MAS NMR as a probe for investigating the distribution of Si---O---Si angles in lithium silicate glasses

Magic-angle-spinning NMR has been used to study Si---O---Si bond-angle distributions associated with various structural elements, Qn, present in lithium silicate glasses of different compositions. It is shown that glasses contain a plurality of structural elements with a broad distribution of Si---O---Si bond angles, and that the width of the distribution is characteristic of a particular Qn species

Distribution of ionic charge carriers and migration barriers in binary alkali silicate glasses

Likely spatial distributions of network-modifying (and mobile) cations in (oxide) glasses are discussed here. At very low modifier concentrations, the ions form dipoles with non-bridging oxygen centres while, at higher levels of modification, the cations tend to order as a result of Coulombic interactions. Activation energies for cation migration are calculated, assuming that the ions occupy (face-sharing) octahedral sites. It is found that conductivity activation energy decreases markedly with increasing modifier content, in agreement with experiment.

Direct correlation between non-random distribution of cations and ion transport mechanism in soda-lime silicate glasses

We report a direct correlation between dissimilar ion pair formation and alkali ion transport in soda-lime silicate glasses established via broad band conductivity spectroscopy and local structural probe techniques. The combined Raman and Nuclear Magnetic Resonance (NMR) spectroscopy techniques on these glasses reveal the coexistence of different anionic species and the prevalence of Na+-Ca2+ dissimilar pairs as well as their distributions. The spectroscopic results further confirm the formation of dissimilar pairs atomistically, where it increases with increasing alkaline-earth oxide content These results, are the manifestation of local structural changes in the silicate network with composition which give rise to different environments into which the alkali ions hop. The Na+ ion mobility varies inversely with dissimilar pair formation, i.e. it decreases with increase of non-random formation of dissimilar pairs. Remarkably, we found that increased degree of non-randomness leads to temperature dependent variation in number density of sodium ions. Furthermore, the present study provides the strong link between the dynamics of the alkali ions and different sites associated with it in soda-lime silicate glasses. (C) 2014 Elsevier B.V. All rights reserved.

Water in silicate glasses

The speciation of water in a variety of hydrous silicate glasses, including simple and rhyolitic compositions, synthesized over a range of experimental conditions with up to 11 weight percent water has been determined using infrared spectroscopy. This technique has been calibrated with a series of standard glasses and provides a precise and accurate method for determining the concentrations of molecular water and hydroxyl groups in these glasses.

For all the compositions studied, most of the water is dissolved as hydroxyl groups at total water contents less than 3-4 weight percent; at higher total water contents, molecular water becomes the dominant species. For total water contents above 3-4 weight percent, the amount of water dissolved as hydroxyl groups is approximately constant at about 2 weight percent and additional water is incorporated as molecular water. Although there are small but measurable differences in the ratio of molecular water to hydroxyl groups at a given total water content among these silicate glasses, the speciation of water is similar over this range of composition. The trends in the concentrations of the H-bearing species in the hydrous glasses included in this study are similar to those observed in other silicate glasses using either infrared or NMR spectroscopy.

The effects of pressure and temperature on the speciation of water in albitic glasses have been investigated. The ratio of molecular water to hydroxyl groups at a given total water content is independent of the pressure and temperature of equilibration for albitic glasses synthesized in rapidly quenching piston cylinder apparatus at temperatures greater than 1000°C and pressures greater than 8 kbar. For hydrous glasses quenched from melts cooled at slower rates (i.e., in internally heated or in air-quench cold seal pressure vessels), there is an increase in the ratio of molecular water to hydroxyl group content that probably reflects reequilibration of the melt to lower temperatures during slow cooling.

Molecular water and hydroxyl group concentrations in glasses provide information on the dissolution mechanisms of water in silicate liquids. Several mixing models involving homogeneous equilibria of the form H_2O + O = 20H among melt species have been explored for albitic melts. These models can account for the measured species concentrations if the effects of non-ideal behavior or mixing of polymerized units are included, or by allowing for the presence of several different types of anhydrous species.

