Avrami exponent of crystallization in tellurite glasses

Nucleation process and crystal growth for three samples of the (20-x)Li(2)O-80TeO(2)-xWO(3) glass system were studied using X-ray diffraction and differential scanning calorimetry techniques. X-ray diffraction data confirmed the amorphous characteristic of the as-quenched samples and indicated the growth of crystalline phases formed due to the thermal treatment for annealed samples. These results reveal the presence of three distinct gamma-TeO(2), alpha-TeO(2) and alpha-Li(2)Te(2)O(5) crystalline phases in the TL sample, and two distinct alpha-TeO(2) and gamma-TeO(2) crystalline phases in the TLW5 and TLW10 samples. The activation energy and the Avrami exponent were determined from DSC measurements. The activation energy values X-ray diffraction data of the TLW10 glass sample suggest that gamma-TeO(2) phase occur before the alpha-TeO(2). The results obtained for the Avrami exponent point to that the nucleation process is volumetric and that the crystal growth is two or three-dimensional.

Relation among optical, thermal and thermo-optical properties and niobium concentration in tellurite glasses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effects of glass-forming histories on the crystallization kinetic of the 20Li(2)O-80TeO(2) glass

In the present work, tellurite 20Li(2)O-80TeO(2) glasses were prepared with identical nominal composition under different glass-forming histories to produce a stressed and stress-free samples. X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC) techniques were used to study the effects of the glass-forming histories on the thermal and structural properties of these glasses. The gamma-TeO2 (metastable), alpha-TeO2 and alpha-Li2Te2O5 phases were identified during the controlled devitrification in these glasses. The mestastable character of the gamma-TeO2 phase was clearly observed in the glass under stress but this effect is not so clear in the stress-free glass. The gamma-TeO2 and alpha-TeO2 phases crystallizes during the initial stages of crystallization in both studied glasses while the alpha-Li2Te2O5 phase crystallize in the final stages of the crystallization. The activation energies and Avrami exponent were calculated for both studied glasses with different particle size leading to E-3 > E-2 > E-1 for stressed glass and E-3 > E-2 approximate to E-1 for stress-free glass, where E-1, E-2 and E-3 were associated to the gamma-TeO2, alpha-TeO2 and alpha-Li2Te2O5 phases, respectively. The observed distinct (n) over bar (1) < <(n)over bar>(2) < <(n)over bar>(3) in both glasses is an indicative that nucleation and growth takes place by more than one mechanism in the early stages of the crystallization. (C) 2011 Elsevier B.V. All rights reserved.

PHYSICAL PROPERTIES of TELLURITE GLASSES PREPARED UNDER DIFFERENT THERMAL HISTORIES

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermally stimulated crystallization glass system of (20-x)LiO2-80TeO(2)-xWO(3)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

1.5 mu m and visible up-conversion emissions in Er3+/Yb3+ co-doped tellurite glasses and optical fibers for photonic applications

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Local order around rare earth ions during the devitrification of oxyfluoride glasses

Erbium L-3-edge extended x-ray absorption fine structure (EXAFS) measurements were performed on rare earth doped fluorosilicate and fluoroborate glasses and glass ceramics. The well known nucleating effects of erbium ions for the crystallization of cubic lead fluoride (based on x-ray diffraction measurements) and the fact that the rare earth ions are present in the crystalline phase (as indicated by Er3+ emission spectra) seem in contradiction with the present EXAFS analysis, which indicates a lack of medium range structural ordering around the Er3+ ions and suggests that the lead fluoride crystallization does not occur in the nearest neighbor distance of the rare earth ion. Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er3+ ions were performed, and results indicate that Er3+ ions lower the devitrification temperature of PbF2, in good agreement with the experimental results. The genuine role of Er3+ ions in the devitrification process of PbF2 has been investigated. Although Er3+ ions could indeed act as seeds for crystallization, as experiments suggest, molecular dynamics simulation results corroborate the experimental EXAFS observation that the devitrification does not occur at its nearest neighbor distance. (c) 2008 American Institute of Physics.

