Evidence of fluoride oxidation for development of the electrochemically-induced crystallization observed in lead oxyfluoroborate glasses

This work reports on a distinct experimental procedure conceived to closely approach the question of development of crystallization in lead oxyfluoroborate glasses in the presence of an electric field. After proposing earlier that this phenomenon should involve occurrence of redox-type electrochemical reactions occurring at the electrodes. it was in fact recently shown that a direct contact of the glasses with both the cathode and anode revealed essential, provided that crystallization did not develop when ions migration to these electrodes became frustrated. The present study demonstrates that. even in Pt,Ag/Glass/YSZ:PbF(2)/Ag,Pt-type electrochemical cells subjected to electric field action, where YSZ:PbF(2) represents composite-like mixtures (formed by Y(2)O(3)-doped ZrO(2) and PbF(2)) placed between the glass and anode. crystallization was observable in given cases. In summary, supported by (micro)structural and electrical characterizations, clear evidence is provided here that, besides Pb(2+) reduction at the cathode, crystallization really involves simultaneous F(-) oxidation at the anode, completing thus the whole redox electrochemical reaction so far postulated. In these cases, F(-) migration to the anode was achievable following PbF(2) percolative-like paths through the YSZ:PbF(2) mixtures. (C) 2010 Elsevier B.V. All rights reserved.

Structural role of fluoride in the ion-conducting glass system B(2)O(3)-PbO-LiF studied by single- and double-resonance NMR

The local structure of an ion-conducting glass with nominal composition 50B(2)O(3)-10PbO-40LiF has been investigated by complementary (7)Li, (11)B, (19)F, and (207)Pb single- and double-resonance experiments. The results give insight into the structural role of the lithium fluoride additive in borate glasses: (1) LiF is seen to actively participate in the network transformation process contributing to the conversion of three- into four-coordinate boron units, as shown by (11)B single-resonance as well as by (11)B{(19)F} and (19)F{(11)B} double-resonance experiments. (2) (19)F signal quantification experiments suggest substantial fluoride loss, presumably caused by formation of volatile BF(3). A part of the fluoride remains in the dopant role, possibly in the form of small LiF-like cluster domains, which serve as a mobile ion supply. (3) The extent of lithium-fluorine and lead-fluorine interactions has been characterized by (7)Li{(19)F} and (207)Pb{(19)F} REDOR and SEDOR experiments. On the basis of these results, a quantitative structural description of this system has been developed.

Investigation of some dielectric properties of phosphate glasses doped with iron oxides, by a microwave technique

The effects of iron ions on dielectric properties of lithium sodium phosphate glasses were studied by non-usual, fast and non-destructive microwave techniques. The dielectric constant (epsilon`). insertion loss (L) and microwave absorption spectra (microwave response) of the selected glass system xFe(2)O(3)center dot(1 - x)(50P(2)O5 center dot 25Li(2)O center dot 25Na(2)O), being x = 0, 3, 6, ....,15 expressed in mol.%, were investigated. The dielectric constant of the samples was investigated at 9.00 GHz using the shorted-line method (SLM) giving the minimum value of epsilon` = 2.10 +/- 0.02 at room temperature, and increasing further with x, following a given law. It was observed a gradual increasing slope Of E in the temperature range of 25 <= t <= 330 degrees C, at the frequency of 9.00 GHz. Insertion loss (measured at 9.00 GHz) and measurements of microwave energy attenuation, at frequencies ranging from 8.00 to 12.00 GHz were also studied as a function of iron content in the glass samples. (C) 2009 Elsevier Ltd. All rights reserved.

An alternative method to study the cooling of glasses from melt to solid phase

The aim of this preliminary work was to present a novel method, suitable to investigate the glass cooling, from melt to solid state, based on a fast, non-usual and easy microwave method. The following glass system xBaO . (100-x)B(2)O(3) (x = 0% and 40%) was selected as an example for this study. The melt was poured inside a piece of waveguide and then, its cooling was monitored by the microwave signal as a function of time. The variations in the signal can provide valuable informations about some structural changes that take place during the cooling stages, such as relaxation processes. This method can be useful to investigate the cooling and heating of other materials, opening new possibilities for investigation of dielectric behavior of materials under high temperatures. (C) 2008 Elsevier Inc. All rights reserved.

