Time-resolved Z-scan and thermal lens measurements in Er+3 and Nd+3 doped fluoroindate glasses

In rare earth ion doped solids, a resonant non-linear refractive index, n2, appears when the laser pumps one of the ion excited states and the refractive index change is proportional to the excited state population. In these solids there are usually thermal and non-thermal lensing effects, where the non-thermal one is due to the polarizability difference, Δα, between excited and ground states of the ions. We have used the time resolved Z-scan and a mode-mismatched thermal lens technique with an Ar+ ion laser in Er+3 (20ZnF2-20SrF2-2NaF-16BaF2-6GaF3-(36 - x)InF3-xErF3, with x= 1, 2, 3 and 4 mol%) and Nd+3 (20SrF2-16BaF2-20ZnF2-2GdF3-2NaF-(40 - x)InF3-xNdF3, with x = 0.1, 0.25, 0.5-1 mol%) doped fluoroindate glasses. In both samples we found that the non-linear refraction is due to the thermal effect, while the non-thermal effect is negligible. This result indicates that in fluoride glasses Δα is very small (less than 10-26 cm3). We also measured the imaginary part of the non-linear refractive index (n″2) due to absorption saturation.

Stabilization of fluoroindate glasses by magnesium fluoride

This paper describes the stabilizing effect of MgF2 on the binary system InF3-BaF2. A complete investigation of the In-Ba-Mg system led to samples up to 5 mm in thickness. Further optimization of this system was achieved by incorporation of other fluorides, resulting in increased resistance to devitrification. Thermal and optical data are reported.

Spectroscopy of InF3 based glasses containing a large amount of GdF3

Glass formation in the pseudo ternary system ZnF2-GdF3-BaF2-InF3 and other complex systems stabilized by NaF, CaF2, AlF3 and YF3 have been investigated. Samples with greater stability have been prepared and their properties measured. Optical absorption and emission spectra of Gd3+ ions doped glasses with 2, 4, 10 and 20% concentrations have been measured. Using the Judd-Ofelt theory and the experimental oscillator strengths, the Judd-Ofelt parameters have been calculated. The emission of Gd3+ ions from 6I and 6P has been detected and the lifetime has been measured.

SAXS measurements of the porosity in Cu(II)-doped SnO2 xerogels during crystallization

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Crystallization of ZrF4-LaF3-AlF3 glasses

0.7125ZrF4-0.2375(1 - xLaF3 • xLnF3)-0.05AIF3 with x = 0.01, 0.02 and 0.03 for Ln = Er and x = 0.03 for Ln = Pr, Nd glasses were studied by differential thermal analysis (DTA), X-ray diffraction and optical spectroscopy. Avrami parameters (Ec and n) were obtained from DTA curves. With La3+ substitution a decrease in the stability against crystallization was observed. This decrease follows the order Er3+ > Nd3+ ≈ Pr3+ for 3% molar substitution. n values suggest an interface controlled growth mechanism with grain edge nucleation abler saturation. Two crystalline polymorphs of the LaZr3F15 phase were identified. With the substitution of 3 mol% of Pr3+, Nd3+ or Er3+ for La3+ only the crystallization of the rhombohedral α-LnZr3F15 phase was observed. An increase in Ω6 Judd's intensity parameter occurs with crystallization and also an increase in the 1.04 μm peak emission cross-section for Nd3+ 4I3/2 state suggesting the potential application of these glass ceramics in optical amplification devices. © 1997 Elsevier Science B.V.

Crystallization of fluorindate and fluorogallate glasses

Crystallization of binary InF3-MF2 and GaF3-MF2 (where M = Ba, Sr and Ca) glasses was studied. Characteristic temperatures and kinetic parameters E (activation energy) and n (Avrami exponent) were obtained. Stability against devitrification is discussed in terms of the above cited parameters and also of some others parameters proposed in literature. Optical properties (IR and upconversion emissions) are reported in different crystallized samples containing Nd3+. The main observation is that up conversion emission presents an enhanced sensibility to crystallization when compared to conventional emission. © 1997 Published by Elsevier Science B.V.