Time dependence and energy-transfer mechanisms in Tm3+Ho3+ and Tm3+-Ho3+ co-doped alkali niobium tellurite glasses sensitized by Yb3+

Glass samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing Yb3+, Tm3+ and Ho3+. The energy transfer and energy back transfer mechanisms in samples containing 5% Yb3+-5% Tm3+ and 5% Yb3+-5% Tm3+-0.5% Ho3+ were estimated by measuring the absorption and fluorescence spectra together with the time dependence of the Yb3+ F-2(5/2) excited state. A good fit for the luminescence time evolution was obtained with the Yokota-Tanimoto's diffusion-limited model. The up-conversion fluorescence was also studied in 5% Yb-5% Tm. 5% Yb-0.5% Ho and 5% Yb-5% Tm-0.5% Ho tellurite glasses under laser excitation at 975 nm. Strong emission was observed from (1)G(4) and F-3(2) Tm3+ energy levels in all samples. The S-5(2) Ho3+ emission was observed only in Yb3+Ho3+ samples being completely quenched in Yb3+/Tm3+/Tm3+ samples. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Red-green-blue upconversion emission and energy-transfer between Tm3+ and Er3+ ions in tellurite glasses excited at 1.064 mu m

Red, green, and blue emission through frequency upconversion and energy-transfer processes in tellurite glasses doped with Tm3+ and Er3+ excited at 1.064 mum is investigated. The Tm3+/Er3+-codoped samples produced intense upconversion emission signals at around 480, 530, 550 and 660 nm. The 480 nm blue emission was originated from the (1)G(4)-->H-3(6) transition of the Tm3+ ions excited by a multiphoton stepwise phonon-assisted excited-state absorption process. The 5 30, 5 50 nm green and 660 mn red upconversion luminescences were identified as originating from the H-2(11/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) --> I-4(15/2) transitions of the Er3+ ions, respectively, populated via efficient cross-relaxation processes and excited-state absorption. White light generation employing a single infrared excitation source is also examined. (C) 2003 Elsevier B.V. (USA). All rights reserved.

Temperature investigation of infrared-to-visible frequency upconversion in erbium-doped tellurite glasses excited at 1540 nm

Temperature investigation of infrared-to-visible frequency upconversion in erbium-doped tellurite glasses excited by CW laser radiation at 1540 nm and under cryogenic temperatures is reported. Intense upconversion emission signals around 530, 550 and 660 nm corresponding to the H-2(11/2), S-4(3/2), and F-4(9/2) transitions to the I-4(15/2) ground state were generated and studied as a function of the laser intensity and temperature. The upconversion excitation mechanism of the Er3+ ions emitting energy levels was accomplished via stepwise multiphoton absorption. The green upconversion luminescence exhibited a fivefold intensity enhancement when the temperature of the sample was varied in the range between 5 and 300 K. A maximum green upconversion intensity was attained around 120 K and a steady decreasing behavior for higher temperatures up to 300 K was observed. A model based upon conventional rate equations was used to model the observed temperature evolution of the upconversion luminescence. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Infrared-to-visible frequency upconversion in Pr3+/Yb3+- and Er3+/Yb3+-codoped tellurite glasses

Upconversion luminescence and thermal effects in Pr3+/Yb3+- and Er3+/Yb3+-codoped 60TeO(2)-10GeO(2)-10K(2)O-10Li(2)O-10Nb(2)O(5) tellurite glasses excited by CW infrared radiation at 1.064 mum is reported. Generation of intense green and red fluorescence emission in Er3+/Yb3+-codoped samples and appreciable upconversion luminescence in the wavelength region of 450-680 nm in Pr3+/Yb3+-codoped samples is observed. Temperature-induced enhancement of X12 in the upconversion efficiency in Er3+/Yb3+- and X10 in the Pr3+/Yb3+-doped samples is demonstrated. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Raman scattering, differential scanning calorimetry and Nd3+ spectroscopy in alkali niobium tellurite glasses

