Production of defects in ZBLAN, ZBLAN : Tm3+ and ZBLAN : Cr3+ glasses by ultra-short pulses laser interaction

In this work we have studied pure and thulium- and chromium-doped ZBLAN glasses irradiated by ultra-short laser pulses. A Ti:sapphire CPA system was used, producing a 500 Hz train of pulses, centered at 830 nm, with 375 mu J of energy and 50 fs of duration (FWHM). The beam was focused by a 20 Him lens, producing a converging beam with a waist of 12 pin. The absorption spectra before and after laser irradiation were obtained showing production of color centers in pure, thulium-doped and chromium-doped ZBLAN glasses. A damage threshold of 9.56 TW/cm(2) was determined for ZBLAN. (C) 2007 Elsevier Ltd. All rights reserved.

Excited state dynamics of the Ho3+ ions in holmium singly doped and holmium, praseodymium-codoped fluoride glasses

The deactivation of the two lowest excited states of Ho3+ was investigated in Ho3+ singly doped and Ho3+, Pr3+-codoped fluoride (ZBLAN) glasses. We establish that 0.1-0.3 mol % Pr3+ can efficiently deactivate the first excited (I-5(7)) state of Ho3+ while causing a small reduction of similar to 40% of the initial population of the second excited (I-5(6)) state. The net effect introduced by the Pr3+ ion deactivation of the Ho3+ ion is the fast recovery of the ground state of Ho3+. The Burshstein model parameters relevant to the Ho3+-> Pr3+ energy transfer processes were determined using a least squares fit to the measured luminescence decay. The energy transfer upconversion and cross relaxation parameters for 1948, 1151, and 532 nm excitations of singly Ho3+-doped ZBLAN were determined. Using the energy transfer rate parameters we determine from the measured luminescence, a rate equation model for 650 nm excitation of Ho3+-doped and Ho3+, Pr3+-doped ZBLAN glasses was developed. The rate equations were solved numerically and the population inversion between the I-5(6) and the I-5(7) excited states of Ho3+ was calculated to examine the beneficial effects on the gain associated with Pr3+ codoping. (c) 2007 American Institute of Physics.

XPS study on water corrosion of fluorzirconate glasses and their protection by a layer of surface modified tin dioxide nanoparticles

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, Z-BLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)), and the corrosion protection efficiency of a nanocrystalline transparent SnO2 layer were investigated by X-ray photoelectron spectroscopy. The tin oxide film was deposited by the sol-gel dip-coating process in the presence of Tiron(R) as particle surface modifier agent. The chemical bonding structure and composition of the surface region of coated and non-coated ZBLAN were studied before water contact and after different immersion periods (5-30 min). In contrast to the effects occurring for non-coated glass, where the surface undergoes a rapid selective dissolution of the most soluble species inducing the formation of a new surface phase consisting of stable zirconium oxyfluoride, barium fluoride and lanthanum fluoride species, the results for the SnO2-coated glass showed that the hydrolytic attack induces a filling of the film nanopores by dissolved glass material and the formation of tin oxylluoride and zirconium oxyfluoride species. This process results in a modified film, which acts as a hermetic diffusion barrier protecting efficiently the glass surface. (C) 2006 Elsevier B.V. All rights reserved.

XPS study of the corrosion protection of fluorozirconate glasses dip-coated with SnO2 transparent thin films

Tin oxide nanoparticles prepared by an aqueous sol-gel method were deposited by dip-coating on fluorozirconate glass, ZBLAN (53%ZrF4-20%BaF2-4%LaF3-3%AlF3-20%NaF) to improve its resistance against wet corrosion. The aqueous leaching of uncoated and SnO2-coated fluorozirconate glass was studied by X-ray photoemission spectroscopy (XPS) and it was shown that even an ultra thin tin dioxide film provides good protection of the glass surface against the bulk propagation of the hydrolytic attack.

Study on the initial stages of water corrosion of fluorozirconate glasses

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, ZBLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)) was investigated using X-ray photoelectron spectroscopy (XPS), grazing-incidence small angle X-ray scattering (GISAXS), X-ray reflectivity (XRR) and scanning electron microscopy (SEM). After a short exposure period (25 min) of the glass surface to deionized water the XPS data indicate an increase of the oxygen content accompanied by a decrease of fluorine concentration. The analysis of the chemical bonding structure identified the predominant surface reaction products as zirconium hydroxyfluoride and oxyfluoride species. The second most abundant glass component, bariumfluoride, remains almost unaffected by oxygen, while sodium fluoride is completely removed from the attacked surface region. The detected structural and compositional changes are related to the selective dissolution of the glass components leading to the formation of a new surface phase. This process is accompanied by a visible surface roughening caused by reprecipitated species, observed by SEM. The modification of the glass surface is responsible for an increase of the GISAXS intensity. The scattering was attributed to nanovoids formed at the surface region of the glass with an average size of 2.4 +/- 0.05 nm. (C) 2004 Elsevier B.V. All rights reserved.

