Crystallization of monoclinic WO3 in tungstate fluorophosphate glasses

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

Optical spectroscopy and frequency upconversion properties of Tm3+ doped tungstate fluorophosphate glasses

Tungstate fluorophosphate glasses of good optical quality were synthesized by fusion of the components and casting under air atmosphere. The absorption spectra from near-infrared to visible were obtained and the Judd-Ofelt parameters determined from the absorption bands. Transition probabilities, excited state lifetimes and transition branching ratios, were, determined from the measurements. Pumping with a 354.7 nm beam from a pulsed laser. resulted in emission at 450 nm. due to transition D-1(2)-->F-3(4) in Tm3+ ions and a broadband emission centered at approximate to 550 nm attributed to the glass matrix. When pumping at 650 nm, two emission bands at 450 nm (D-1(2)-->F-3(4)) and at 790 nm (H-3(4)-->H-3(6)) were observed. Excitation spectra were also obtained in order to understand the origin of both emissions. Theoretical and experimental lifetimes were determined and,the results were explained in terms of multiphonon relaxation. (C) 2003 American Institute of Physics.

Scandium fluorophosphate glasses: a structural approach

A systematic investigation on glass formation in the ternary system InF3-BaF2-[Sc(PO3)(3)](n) has been carried out. Scandium polyphosphate [Sc(PO3)(3)](n) has been used as a third component in order to investigate the possibilities of obtaining new stable glasses. The above long-chain polyphosphate has been prepared using a specially elaborated cryo-technique, which allowed the preparation of high-purity product. Stable ternary compositions have been obtained within the compositions range (in mol%): 5-75 InF3, 0-80% BaF2, 0-50% [Sc(PO3)(3)](n). Glasses were characterized by Differential Scanning Calorimetry, vibrational spectroscopy (Raman) and P-31 NMR. Structural features for the glass were put forward. Isolated P(O,F)4 groups or fluoroindated metaphosphate units could be identified depending on glass compositions. (C) 2002 Academie des sciences / Editions scientifiques et medicales Elsevier SAS.

Nonlinear optical properties of tungstate fluorophosphate glasses

The optical nonlinearity of tungstate fluorophosphate glasses, synthesized in the NaPO3-BaF2-WO3 system, was investigated through experiments based on the third-order susceptibility, chi((3)). Nonlinear (NL) refraction and NL absorption measurements in the picosecond regime were performed using the Z-scan technique at 532 nm. NL refractive index, n(2)proportional toRe chi((3)), ranging from 0.4x10(-14) cm(2)/W to 0.6x10(-14) cm(2)/W were determined. The two-photon absorption coefficient, alpha(2)proportional toIm chi((3)), for excitation at 532 nm, vary from 0.3 to 0.5 cm/GW. Light induced birefringence experiments performed in the femtosecond regime indicate that the response time of the nonlinearity at 800 nm is faster than 100 fs. The experiments show that chi((3)) is enhanced when the WO3 concentration increases and this behavior is attributed to the hyperpolarizabilities associated to W-O bonds. (C) 2004 American Institute of Physics.

Local order around tungsten atoms in tungstate fluorophosphate glasses by X-ray absorption spectroscopy

X-ray absorption spectroscopy was used to study the local environment of tungsten atoms in NaPO3-BaF2,-WO3 glasses and the results were compared with crystalline references Na2WO4 and WO3. XANES measurements at the W-L-1 edge allowed to determine a distorted octahedral environment of tungsten atoms in these glasses similar to the local order of tungsten in monoclinic WO3. Extended X-ray absorption fine structure (EXAFS) has been used as a local probe to monitor the effect of WO3 concentration on the tungsten environment. Based on an analysis of the EXAFS data, we proposed a three-shell model of oxygen atoms around tungsten as in monoclinic WO3. With increasing WO3 concentration, it was found that R-2 decreases from 1.96 to 1.92 angstrom whereas R-3 increases from 2.07 to 2.12 angstrom. (c) 2005 Elsevier B.V. All rights reserved.

New tungstate fluorophosphate glasses

\A new class of tungstate fluorophosphate glasses was identified in the NaPO3-BaF2-WO3 ternary system. The variation of several physical properties was determined with respect to chemical composition. Characteristic temperatures, density and refractive index increase as tungsten oxide content increases. The optical transmission range and specially the energy bandgap depend of the WO3 amount. No crystallization could be observed for the Most WO3 concentrated vitreous samples (greater than or equal to20% molar). Color and optical properties of the glasses depend of the melting time because of the presence of reduced tungsten species like W5+ and W4+. In addition, photodarkening is observed in tungsten rich glass samples under UV laser illumination and this phenomenon can be reversible by heat treatment near the glass transition temperature. (C) 2004 Published by Elsevier B.V.

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO3-BaF2 WO3 tertiary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L-I and L-III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (≥ 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

Tungstate fluorophosphate glasses as optical limiters

Nonlinear absorption measurements were performed on fluorophosphate glasses with high concentrations of tungsten oxide. Large two-photon absorption coefficients, alpha(2), were determined at 660 nm using nanosecond laser pulses. It was observed that alpha(2) increases for increasing tungsten oxide concentrations and, hence, the optical limiting performance of this glass composition can be controlled. (C) 2002 American Institute of Physics.

Optical limiting behavior of tungstate fluorophosphate glasses

Nonlinear absorption measurements were performed on fluorophosphate glasses with high concentration of tungsten oxide. Large two-photon absorption coefficients, α2, were determined at 660 nm using nanosecond laser pulses. It was observed that α2 increases for increasing tungsten oxide concentrations and therefore the optical limiting performance of this new glass composition can be controlled.