Alkali niobium tellurite glasses have been prepared and some of their properties measured by differential scanning calorimetry and Raman scattering. The vitreous domain was established in the pseudo ternary phases diagram for the system TeO2-Nb2O5-(0.5K(2)O-0.5Li(2)O). Raman scattering shows that for samples in the TeO2 rich part of the phase diagram the vitreous structure is composed essentially of (TeO4) units connected by the vertices, as in the alpha-TeO2 crystal. The addition of alkali and niobium oxides causes depolymerization to occur with structures composed essentially of (TeO3) and (NbO6) units. Samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing up to 10% mol Nd3+. The addition of this oxide increases the rigidity of the vitreous network shifting characteristic temperatures to higher temperatures. For the 10% Nd3+ sample amorphous phase separation is assumed to exist from the observation of two glass transition temperatures. Spectroscopic properties such as Judd-Ofelt Omega(lambda) intensity parameters, radiative emission probabilities, and induced emission cross sections were calculated. From these results and also from the emission quenching observed as a function of Nd3+ concentration, we suggest that these glasses could be utilized in optical amplifying devices. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Study of fluorine losses in oxyfluoride glasses

Glasses in PbGeO3-PbF-CdF2 and GeO2-PbO-PbF2-CdF2 systems were studied and the fluorine losses during synthesis were investigated. Samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction, Fourier transform infrared spectroscopy (FTIR) and Raman scattering spectroscopy. The use of stoichiometric germanate glass, PbGeO3, instead of introducing individual oxides (GeO2 + PbO) lead to decreasing fluorine losses, as detected by a fluorine ion selective electrode. The main structural features obtained from vibrational spectroscopy could be described by a metagermanate basic structure permeating fluorine rich regions. (c) 2005 Elsevier B.V. All rights reserved.

Sol-gel Eu3+/Tm3+ doped transparent glass-ceramic waveguides

Eu3+ and Tm3+ doped lanthanum fluoride and lanthanum oxyfluoride are obtained from Eu3+, Tm3+ containing lanthanum fluoracetate solutions. The nature of the crystal phase obtained could be controlled by the temperature of heat treatment. Spectral characteristics of Eu3+ doped crystal phases were sufficiently different to allow utilization of Eu3+ as structural probes. Tm3+ emission at the technologically important spectral region of 1450nm could be observed for the fluoride and oxyfluoride crystal phases. The large bandwidth obtained (around 120nm) suggests potential applications in optical amplification. SiO2-LaF3-LaOF composite materials were also prepared. It is observed that for heat treatments above 800degreesC, fluorine loss, probably in the form of SiF4 hinder the observation of Tm3+ emission. Eu3+ spectroscopic characteristics clearly show the evolution of a fluoride like environment to an amorphous oxide one as the temperature of heat treatment increased. Thin films obtained by dip-coating on V-SiO2 substrates and treated at 300degreesC, 500degreesC and 800degreesC display guided modes in the visible and infrared regions. Optical characteristics (refractive index and films thickness) were obtained at 543.5, 632.8 and 1550nm. Attenuation as low as 1.8dB/cm was measured at 632.8nm. (C) 2004 Published by Elsevier B.V.

Conductivity and F-19 NMR in PbGeO3-PbF2-CdF2 glasses and glass-ceramics

The temperature dependence of the electrical conductivity and the F-19 nuclear magnetic resonance (NMR) of PbGeO3-PbF2CdF, glasses and glass ceramics are investigated. The measured conductivity values of the glasses are above 10(-5) Skin at 500 K, and increase with increasing lead fluoride content. Activation energies extracted from the conductivity data are in the range 0.59-0.73 eV. Results are consistent with the hypothesis that in these oxyfluoride glasses lead fluoride rich clusters are dispersed in a metagermanate based matrix providing increasing mobility pathways for conducting ions. The conductivity of a sample of the glass ceramic of composition (mol%) 60PbGeO(3-)20PbF(2)-20CdF(2) was found to be smaller than that in the corresponding glass, suggesting that there are poor ionic conducting regions in the interface between the nanometer sized crystals. The temperature dependence of the F-19 relaxation times, measured in the range 100-800 K, exhibit the qualitative features associated with high fluorine mobility in both, glass and glass ceramics materials. We suggest that de-convolution of the spin-lattice relaxation rates observed in the glass ceramics shows that the observed high temperature rate maximum is associated with the diffusional motions of the fluorine ions in beta-PbF2 crystals. (c) 2005 Elsevier B.V. All rights reserved.