Evaluation of laser level populations of erbium-doped glasses

A simulation of erbium-doped glass systems, which provides population density for the excited states involved in the 1.5 mu m and also for 2.7 mu m emissions when pumped around 980 nm, is presented. To describe the diode pump laser processes, a theoretical model based in a coupled system of differential rate equations was developed. The approach used and the obtained spectroscopic parameters are discussed. The materials under study are two oxide glasses, lead fluoroborate (PbO-PbF2-B2O3), and heavy metal oxide (Bi2O3 PbO-Ga2O3) and a fluoride glass (ZrF4-BaF2-LaF3-AlF3-NaF), all of them doped with Er3+. (c) 2006 Elsevier B.V. All rights reserved.

Mechanical behaviour of self-compacting concrete with hybrid fibre reinforcement

In this study, fibre-reinforced self-compacting concretes were developed for precast building components, incorporating either adherent metal fibres or polymeric synthetic slipping fibres or a combination of both. To achieve the warranted workability, compressive and splitting tensile strengths, compositions were determined by preliminary tests on self-compacting materials with various proportions of metal fibres. Bending tests in controlled deflection confirmed the positive contribution of fibres in the mechanical behaviour of self-compacting concrete. The comparison between vibrated and self-compacting concretes of similar mechanical characteristics indicated a possible better fibre-matrix bond in the case of self-compacting types. The results also showed that the properties of the hybrid fibre-reinforced self-compacting concrete could be inferred from the properties of the individual single-fibre reinforcements and their respective proportions through simple mix-rules.

Above bandgap induced photoexpansion and photobleaching in Ga-Ge-S based glasses

Photoexpansion and photobleaching effects have been examined in glass compositions Ga10Ge25S65 and Ga5Ge25As5S65. Such compositions are promising for optical storage and planar waveguide applications. To evaluate the photoinduced effect, samples were exposed to 351 nm light, varying power density (3-10 W/cm(2)) and exposure time (0-120 min). The exposed areas have been analyzed using atomic force microscopy (AFM) and an expansion of 800 nm is observed for composition Ga10Ge25S65 exposed during 120 min and 5 W/cm(2) power density. The optical absorption edge measured by a spectrophotometer indicates a blue shift (80 nm) after illumination in the composition Ga10Ge25S65. The morphology was examined using a scanning electron microscopy (SEM). The chemical compositions measured using a energy dispersive analyzer (EDX) indicate an increase of the number of sulfur atoms in the irradiated area. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Multi-scale structural description of siloxane-PPO hybrid ionic conductors doped by sodium salts

Alkaline metal doped organic - inorganic hybrids have potential applications in the field of portable energy sources. Attractive sol - gel derived urea cross-linked polyether, siloxane - PPO ( poly( propylene oxide)) hybrids doped with sodium salts ( NaClO4 and NaBF4) were examined by multi-spectroscopic approach that includes complex impedance, X-ray powder diffraction (XRPD), small angle X-ray scattering (SAXS), Si-29 and Na-23 magic-angle spinning nuclear magnetic resonance (NMR/MAS), Na K-edge X-ray absorption near edge structure (XANES) and Raman spectroscopies. The goals of this work were to determine which cation coordinating site of the host matrix ( ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the thermal and electrical properties. The main conclusion derived from this study is that the NaBF4 salt has a much lower solubility in the hybrid matrix than the NaClO4 salt. Furthermore, the addition of a large amount of salt plays a major role in the hybrid nanostructure and electrical properties, modifying the PPO chain conformation, weakening or breaking the hydrogen bond of the polyether - urea associations and changing the polycondensation and aggregation processes involving the siloxane species.

Glasses in the SbPO4-WO3 system

Glasses in the binary system (100 - x)SbPO4-xWO3 (20 <= x <= 60, x in mol%) have been prepared and characterized. Differential thermal analysis (DTA) shows that the glass transition temperature, T-g increases from 412 degrees C, for samples containing 20 mol% of WO3 to 481 degrees C observed for glass containing 60 mol%. Sample containing 40 mol% in WO3 were observed to be the most stable against devitrification. The structural organization of the glasses has been studied by using Fourier transform infra-red (FTIR), Raman, P-31 Magic angle spinning (MAS) and spin echo nuclear magnetic resonance (NMR) spectroscopies. Results suggest two distinct networks comprising the glass structure, one with high SbPO4 content and the other characteristic of the highest WO3 content samples. The glasses present photochromic properties. Colour changes are observed for samples after exposure to ultraviolet or visible laser light. XANES, at L-1 absorption edge of tungsten, suggests partial reduction from W6+ to W5+ species during the laser irradiation. The photochromic effects and the colour changes, promoted by laser excitation, are reversible and easily removed by heat for during 1 h at 150 degrees C. Subsequent 'write/erase' cycles can be done without degradation of the glasses. (C) 2007 Elsevier B.V. All rights reserved.

