Characterization of lithium borate–bismuth tungstate glasses and glass-ceramics by impedance spectroscopy

Transparent glasses in the system (1−x)Li2B4O7–xBi2WO6 (0≤x≤0.35) were prepared via melt quenching technique. Differential thermal analysis was employed to characterize the as-quenched glasses. Glass-ceramics with high optical transparency were obtained by controlled heat-treatment of the glasses at 720 K for 6 h. The amorphous nature of the as-quenched glass and crystallinity of glass-ceramics were confirmed by X-ray powder diffraction studies. High resolution transmission electron microscopy (HRTEM) shows the presence of nearly spherical nanocrystallites of Bi2WO6 in Li2B4O7 glass matrix. Capacitance and dielectric loss measurements were carried out as a function of temperature (300–870 K) in the frequency range 100 Hz–40 MHz. Impedance spectroscopy employed to rationalize the electrical behavior of glasses and glass-ceramics suggest the coexistence of electronic and ionic conduction in these materials. The thermal activation energies for the electronic conduction and ionic conduction were also estimated based on the Arrhenius plots.

New transparent Er3+-doped oxyfluoride tellurite glass ceramic with improved near infrared and up-conversion fluorescence properties

Transparent glass ceramics have been obtained by nucleation and growth of Y2Te6O15 or Er2Te5O13 cubic phase in a new Er3+-doped oxyfluoride tellurite glass. Effect of beat treatment on absorption spectra, luminescence and up-conversion properties in the oxyfluoride tellurite glass has been investigated. With heat treatment the ultraviolet absorption edge red shifted evidently for the oxyfluoride telluride glass. The near infrared emission that corresponds to Er3+:I-4(13/2)-> I-4(15/2) can be significantly enhanced after heat treatment. Under 980 nm LD pumping, red and green up-conversion intensity of Er3+ in the glass ceramic can be observed much stronger than that in the base glass. (C) 2006 Elsevier B.V. All rights reserved.

Intense blue up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics containing beta-PbF2 nanocrystals

Up-conversion luminescence properties of a Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980nm excitation are investigated. Intense blue emission centered at 476nm, corresponding to (1)G(4) -> H-3(6) transitions of Tm3+ was simultaneously observed in the transparent oxyfluoride glass ceramics at room temperature. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The reason for the intense TM3+ up- conversion luminescence in the oxyfluoride glass-ceramics is discussed. The dependence of up-conversion intensities on excitation power and possible up-conversion mechanism are also evaluated. (c) 2005 Elsevier B.V. All rights reserved.

Multi-color long-lasting phosphorescence in Mn2+-doped ZnO-B2O3-SiO2 glass-ceramics

Multi-color LLP phenomenon was observed in Mn2+-doped ZnO-B2O3-SiO2 glassceramics after the irradiation of a UV lamp at room temperature. Transparent ZnO-B2O3-SiO2 glass emitted reddish LLP while opaque glass-ceramics prepared by the glass sample after heat treatment emitted yellowish or greenish LLP. The change of the phosphorescence is due to the alteration of co-ordination state of Mn2+. The phosphorescence of the samples was seen in the dark with naked eyes even 12 h after the irradiation with a UV lamp (lambda(max) = 254 nm) for 30 min. Based on the approximative t(-1) decay law of the phosphorescence, we suggest that the LLP is attributed to the thermally assisted electron-hole recombination.

Infrared to visible up-conversion emission in Er3+/Yb 3+ codoped fluoro-phosphate glass-ceramics

Erbium Er3+ and ytterbium Yb3+ codoped fluoro-phosphate glasses belonging to the system NaPO3-YF 3-BaF2-CaF2 have been prepared by the classical melt-quenching technique. Glasses containing up to 10 wt% of erbium and ytterbium fluorides have been obtained and characterized using differential scanning calorimetry (DSC) and UV-visible and near-infrared spectroscopy. Transparent and homogeneous glass-ceramics have been then reproducibly synthetized by appropriate heat treatment above glass transition temperature of a selected parent glass. Structural investigations of the crystallization performed through X-ray diffractometry (XRD) and scanning electron microscopy (SEM) have evidenced the formation of fluorite-type cubic crystals based during the devitrification process. Finally, infrared to visible up-conversion emission upon excitation at 975 nm has been studied on the Er3+ and Yb 3+ codoped glass-ceramics as a function of thermal treatment time. A large enhancement of intensity of the up-conversion emissions-about 150 times- has been observed in the glass-ceramics if compared to the parent glass one, suggesting an incorporation of the rare-earth ions (REI) into the crystalline phase. © 2012 The American Ceramic Society.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Low-temperature internal friction of glass ceramics