Energy transfer between Pr3+ ions in a fluoroindate glass

The efficiency of energy transfer (ET) between Pr3+ ions in a fluoroindate glass is determined. ET rates, WET, were determined for dilute samples and the results show a dependence of WET on the Pr3+ concentration. ET processes which contribute to resonance fluorescence and frequency upconversion emission were studied. The origin of the interaction energy among the Pr3+ ions was determined to be dipole - dipole. © 1998 Elsevier Science B.V. All rights reserved.

Magneto-optical rotation of heavy-metal oxide glasses

Magneto-optical rotation was measured at room temperature for glasses containing Bi2O3-CdO-GeO2 (BCG), and Bi2O3-PbO-GeO2-B2O3 (BPGP). A pulsed magnetic field between 50 and 80 KG was used to measure Faraday rotation at 632.8 nm as a function of the concentration of Bi and Cd for BCG and Bi and Pb for BPGB. Verdet constant as high as 0.162 min G-1 cm-1 at 632.8 nm for the BPGB sample with the highest concentrations of Bi and Cd was found. Verdet constant increases linearly with the heavy-metal concentration for the BPGB whereas it reaches some saturation for the BCG system. Measurements of the magneto-optical rotation at other wavelengths in the visible and the refractive index at 632.8 nm are also reported. © 1998 Elsevier Science B.V. All rights reserved.

Giant non-linear absorption in Er3+-doped fluoroindate glass

Non-linear absorption is observed in Er3+-doped fluoroindate glass (in mol% 37InF2:20ZnF2:20SrF2:16BaF2:2GdF2: 2NaF:1GaF3:2ErF3) when the sample is irradiated with a CW laser emitting at 650 nm. An intensity dependence of the optical transmittance is detected. Saturation and sequential absorption of two photons are responsible for the decrease of 50% in the transmittance. The results are explained by simple models which are solved based on rate-equations for the populations of energy levels.

Chromium-containing silica materials

Chromium-containing silica samples were obtained from soluble sodium silicate solutions in the presence of different chromium nitrate concentrations. Precipitation was carried out in ethanolic media. Gel precipitate was dried by liophylization and samples measured by transmission electron microscopy (TEM), X-ray energy-dispersive spectrometer, X-ray mapping, X-ray photoemission spectroscopy (XPS), and particle size analysis. Spherical chromium containing silica particles with 3.5% and 4.8% (at.%) of chromium were obtained. Particle size analysis results showed that with increased addition of chromium in sodium silicate solutions produces agglomerates whose sizes range from 1 to 0.2 μm. Chromium mapping and XPS results show that chromium oxide is preferentially segregated on particle surfaces. Chromium oxide was detected on particle surface with a binding energy of 576.77 ± 0.05 eV as obtained from XPS analysis. During the hydrolysis and condensation processes chromium oxide precipitates on the silica surface and it affects the silica chain size. © 2000 Elsevier Science B.V. All rights reserved.

Densification and residual stresses induced in glass surfaces by Vickers indentations

Images and profiles of Vickers impressions produced on as-received float-glass were obtained using atomic force microscopy (AFM). The images show that the impression edges undergo elastic recovery parallel to surface. The profiles made it possible to measure vertical elastic recovery, ev(r). For a 40 g nominal load, maximum penetration depth of indenter was (2.20 ± 0.03) μm, and recovery at the impression center was ev(0) = (0.98 ± 0.03) μm. Vertical elastic recovery was non-uniform along profiles. Permanent impressions produced resulted from glass mass displacement downward, producing an increase in glass density in impression vicinity, which is discussed in terms of changes in O-Si-O and Si-O-Si bond angles and Si-O bond length. Near impression edges, pileup was observed for which a simplified model is proposed taking into account the compaction and stresses near the impressions. © 2000 Elsevier Science B.V. All rights reserved.