Dielectric properties and physical features of phosphate glasses containing iron oxide

Microwave techniques were applied to the study of dielectric properties of phosphate glasses on the basis of contributions from permanent and induced dipolar polarization of local structural units interacting with the electrical component of the electromagnetic radiation. The dielectric constant of the selected glass system (100-x)(50P(2)O(5)center dot 25Li(2)O center dot 25Na(2)O)center dot xFe(2)O(3), where 0 <= x <= 21 is in mol%, was measured using a microwave setup assembled to measure the phase shift of the standing wave pattern produced by the insertion of the sample. It is shown that the Fe2+ ions contribute effectively to the dielectric constant, as expected from the interactions of the dipoles of the local charge compensation pairs with the microwave radiation. However, there is the possibility of occurrence of some ions Fe3+, in general, at low iron content, which reinforces the glass structure and, therefore, decreases the dielectric constant. There is a gradual conversion from Fe3+ to Fe2+ as the iron ions increases. This is possibly the reason of the anomaly in the dielectric constant values observed in the results. These assumptions can be checked by results of electronic paramagnetic resonance (EPR) and optical absorption (OA). The dielectric constant of the glasses studied in this work was found to increase with the temperature in the range of 25-330 degrees C. (C) 2007 Elsevier B.V. All rights reserved.

EPR of gamma-induced paramagnetic centers in tellurite glasses

Intrinsic paramagnetic responses were observed in the 60TeO(2)-25ZnO-15Na(2)O and 85TeO(2)-15Na(2)O mol% glasses, after gamma-irradiation at room temperature: (1) a shoulder at g(1) = g(parallel to) = 2.02 +/- 0.01 and an estimated g(perpendicular to)similar to 2.0 attributed to tellurium-oxygen hole center (TeOHC); (2) a narrow resonance at g(2)= 1.9960 +/- 0.0005 related to the modifiers and (3) a resolved resonance at g(3) = 1.9700 +/- 0.0005 ascribed to a tellurium electron center (TeEC) of an electron trapped at an oxygen vacancy (V(o)(+)) in a tellurium oxide structural center. It is suggested that the creation of (NBO(-),V(o)(+)) pair follows a mechanism where the modifier oxide molecule actuates as a catalyser. An additional model for the NBO radiolysis produced by the gamma-irradiation is proposed on the basis of the evolution of the g(1), g(2) and g(3) intensities with increasing dose (kGy). Crown Copyright (C) 2010 Published by Elsevier B.V. All rights reserved.

Electronic properties of liquid hydrogen fluoride: A sequential quantum mechanical/Born-Oppenheimer molecular dynamics approach

The electronic properties of liquid hydrogen fluoride (HF) were investigated by carrying out sequential quantum mechanics/Born-Oppenheimer molecular dynamics. The structure of the liquid is in good agreement with recent experimental information. Emphasis was placed on the analysis of polarisation effects, dynamic polarisability and electronic excitations in liquid HF. Our results indicate an increase in liquid phase of the dipole moment (similar to 0.5 D) and isotropic polarisability (5%) relative to their gas-phase values. Our best estimate for the first vertical excitation energy in liquid HF indicates a blue-shift of 0.4 +/- 0.2 eV relative to that of the gas-phase monomer (10.4 eV). (C) 2010 Elsevier B.V. All rights reserved.