New glasses in the system InF3-BaF2-ErPO4

New glasses have been obtained in the system InF3-BaF2-ErPO4. Glass compositions with up to 30% mol Er3+ were shown to exist and characterized by thermal analysis, x-ray: diffraction, IR absorption and electronic spectroscopy. The systems with high Er3+ content were studied recording IR and visible emission spectral characteristics. A specially elaborated technique allowed the preparation of a high purity phosphate precursor ErPO4. X-ray identification of the crystalline phases appearing during thermal treatment have been carried out and parameters of a mixed fluoride Ba4In3-nErnF17 calculated.

Fission-track dating of South American natural glasses: an overview

Although many glass-bearing horizons can be found in South American volcanic complexes or sedimentary series, only a relatively few tephra and obsidian-bearing volcanic fields have been studied using the fission-track (FT) dating method. Among them, the volcanics located in the Sierra de Guamani (east of Quito, Ecuador) were studied by several authors. Based upon their ages, obsidians group into three clusters: (1) very young obsidians, similar to 0.2Ma old, (2) intermediate-age obsidians, similar to 0.4- similar to 0.8 Ma old, and (3) older obsidians, similar to 1.4- similar to 1.6 Ma old. The FT method is also an efficient alternative technique for identification of the sources of prehistoric obsidian artefacts. Provenance studies carried out in South America have shown that the Sierra de Guamani obsidian occurrences were important sources of raw material for toot making during pre-Columbian times. Glasses originated from these sources were identified in sites distributed over relatively wide areas of Ecuador and Colombia.Only a few systematic studies on obsidians in other sectors were carried out. Nevertheless, very singular glasses have been recognised in South America, such as Macusanite (Peru) and obsidian Quiron (Argentina), which are being proposed as additional reference materials for FT dating. Analyses of tephra beds interstratified with sedimentary deposits revealed the performance of FT dating in tephrochronological studies. A remarkable example is the famous deposit outcropping at Farola Monte Hermoso, near Bahia Blanca (Buenos Aires Province), described for the first time by the middle of the 19th century by Charles Darwin.Considering the large number of volcanic glasses that were recognised in volcanic complexes and in sedimentary series, South America is a very promising region for the application of FT dating. The examples given above show that this technique may yield important results in different disciplinary fields. (c) 2005 Elsevier Ltd. All rights reserved.

Fission-track dating of Macusanite glasses with plateau and size correction methods

Two Macusanite pebbles (MB1 and MB2) were dated with the fission-track method. Six irradiations were carried out in different nuclear reactors: Pavia (Italy), IPEN-CNEN (Brazil) and IPEN-Lima (Peru). Measurements of the thorium and uranium induced-fission per target nucleus using natural thorium thin films and natural U-doped glasses calibrated against natural uranium thin films, together with lambda(F) of 8.46 x 10(-17) a(-1) were used to determine the ages. The apparent ages were corrected using the plateau and size correction methods. Track measurements were performed by different analysts, using different counting criteria. In addition, tracks were measured on samples which had been submitted to thermal treatment as well as on samples which had not been heated. Thermal treatments were carried out to erase the fossil tracks before neutron irradiation. No significant differences have been found in individual results, using the two Macusanite pebbles and the different nuclear reactors, age correction techniques, analysts, track-counting criteria, and thermal treatments before neutron irradiation. The great majority of the results (14/17) is compatible with the Ar-Ar ages of 5.12 +/- 0.11 and 5.10 +/- 0.11 Ma, Macusanite MB1 and MB2, respectively. However, the fission-track ages are systematically less (similar to8%) than the Ar-Ar ages of the two Macusanite samples studied. (C) 2003 Published by Elsevier Ltd.

New constraints on ages of glasses proposed as reference materials for fission-track dating

New analyses have been performed in order to enhance the data-set on the independent ages of four glasses that have been proposed as reference materials for fission-track dating. The results are as follows. Moldavite - repeated (40)Ar/(39)Ar age determinations on samples from deposits from Bohemia and Moravia yielded an average of 14.34 +/- 0.08 Ma. This datum agrees with other recent determinations and is significantly younger than the (40)Ar/(39)Ar age of 15.21 +/- 0.15 Ma determined in the early 1980s. Macusanite (Peru) -four K-Ar ages ranging from 5.44 +/- 0.06 to 5.72 +/- 0.12 Ma have been published previously. New (40)Ar/(39)Ar ages gave an average of 5.12 +/- 0.04 Ma. Plateau fission-track ages determined using the IRMM-540 certified glass and U and Th thin films for neutron fluence measurements agree better with these new (40)Ar/(39)Ar ages than the previously published ages. Roccastrada glass (Italy) - a new (40)Ar/(39)Ar age, 2.45 +/- 0.04 Ma, is consistent with previous determinations. The Quiron obsidian (Argentina) is a recently discovered glass that has been proposed as an additional reference material for its high spontaneous track density (around 100 000 cm(-2)). Defects that might produce spurious tracks are virtually absent. An independent (40)Ar/(39)Ar age of 8.77 +/- 0.09 Ma was determined and is recommended for this glass. We believe that these materials, which will be distributed upon request to fission-track groups, will be very useful for testing system calibrations and experimental procedures.

A GC-FID Method to Determine Styrene in Polystyrene Glasses

The styrene levels of polystyrene (PS) glasses from the most consumed brands of disposable glasses intended for water and coffee in Brazil were determined. A GC-FID method was developed and validated, showing good precision and accuracy. The method was successfully used to determine styrene in 11 PS glass brands. The styrene levels ranged from 1.68 to 43.69 mg/100 g glass, depending on the kind of polymer, thickness, and glass brand. It could be used to control the content of styrene in the polymer. The migration of styrene from the glasses into water and 20 % ethanol was not detected.

Thermo and photochromic properties of Na2O-WO3-SbPO4 glasses

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