Formation of colloidal particles of hydrous iron oxide by forced hydrolysis

The mechanism of formation and growth of hydrous iron oxide (FeOOH) during the initial stages of forced hydrolyses of ferric chloride aqueous solution was studied by small angle X-ray scattering (SAXS). The effect of the hydrolysis temperature (60°C, 70°C and 80°C) and of the addition of urea on the formation of colloidal particles under isothermal conditions were investigated. Based on the experimental scattering functions in the Guinier range, we suggest the presence of elongated colloidal particles. The particle diameter and length, and their variation with time, were determined by fitting the form factor of prolate ellipsoids to the experimental scattering functions. We have assumed that our solutions are in a dilute state and that all colloidal particles are approximately of the same size. The colloidal particles have geometrical shapes similar to those of the subcrystals that build up the superstructure of β-FeOOH crystals, indicating that the formation of this hydrous iron oxide is governed by an aggregation process. Otherwise, the addition of urea hinders the growth and yields smaller particles, with a reduction in size greater than 50%. © 2000 Elsevier Science B.V. All rights reserved.

Crystallization mechanism and properties of a blast furnace slag glass

The complex crystallization process of a Brazilian blast-furnace slag glass was investigated using differential scanning calorimetry (DSC), X-ray diffraction, optical microscopy, transmission electron microscopy (TEM), selected area diffraction (SAD), energy dispersive spectroscopy (EDS) and micro-Raman spectroscopy. Three crystalline phases (merwinite, melilite and larnite) were identified after heat treatment between Tg (742°C) and the DSC crystallization peak (T = 1000°C). Merwinite was identified as a metastable phase. A small amount (0.004 wt%) of metallic platinum was found in the glass composition. Particles of Pt3Fe, detected by EDS and SAD-TEM, were the starting points of crystallization acting, therefore, as heterogeneous nucleating sites. Only melilite and larnite precipitated in a glass sample heat-treated at 1000°C for 1 h. The flexural strength of this crystallized sample was less than that of the glass, probably due the allotropic phase transformation of larnite. © 2000 Published by Elsevier Science B.V. All rights reserved.

Non-isothermal study of the devitrification kinetics of fluoroindate glasses

The understanding of the kinetics of devitrification of a glass is important for anticipating its stability in a particular purpose, such as fiber-drawing processes. The crystallization kinetics of (BaF2)16(ZnF2)20(SrF 2)20(NaF)2 (GaF3)5(InF3)36(GdF 3)1 glass prepared by quenching were studied by differential scanning calorimetry (DSC). Avrami's exponent (n) obtained by a non-isothermal method was 4.3 for a solid and 2.4 for a powdered sample. According to the classical interpretation of n, these magnitudes correspond to an interface-controlled crystal growth and a diffusion-controlled crystal growth, respectively. The activation energies for crystallization (E) was 62 ± 1 kJ/mol for solid glass and 245 ± 2 kJ/mol for powdered glass. These results are discussed in terms of glass particle size. © 2000 Elsevier Science B.V. All rights reserved.

Evolution of the viscoelastic properties of SnO2 colloidal suspensions during the sol-gel transition

This paper describes the effect of the concentration of electrolyte and pH on the kinetics of aggregation and gelation processes of SnO2 colloidal suspensions. Creep, creep-recovery, and oscillatory rheological experiments have been done in situ during aggregation and gelation. A phenomenological description of the structure of the colloidal system is given from the time evolution of rheological parameters. The dependence of the equilibrium steady-state shear compliance on the terminal region of clusters or aggregates seems to be a way to determine the beginning of interconnection of aggregates and the gel point. We propose that at this point the equilibrium steady-state compliance is a minimum. The steady-state viscosity determined from creep experiment can be fit with a power law with the extent of the transformation, giving critical exponent s = 0.7 ± 0.1. The value of the critical exponent Δ = 0.78 ± 0.05 was determined from oscillatory experiment. These results indicate that gelation of SnO2 colloidal suspension exhibits the typical scale expected from the scalar percolation theory. © 2000 Elsevier Science B.V. All rights reserved.