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.

Temperature and wavelength dependence of the thermo-optical properties of tellurite and chalcogenide glasses

The refractive index and the temperature coefficient of the optical path length change of tellurite (80TeO(2):20Li(2)O) and chalcogenide glasses (72.5Ga(2)S(3):27.5La(2)O(3)) were determined as a function of temperature (up to 150 degrees C) and wavelength (in the range between 454 and 632.8 nm). The tellurite glass exhibits the usual refractive index dispersion in the wavelength range analyzed, while anomalous refractive index dispersion was observed for the chalcogenide glass between 454 and 530 nm. The dispersion parameters were determined by means of the single-effective oscillator model. In addition, a strong dependence of the temperature coefficient of the optical path length on the photon energy and temperature was found for the chalcogenide glass. The latter was correlated to the shift of the optical band gap (or electronic edge) with temperature, which was interpreted by the electron-phonon interaction model. (C) 2007 American Institute of Physics.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO3-x% MoO3 (0 <= x <= 70) glass-forming system by a modified melt method that allowed good optical quality samples to be obtained. The structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), Raman scattering, and solid-state nuclear magnetic resonance (NMR) for P-31, Na-23, and Mo-95 nuclei. Addition of MoO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures up to x = 45, suggesting a significant increase in network connectivity. For this same composition range, vibrational spectra suggest that the Mo6+ ions are bonded to some nonbridging oxygen atoms (Mo-O- or Mo=O bonded species). Mo-O-Mo bond formation occurs only at MoO3 contents exceeding x = 45. P-31 magic-angle spinning (MAS) NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. These sites are denoted as Q(2Mo)((2)), Q(1Mo)((2)), and Q(0Mo)((2)), respectively. For x < 0.45, the populations of these sites can be described along the lines of a binary model, according to which each unit of MoO3 converts two Q(nMo)((2)) sites into two Q((n+1)Mo)((2)) sites (n = 0, 1). This structural model is consistent with the presence of tetrahedral Mo(=O)(2)(O-1/2)(2) environments. Indeed, Mo-95 NMR data suggest that the majority of the molybdenum species are four-coordinated. However, the presence of additional six-coordinate molybdenum in the MAS NMR spectra indicates that the structure of these glasses may be more complicated and may additionally involve sharing of network modifier oxide between the network formers phosphorus and molybdenum. This latter hypothesis is further supported by Na-23{P-31} rotational echo double resonance (REDOR) data, which clearly reveal that the magnetic dipole-dipole interactions between P-31 and Na-23 are increasingly diminished with increasing molybdenum content. The partial transfer of modifier from the phosphate to the molybdate network former implies a partial repolymerization of the phosphate species, resulting in the formation of Q(nMo)((3)) species and accounting for the observed increase in the glass transition temperature with increasing MoO3 content that is observed in the composition range 0 <= x <= 45. Glasses with MoO3 contents beyond x = 45 show decreased thermal and crystallization stability. Their structure is characterized by isolated phosphate species [most likely of the P(OMo)(4) type] and molybdenum oxide clusters with a large extent of Mo-O-Mo connectivity.

Totally visible transparent chloro-sulphide glasses based on Ga2S3-GeS2-CsCI

In this paper, the influence on optical properties of alkali halides such as CsCl in a covalent glassy matrix has been investigated. Chalcogenide glasses belonging to the (GeS2)-(Ga2S3)-CsCI system with high ratio of CsCl present an entire transparency in the visible range. These glasses maintain good transmission up to 12 mu m. Furthermore, the thermo-mechanical properties and the glass hygroscopicity have been investigated as function of the CsCl amount. This new generation of glasses presents a great interest for optical application. They could be used both for passive applications (multi-spectral imaging) and active applications for rare-earth doping due to their good transmission in the visible range, increasing optical pumping possibilities.

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.

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 (&GE; 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

Titania-based organic-inorganic hybrid planar waveguides

Eu3+ -doped titania-silica planar waveguides were prepared from tetraethylorthotitanate (TEOT) and modified silane 3-amino-propyltriethoxysilane (APTS). Films were deposited on borosilicate glass substrates by a dip-coating technique. The refractive index, the thickness and the total attenuation coefficient of the waveguides were measured at 632.8 and 1550 nm by prism coupling technique. Starting from pure titania films, the addition of modified silane leads to a decrease in the refractive index and an increase in thickness. Squared electric field simulation has shown that the light confinement in the waveguide increases with the silane content of the so]. Emission spectra present a broad emission band due to the modified silane and EU emission transitions arising mainly from the D-5(0) level to the F-7(J) (J = 0-4) manifolds. The dependence of transition intensities and excited state lifetimes on the initial composition and also on the heat treatment performed was interpreted in terms of structural changes occurring during the preparation process. (C) 2002 Elsevier B.V. B.V. All rights reserved.