Low-temperature internal-friction measurements have been used to study the universal low-energy excitations in glasses before and after crystallization in two glass ceramics, one based on MgO-Al2O3-SiO2 (Corning Code 9606) and one based on Li2O-Al2O3-SiO2 (Corning Code 9623). In the Code 9606 sample, the number density of excitations is greatly reduced, while in the Code 9623 sample, their number density remains practically unaltered in the crystallized state. These measurements confirm the conclusions reached by Cahill et al. (preceding paper), which were based on thermal measurements up to room temperature. These measurements also demonstrate the usefulness of internal friction as a tool for the study of these low-energy excitations, since internal friction is less sensitive to defects common to glass ceramics, like magnetic impurities and grain boundaries, which tend to dominate low-temperature specific heat and thermal conductivity, respectively.

Mesoporous bioactive glass and glass-ceramics: Influence of the local structure on in vitro bioactivity

Mesoporous quaternary bioactive glasses and glass-ceramic with alkali-alkaline-earth oxide were successfully synthesized by using non-ionic block copolymer P123 and evaporation induced self assembly (EISA) process followed by acid treatment assisted sal-gel method. As prepared samples has been characterized for the structural, morphological and textural properties with the various analytical techniques. Glass dissolution/ion release rate in simulated body fluid (SBF) was monitored by inductively coupled plasma (ICP) emission spectroscopy, whereas the formation of apatite phase and its crystallization at the glass and glass-ceramic surface was examined by structural, textural and microscopic probes. The influence of alkaline-earth oxide content on the glass structure followed by textural property has become more evident. The pristine glass samples exhibit a wormhole-like mesoporous structure, whereas the glass-ceramic composition is found to be in three different phases, namely crystalline hydroxyapatite, wollastonite and a residual glassy phase as observed in Cerabone (R) A/W. The existence of calcium orthophosphate phase is closely associated with the pore walls comprising nanometric-sized ``inclusions''. The observed high surface area in conjunction with the structural features provides the possible explanation for experimentally observed enhanced bioactivity through the easy access of ions to the fluid. On the other hand, presence of multiple phases in glass-ceramic sample inhibits or delays the kinetics of apatite formation. (C) 2013 Elsevier Inc. All rights reserved.

Frequency and Temperature-Independent Electrical Transport Properties of 2BaO-0.5Na(2)O-2.5Nb(2)O(5)-4.5B(2)O(3) Glass-Ceramics

The temperature (300-973K) and frequency (100Hz-10MHz) response of the dielectric and impedance characteristics of 2BaO-0.5Na(2)O-2.5Nb(2)O(5)-4.5B(2)O(3) glasses and glass nanocrystal composites were studied. The dielectric constant of the glass was found to be almost independent of frequency (100Hz-10MHz) and temperature (300-600K). The temperature coefficient of dielectric constant was 8 +/- 3ppm/K in the 300-600K temperature range. The relaxation and conduction phenomena were rationalized using modulus formalism and universal AC conductivity exponential power law, respectively. The observed relaxation behavior was found to be thermally activated. The complex impedance data were fitted using the least square method. Dispersion of Barium Sodium Niobate (BNN) phase at nanoscale in a glass matrix resulted in the formation of space charge around crystal-glass interface, leading to a high value of effective dielectric constant especially for the samples heat-treated at higher temperatures. The fabricated glass nanocrystal composites exhibited P versus E hysteresis loops at room temperature and the remnant polarization (P-r) increased with the increase in crystallite size.