A thermodynamic model for hydrous albitic melts has been developed based on the assumption that the activity of water in the melt is equal to the mole fraction of molecular water determined by infrared spectroscopy. This model can account for the position of the watersaturated solidus of crystalline albite, the pressure and temperature dependence of the solubility of water in albitic melt, and the volumes of hydrous albitic melts. To the extent that it is successful, this approach provides a direct link between measured species concentrations in hydrous albitic glasses and the macroscopic thermodynamic properties of the albite-water system.

The approach taken in modelling the thermodynamics of hydrous albitic melts has been generalized to other silicate compositions. Spectroscopic measurements of species concentrations in rhyolitic and simple silicate glasses quenched from melts equilibrated with water vapor provide important constraints on the thermodynamic properties of these melt-water systems. In particular, the assumption that the activity of water is equal to the mole fraction of molecular water has been tested in detail and shown to be a valid approximation for a range of hydrous silicate melts and the partial molar volume of water in these systems has been constrained. Thus, the results of this study provide a useful thermodynamic description of hydrous melts that can be readily applied to other melt-water systems for which spectroscopic measurements of the H-bearing species are available.

Infrared luminescence properties of bismuth-doped barium silicate glasses

Infrared (IR) luminescence covering 1.1 to similar to 1.6 mu m wavelength region was observed from bismuth-doped barium silicate glasses, excited by a laser diode at 808 nm wavelength region, at room temperature. The peak of the IR luminescence appears at 1325 nm. A full width half-maximum (FWHM) and the lifetime of the fluorescence is more than 200 nm and 400 mu s, respectively. The fluorescence intensity increases with Al2O3 content, but decreases with BaO content. We suggest that the IR luminescence should be ascribed to the low valence state of bismuth Bi2+ or Bi+, and Al3+ ions play an indirect dispersing role for the infrared luminescent centers.

Improved fluorescence from Tm3+/Er3+/Ce3+ triply doped bismuth-silicate glasses for S+C-bands amplifiers

Fluorescence of Tm3+/Er3+ codoped bismuth-silica (BS) glasses and the sensitization of Ce3+ are investigated. It shows that Ce3+ codoping with Tm3+/Er3+ in BS glasses results in a quenching of Tm3+ ion emission from F-3(4) to the H-3(6) level. Consequently, the 1.47 mu m emission occurs after the population inversion between the H-3(4) and F-3(4) levels. Furthermore, the codoped glasses show the broad emission spectra over the whole S and C bands with full-width at half-maximum (FWHM) up to about 119nm, as it combines 1.55 mu m emission band of Er3+ with 1.47 mu m emission band of Tm3+ under 800nm excitation.

Optical spectroscopy and energy transfer of Er3+/Ce3+ in B2O3-doped bismuth-silicate glasses

Ce3+ and B2O3 are introduced into erbium-doped Bi2O3-SiO2 glass to enhance the luminescence emission and optic spectra characters of Er3+. The energy transfer from Er3+ to Ce3+ will obviously be improved with the phonon energy increasing by the addition of B2O3. Here, the nonradiative rate, the lifetime of the I-4(11/2) -> I-4(3/2) transition, and the emission intensity and bandwidth of the 1.5 mu m luminescence with the I-4(13/2) -> I-4(5/2) transition of Er3+ are discussed in detail. The results show that the optical parameters of Er3+ in this bismuth-borate-silicate glass are nearly as good as that in tellurite glass, and the physical properties are similar to those in silicate glass. With the Judd-Ofelt and nonradiative theory analyses, the multiphonon decay and phonon-assisted energy-transfer (PAT) rates are calculated for the Er3+/Ce3+ codoped glasses. For the PAT process, an optimum value of the glass phonon energy is obtained after B2O3 is introduced into the Er3+/Ce3+ codoped bismuth-silicate glasses, and it much improves the energy-transfer rate between Er3+ I-4(11/2)-I-4(13/2) and Ce3+ F-2(5/2) -> F-2(7/2), although there is an energy mismatch. (c) 2007 Optical Society of America.