Dynamics of Tm-Ho energy transfer and deactivation of the F-3(4) low level of thulium in fluorozirconate glasses

The mechanism involved in the Tm3+ (F-3(4))-->Ho3+ (I-5(7)) energy transfer and Tm3+ (H-3(4), H-3(6))-->Tm3+ (F-3(4), F-3(4)) cross relaxation as a function of the donor and acceptor concentrations was investigated in Tm-Ho-codoped fluorozirconate glasses. The experimental transfer rates were determined for the Tm-->Ho energy transfer from the best fit of the acceptor luminescence decay using an expression which takes into account the Inokuti-Hirayama model and localized donor-to-acceptor interaction solution. The original acceptor solution derived from the Inokuti-Hirayama model fits well the acceptor luminescence transient only for low-concentrated systems. The results showed that a fast excitation diffusion that occurs in a very short time (t<ZBLAN. The fast excitation diffusion effect was observed to dominate both the Tm-->Tm cross relaxation and Tm-->Ho energy transfer ions from H-3(4) and F-3(4) thulium states, respectively. (C) 2004 American Institute of Physics.

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.

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

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

Effect of PbS impurity on crystallization mechanism of phosphate glasses studied by differential scanning calorimetry

In this work, differential scanning calorimetry (DSC) was used to study effect of PbS impurity on crystallization mechanism of phosphate glasses. Bulk glasses presented one crystallization peak while powdered glasses presented two distinct crystallization peaks. For both undoped and doped glasses were determined the activation energies for the crystallization and the Avrami n parameters. The activation energies for undoped phosphate glass were 336 +/- 6 and 213 +/- 3 kJ mol(-1), respectively, associated with first and second crystallization peaks. For doped glass, the obtained energies were 373 +/- 9 and 286 +/- 7 kJ mol(-1). The calculated Avrami parameters, based on first crystallization peaks, for undoped and doped glasses were 2.25 +/- 0.01 and 1.75 +/- 0.02, respectively. These values suggest that the first DSC peak, in both glasses, may be associated with surface crystallization. (C) 2002 Elsevier B.V. B.V. All rights reserved.

DSC studies on crystallization mechanisms of tellurite glasses

The purpose of this work is to study the 20Li(2)O-80TeO(2) glass using the differential scanning calorimetry (DSC) and X-ray diffraction (XRD) techniques in order to understand the crystallization kinetics on this glass matrix. To study the glass by DSC, screened samples with different particle sizes to resolve the observed asymmetrical crystallization peak were used. DSC curves for particles smaller than 38 mum in size show two distinct crystallization peaks, associated to distinct phase transformation in this glass, leading to activation energies at 301 and 488 kJ mol(-1). XRD analysis reveals that the first crystallization peak is attributed to TeO2 crystalline phase while the second one to the alpha-TeO3 and an unidentified phase.(C) 2004 Elsevier B.V. All rights reserved.

The temperature coefficient of the optical path length as a function of the temperature in different optical glasses

An interferometric technique was used to determine the temperature coefficient of the optical path length (dS/dT) as a function of the temperature in several optical glasses. The temperature range was between 25degreesC and 180degreesC. The studied samples included undoped and doped oxide glasses, such as low silica calcium aluminosilicate, phosphates, borates and also chalcogenides. The oxide glasses had dS/dT between 10 X 10(-6) K-1 and 20x10(-6) K-1, while for the chalcogenides, these were around 70 x 10(-6)K(-1). The results showed that dS/dTs increased with the temperature in all samples. For samples doped with Nd the dS/dT values were found to be independent of concentration. on the other hand, for the phosphate glass doped with Cr, dS/dT increased about 5% when compared with the Nd doped one. In conclusion, the used interferometric method, which is a considerably simpler and a lower cost technique, and is a useful tool to measure dS/dT in semi-transparent glasses as a function of the composition and temperature. (C) 2004 Elsevier B.V. All rights reserved.