A model for the stabilization of atomic hydrogen centers in borate glasses

A previously proposed model describing the trapping site of the interstitial atomic hydrogen in borate glasses is analyzed. In this model the atomic hydrogen is stabilized at the centers of oxygen polygons belonging to B-O ring structures in the glass network by van der Waals forces. The previously reported atomic hydrogen isothermal decay experimental data are discussed in the light of this microscopic model. A coupled differential equation system of the observed decay kinetics was solved numerically using the Runge Kutta method. The experimental untrapping activation energy of 0.7 x 10(-19) J is in good agreement with the calculated results of dispersion interaction between the stabilized atomic hydrogen and the neighboring oxygen atoms at the vertices of hexagonal ring structures. (C) 2009 Elsevier B.V. All rights reserved.

Study of the gamma radiation response of watch glasses

Some dosimetric properties of watch glasses were studied applying the thermoluminescence technique. The watch glass samples were powdered, and the selected grains were mixed with Teflon (TM). The mixture was pressed and sintered to produce pellets of watch glass-Teflon (TM) composites. The glow curves of the pellets show two peaks at 130 and 195 degrees C. Reproducibility of TL response was estimated to have a maximum coefficient of variation of 4.0%. The dose-response curve is sublinear between 0.5 and 20.0kGy. The calibration curve is linear between 1.0Gy and 1.0kGy. The minimum detection limits were also determined. The gamma radiation dose response and the thermal stability of the materials were studied with the purpose to establish the best conditions of watch glasses for use in gamma radiation dosimetry. (C) 2007 Elsevier Ltd. All rights reserved.

Thermoluminescent and optical absorption properties of neodymium doped yttrium aluminoborate and yttrium calcium borate glasses

Neodymium doped yttrium aluminoborate and yttrium calcium borate glasses were prepared by the conventional melting-quenching technique with neodymium concentration varying from 0.10 to 1.0 mol%. The obtained glasses present a wide transparency in the UV-visible region (till 240 nm). The thermoluminescent (TL) emission of beta-irradiated samples was measured, showing a broad peak at similar to 240 degrees C with intensities related to the Nd(3+) content, for both glasses. Calcium borate glass samples are about one order of magnitude less luminescent than the aluminoborate glasses. Probably the presence of Ca(2+), instead of Al(3+) and Y(3+) in the matrix, inhibits the production of the intrinsic hole centers. connected to boron and oxygen, known in the literature to act as luminescent centers in TL emission of borate glasses. We suggest that Nd(3+) ions act as electron trapping centers in both glass matrices, as they modify the temperature of emission and the light intensity. Also, the Nd:YAIB glass can be used as a dosimeter in various applications, including radiotherapy. but the sensitivity of this material to neutron should be checked. (C) 2008 Elsevier B.V. All rights reserved.

Is the electrochemically-induced crystallization in lead oxifluoroborate glasses indeed an electrode- or/and an electric field-promoted phenomenon?

While evidence of ion reduction at the cathode has been given, proof of anode activity, in order to account completely for the redox-type electrochemical mechanism so far postulated to originate the electric field-induced non-spontaneous crystallization observed in glasses, is still lacking. This study demonstrates that direct contact of both cathode and anode electrodes with the material is mandatory to promote crystal nucleation. The electrochemical process of concern is established here to involve a solid-state process, electrolytic in nature. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Thermoluminescence, structural and magnetic properties of a Li(2)O-B(2)O(3)-Al(2)O(3) glass system doped with LiF and TiO(2)

A Li(2)O-B(2)O(3)-Al(2)O(3) glass system, un-doped and doped with LiF, and/or TiO(2) was synthesized by the fusion method and its physical properties were investigated by thermoluminescence (TL), X-ray diffraction (XRD), electron paramagnetic resonance (EPR), atomic force microscopy (AFM) and differential thermal analysis (DTA). The samples were subjected to gamma-rays from a colbalt-60 ((60)Co) source. These techniques provided evidence of LiF and LiF doped with Ti crystal formation in the glass system. A TL glow peak at about 433 K was sensitive to (60)Co gamma-rays and showed good linearity with doses and consequently could be used to quantify radiation doses. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Influence of ceria addition on thermal properties and local structure of bismuth germanate glasses