Effect of CdF2 addition on thermal stability and upconversion luminescence properties in Tm3+-Yb3+ codoped oxyfluoride silicate glasses

Tm3+-Yb3+ codoped oxyfluoride silicate glasses suitable for upconversion laser has been fabricated. In this paper, effect of CdF2 addition on thermal stability and upconversion luminescence properties in Tm3+-Yb3+ codoped oxyfluoride silicate glasses have been systematically investigated. The experimental results indicate that, with the substitution CdF2 for PbF2, the glass thermal stability increases and the UV cutoff edge moves to short-wave band slightly. With increasing CdF2 content, the blue and red upconversion luminescence intensity increases slightly at first, and then increases rapidly. While the near infrared (NIR) upconversion emission intensity increases notably at first and then increases slightly. However, the blue and NIR luminescence intensity are much stronger than that of red, indicating these oxyfluoride silicate glasses are more preferable for blue and NIR emissions than red emission. The possible upconversion mechanisms for the blue, red and NIR fluorescence are also estimated and evaluated. (c) 2006 Elsevier B.V. All rights reserved.

Effect of various alkaline-earth metal oxides on the broadband infrared luminescence from bismuth-doped silicate glasses

We report on the effect of various alkaline-earth metal oxides on the broadband infrared luminescence covering 1000-1600 nm wavelength region from bismuth-doped silicate glasses. The full width at half maximum (FWHM) of the infrared luminescence and the fluorescent lifetime is more than 200 nm and 400 mu s, respectively. The fluorescent intensity decreases with increasing basicity of host glasses. Besides the broadband infrared luminescence, luminescence centered at 640 nm was also observed, which should be ascribed to Bi2+ rather than to the familiar Bi3+. We suggest that the infrared luminescence should be assigned to the X-2 (2)Pi (3/2) -> X-1 (2)Pi(1/2) transition of BiO molecules dispersed in the host glasses. (c) 2006 Elsevier Ltd. All rights reserved.

Effect of PbO on precipitation of laser-induced gold nanoparticles inside silicate glasses

We report on three-dimensional precipitation of Au nanoparticles in gold ions-doped silicate glasses by a femtosecond laser irradiation and further annealing. Experimental results show that PbO addition plays the double roles of inhibiting hole-trapped centers generation and promoting formation and growth of gold nanoparticles. Additionally, glass containing PbO shows an increased non-linear absorption after femtosecond laser irradiation and annealing. The observed phenomena are significant for applications such as fabrications of three-dimensional multi-colored images inside transparent materials and three-dimensional optical memory, and integrated micro-optical switches. (c) 2007 Elsevier B.V. All rights reserved.

Photoluminescence of undoped and B-doped ZnO in silicate glasses

Photoluminescence of undoped and B-doped ZnO in silicate glasses was investigated by varying the concentration of ZnO (3550 mol%) and B dopant (0-10 mol%) in the glass matrices. The broad and intense near band edge emissions were observed while the visible light emission was very weak. UV luminescence in all samples was red-shifted relative to the exciton transition in bulk ZnO and enhanced by decreased ZnO concentration due to higher degree of structural integrity and the lower aggregation degree of ZnO. Donor B dopant played the double roles of filling conduction bands to broaden band gap when its concentration was lower than 5 mol%, and emerging with conduction bands to narrow the gap when B dopant exceeded this value. (c) 2007 Elsevier B.V. All rights reserved.

Luminescence properties of bismuth-doped lime silicate glasses

Luminescences from bismuth-doped lime silicate glasses were investigated. Luminescences centered at about 400, 650, and 1300 nm were observed, excited at 280, 532 and 808 nm, respectively. These three luminescence bands arise from three different kinds of bismuth ions in the glasses. The visible luminescences centered at 400 and 650 nm arise from Bi3+, and Bi2+, respectively. The infrared luminescences cover the wavelength range from 1000 to 1600 nm when exited by an 808 nm laser diode. The full width at half maximum (FWHM) of the infrared luminescences is more than 205 urn. The intensity of the infrared luminescence decreases with the increment in CaO content. We suggest that the infrared luminescences might arise from Bi+. Such broadband luminescences indicate that the glasses may be potential candidate material for broadband fiber amplifiers and tunable lasers. (C) 2007 Elsevier B.V. All rights reserved.