charged ions to phosphate groups, this coating acts as specific adsorbent for the rare earth elements which prefer octahedral coordination (starting from samarium, yttrium included). The uptake of lanthanum and neodymium are significantly lower due to different coordination tendencies. Lanthanide fixation upon silica with PO4 groups anchored on its surface may be useful in the manufacturing of special phosphate-silicate glasses. (C) 2003 Elsevier B.V. All rights reserved.

Influence of processing conditions on the thermal decomposition of SrTiO3 precursors

The present work investigates the influence of milling and calcination atmosphere on the thermal decomposition of SrTiO3 powder precursors. Both pure and neodymium-modified SrTiO3 samples were studied. Milling did not significantly influence numerical mass loss value, but reduced the number of decomposition steps, modifying the profiles of the TG and DTA curves. on the other hand, milling increases the amount of energy liberated by the system upon combustion of organic matter. It was also observed that the milling process, associated to the calcination in an oxygen atmosphere, considerably decreases the amount of organic matter and increases the final mass loss temperature.

SrSnO3:Nd obtained by the polymeric precursor method

In this work, the synthesis of Nd-doped SrSnO3 by the polymeric precursor method, with calcination between 250 and 700 A degrees C is reported. The powder precursors were characterized by TG/DTA and high temperature X-ray diffraction (HTXRD). After heat treatment, the material was characterized by XRD and infrared spectroscopy. Ester and carbonate amounts were strictly related to Nd-doping. According to XRD patterns, the orthorhombic perovskite was obtained at 700 A degrees C for SrSnO3 and SrSn0.99Nd0.01O3. For Sr0.99Nd0.01SnO3, the kinetics displayed an important hole in the crystallization process, as no peak was observed in HTXRD up to 700 A degrees C, while a XRD patterns showed a crystalline material after calcination at 250 A degrees C.

Synthesis, thermal properties and spectroscopic study of solid mandelate of light trivalent lanthanides

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

Thermal and structural characterization of SrTi(1-x)Nd(x)O(3)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Re-Os isotope and highly siderophile element systematics of the Parana continental flood basalts (Brazil)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Optical spectroscopy and upconversion luminescence in Nd3+ doped Ga10Ge25S65 glass

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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.

Frequency upconversion in Nd3+-doped fluoroindate glass

We report the observation of frequency upconversion in fluoroindate glasses with the following compositions: (mol%) (39 - x)InF3-20ZnF2-20SrF2-16BaF 2-2GdF3-2NaF-1GaF3-xNdF3 (x = 0.05, 0.1, 0.5, 1, 2, 3). The excitation source was a dye laser in resonance with the 4I9/2→(2G5/2, 2G7/2) transition of the Nd3+ ions. The upconverted fluorescence spectra show emissions from ∼ 350 to ∼ 450 nm, corresponding to transitions 4D3/2→4I9/2 ;4D3/2→4I11/2; 2P3/2→ 4I9/2; 4D3/2→4I13/2; 2P3/2→4I11/2; 4D3/2→4I15/2; and 2P3/2 → 4I13/2. The dependence of the fluorescence signals on the laser intensity indicates that two laser photons participate in the process. The temporal behavior of the signal indicates that energy transfer among the Nd3+ ions is the main mechanism which contributes to upconversion at 354 and 382 nm.

Violet-blue emissions due to frequency up-conversion in Nd3+-doped fluoroindate glasses

We report the observation of intense frequency up-conversion in Nd3+-doped fluoroindate glasses pumped by the second harmonic of a cw mode-locked Nd: YAG laser. Mechanisms for generating the observed emissions are discussed.

Spectroscopic study of the interaction of Nd3+ with amino acids: Phenomenological 4f-4f intensity parameters

We have studied the bevahior of the phenomenological 4f-4f intensity parameters in compounds of the Nd ion with glycine, L-aspartic acid, L-glutamic acid, L-histidine, DL-malic acid and Aspartame™ in aqueous solution, as a function of the pK values and partial charges on the oxygens of the carboxylate groups of these molecules. The results are discussed and qualitatively interpreted in terms of the forced electric dipole and dynamic coupling mechanisms of the 4f-4f intensities, thus indicating that the forced electric dipole mechanism is dominant.

One-dimensional analytical model for oxide thin film growth on Ti metal layers during laser heating in air

This paper presents the theoretical and experimental results for oxide thin film growth on titanium films previously deposited over glass substrate. Ti films of thickness 0.1 μm were heated by Nd:YAG laser pulses in air. The oxide tracks were created by moving the samples with a constant speed of 2 mm/s, under the laser action. The micro-topographic analysis of the tracks was performed by a microprofiler. The results taken along a straight line perpendicular to the track axis revealed a Gaussian profile that closely matches the laser's spatial mode profile, indicating the effectiveness of the surface temperature gradient on the film's growth process. The sample's micro-Raman spectra showed two strong bands at 447 and 612 cm -1 associated with the TiO 2 structure. This is a strong indication that thermo-oxidation reactions took place at the Ti film surface that reached an estimated temperature of 1160 K just due to the action of the first pulse. The results obtained from the numerical integration of the analytical equation which describes the oxidation rate (Wagner equation) are in agreement with the experimental data for film thickness in the high laser intensity region. This shows the partial accuracy of the one-dimensional model adopted for describing the film growth rate. © 2001 Elsevier Science B.V.

Blue upconversion enhancement by a factor of 200 in Tm 3+-doped tellurite glass by codoping with Nd 3+ ions

We investigated near-infrared-to-blue upconversion from thulium (Tm 3+) doped in tellurite glasses upon continuous wave excitation near 800 nm. We observed an enhancement of over two orders of magnitude of the upconverted emission at ∼480nm when neodymium (Nd 3+) ions were codoped with Tm 3+ ions. For comparison, using a Tm 3+:Nd 3+ codoped fluorozirconate glass as a reference material we observed a 40-fold enhancement of the blue emission. Analysis of the blue emission for samples with different doping levels of Nd 3+ ions showed that energy transfer between Nd 3+ and Tm 3+ is the mechanism responsible for the enhancement in upconversion. © 2002 American Institute of Physics. © 2002 American Institute of Physics.