Biocompatibility property of 100% strontium-substituted SiO2-Al2O3-P2O5-CaO-CaF2 glass ceramics over 26 weeks implantation in rabbit model: Histology and micro-Computed Tomography analysis

One of the desired properties for any new biomaterial composition is its long-term stability in a suitable animal model and such property cannot be appropriately assessed by performing short-term implantation studies. While hydroxyapatite (HA) or bioglass coated metallic biomaterials are being investigated for in vivo biocompatibility properties, such study is not extensively being pursued for bulk glass ceramics. In view of their inherent brittle nature, the implant stability as well as impact of long-term release of metallic ions on bone regeneration have been a major concern. In this perspective, the present article reports the results of the in vivo implantation experiments carried out using 100% strontium (Sr)-substituted glass ceramics with the nominal composition of 4.5 SiO2-3Al(2)O(3)-1.5P(2)O(5)-3SrO-2SrF(2) for 26 weeks in cylindrical bone defects in rabbit model. The combination of histological and micro-computed tomography analysis provided a qualitative and quantitative understanding of the bone regeneration around the glass ceramic implants in comparison to the highly bioactive HA bioglass implants (control). The sequential polychrome labeling of bone during in vivo osseointegration using three fluorochromes followed by fluorescence microscopy observation confirmed homogeneous bone formation around the test implants. The results of the present study unequivocally confirm the long-term implant stability as well as osteoconductive property of 100% Sr-substituted glass ceramics, which is comparable to that of a known bioactive implant, that is, HA-based bioglass. (c) 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 103B: 1168-1179, 2015.

Precipitation of nanocrystals in glasses by electron irradiation: An alternative path to form glass ceramics?

This letter demonstrates an alternative method to form gallium silicate glass ceramics using high-energy electron irradiation. Compared with glass ceramics obtained from the conventional thermal treatment method, the distribution and crystal sizes of the precipitated Ga2O3 nanoparticles are the same. An advantage of this method is that the spatial distribution of the precipitated nanoparticles can be easily controlled. However, optically active dopants Ni2+ ions do not participate in the precipitation during electron irradiation. (c) 2007 American Institute of Physics.

Multicolor upconversion of Er3+/Tm3+/Yb3+ doped oxyfluoride glass ceramics

Er3+/Tm3+/Yb3+ tricloped oxyfluoride glass ceramics was synthesized in a general way. Under 980 nm LD pumping, intense red, green and blue upconversion was obtained. And with those primary colors, multicolor luminescence was observed in oxyfluoride glass ceramics with various dopant concentrations. The red and green upconversion is consistent with F-4(9/2) -> I-4(15/2) and H-2(11/2), S-4(3/2) -> I-4(15/2) transition of Er3+ respectively. While the blue upconversion originates from (1)G(4) -> H-3(6) transition of Tm3+. This is similar to that in Er3+/Yb3+ and/or Tm3+/Yb3+ codoped glass ceramics. However the upconversion of Tm3+ is enhanced by the energy transfer between Er3+ and Tm3+. (c) 2006 Published by Elsevier B.V.

Bismuth-doped zinc aluminosilicate glasses and glass-ceramics with ultra-broadband infrared luminescence

Broadband infrared luminescence covering the optical telecommunication wavelength region of 0, E and S bands was observed from bismuth-doped zinc aluminosilicate glasses and glass-ceramics. The spectroscopic properties of the glasses and glass-ceramics depend on the thermal-treatment history. With the appearance of gahnite (ZnAl2O4) crystalline phase, the fluorescent peak moves to longer wavelength, but the fluorescent intensity decreases. The similar to 1300 nm fluorescence with a FWHM larger than 250 nm and a lifetime longer than 600 mu s possesses these optical materials with potential applications in laser devices and broadband amplifiers. The broad infrared luminescence from the bismuth-doped zinc aluminosilicate glasses and glass-ceramics might be from BiO or bismuth clusters rather than from Bi5+ and Bi3+. (c) 2005 Elsevier B.V. All rights reserved.

Mechanisms and concentrations dependence of up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics

The up-conversion properties of Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980 nm excitation were investigated. Intense blue up-conversion luminescence due to the Tm3+: (1)G(4) -> H-3(6) transition was observed in the glass-ceramics. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The up-conversion mechanism is proposed. The reason for the intense Tm3+ up-conversion luminescence in the oxyfluoride glass-ceramics and the concentrations dependence of upconversion luminescence are also discussed. (c) 2005 Elsevier B.V. All rights reserved.