Bismuth germanate glasses are interesting materials due to their physical properties and their unique structural characteristics caused by the coordination changes of bismuth and germanium atoms. Glasses of the bismuth germanate system were prepared by melting/molding method and were investigated concerning their thermal and structural properties. The structural analysis of the samples was carried out by micro-Raman and Fourier transform infrared spectroscopes. It was observed that the glass structure is formed basically by GeO(4) tetrahedral units also having the formation of the GeO(6) octahedral units. BiO(2) was considered a network former by observing the presence of octahedral BiO(6) and pyramidal BiO(3) groups in the local structure of the samples. An absorption band observed at 1103 cm(-1) in the IR spectrum of the undoped glass was attributed to the Bi-O-Ge and/or Bi-O-Bi linkage vibration. The said band shifted to lower wavenumbers after the CeO(2) addition thus reflecting changes in the glass network. Cerium oxide was an efficient oxidant agent to prevent the darkening of the glasses which was probably associated to the reduction of Bi ions. However, CeO(2) was incorporated as a local network modifier in the glass structure even at concentrations of 0.2 mol%. (C) 2010 Elsevier B.V. All rights reserved.

Structural Characterization of Rare-Earth Doped Yttrium Aluminoborate Laser Glasses Using Solid State NMR

The structure of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-x)(Y(2)O(3))(x)} (0.1 <= x <= 0.25) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as Y-3d core-level X-ray photoelectron spectroscopy, (11)B magic-angle spinning (MAS) NMR spectra reveal that the majority of the boron atoms are three-coordinated, and a slight increase of four-coordinated boron content with increasing x can be noticed. (27)Al MAS NMR spectra show that the alumina species are present in the coordination states four, five and six. All of them are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, nonsegregated glass structure. For the first time, (89)Y solid state NMR has been used to probe the local environment of Y(3+) ions in a glass-forming system. The intrinsic sensitivity problem associated with (89)Y NMR has been overcome by combining the benefits of paramagnetic doping with those of signal accumulation via Carr-Purcell spin echo trains. Both the (89)Y chemical shifts and the Y-3d core level binding energies are found to be rather sensitive to the yttrium bonding state and reveal that the bonding properties of the yttrium atoms in these glasses are similar to those found in the model compounds YBO(3) and YAl(3)(BO(3))(4), Based on charge balance considerations as well as (11)B NMR line shape analyses, the dominant borate species are concluded to be meta- and pyroborate anions.

Energy transfer processes in Yb(3+)-Tm(3+) co-doped sodium alumino-phosphate glasses with improved 1.8 mu m emission

Sodium alumino-phosphate glasses co-doped with Yb(3+) and Tm(3+) ions have been prepared with notably low OH(-) content, and characterized from the viewpoint of their spectroscopic properties. In these glasses, Yb(3+) acts as an efficient sensitizer of excitation energy at 0.98 mu m - which can be provided by high power and low cost diode lasers, and subsequently undergoes non-resonant energy transfer to Tm(3+) ions ((2)F(5/2), (3)H(6) --> (2)F(7/2), (3)H(5)). Through this process, the emitting level (3)F(4) is rapidly populated, generating improved emission at 1.8 mu m ((3)F(4) --> (3)H(6)). In order to guarantee the efficiency of such favorable energy transfer, energy losses via multiphonon decay, Yb-Yb radiative trapping, and non- radiative transfer to OH(-) groups were evaluated, and minimized when possible. The dipole - dipole energy transfer microscopic parameters corresponding to Yb(3+) --> Tm(3+), Yb(3+) --> Yb(3+) and Tm(3+) --> Tm(3+) transfers, calculated by the Forster-Dexter model, are C(Yb-Tm) = 2.9 x 10(-40) cm(6) s(-1), C(Yb-Yb) = 42 x 10(-40) cm(6) s(-1) and C(Tm-Tm) = 43 x 10(-40) cm(6) s(-1), respectively.