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.

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 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.

Spectroscopic investigations of OH- influence on near-infrared fluorescence quenching of Yb3+/Tm3+ co-doped sodium-metaphosphate glasses

Energy transfer processes were studied in two sets of Yb3+ and Tm3+ co-doped sodium-metaphosphate glasses, prepared in air and nitrogen atmospheres. Using Forster, Dexter, and Miyakawa theoretical models, the energy transfer parameters were calculated. The main ion-ion energy transfer processes analyzed were energy migration among Yb3+ ions, cross-relaxations between Yb3+ and Tm3+ ions, and interactions with OH- radicals. The results indicated that Yb -> Tm energy transfer favors 1.8 mu m emissions, and there is no evidence of concentration quenching up to 2% Tm2O3 doping. As expected, samples prepared in nitrogen atmosphere present higher fluorescence quantum efficiency than those prepared in air, and this feature is specially noted in the near-infrared region, where the interaction with the OH- radicals is more pronounced. (c) 2007 Published by Elsevier B.V.

Erbium and Ytterbium Codoped Titanoniobophosphate Glasses for Ion-Exchange-Based Planar Waveguides

This work presents the optical properties of erbium-doped and erbium/ytterbium codoped Na(2)O-Al(2)O(3)-TiO(2)-Nb(2)O(5)-P(2)O(5) glass systems and also the characterization of planar waveguides obtained by typical thermally assisted Ag+<-> Na+ ion-exchange process. The glass systems allow the preparation of single mode and multimode planar waveguides presenting a strong and relatively broad emission at 1536 nm. The emission signal in the infrared region is intensified for silver-containing samples when compared with free-silver samples. The emission signal intensification may be attributed to a nonplasmonic energy transfer from silver species to Er3+ ions as no bands related to surface plasmon resonance (SPR) of silver nanoparticles were observed.

Fluorescent AlPO(4) gels and glasses doped with Rhodamine 6G: Preparation, structural and optical characterization

Fluorescent AlPO(4) xerogels doped with different amounts of Rhodamine 6G (Rh6G) laser dye were prepared by a one-step sal-gel process. In addition, mesoporous AlPO(4) glasses obtained from undoped gels were loaded with different amounts of Rh6G by wet impregnation. Optical excitation and emission spectra of both series of samples show significant dependences on Rh6G concentration, revealing the influence of dye molecular aggregation. At comparable dye concentrations the aggregation effects are found to be significantly stronger in the gels than in the mesoporous glasses. This effect might be attributed to stronger interactions between the dye molecules and the glass matrix, resulting in more efficient dye dispersion in the latter. The interaction of Rh6G with the glassy AlPO(4) network has been probed by (27)Al and (31)P solid-state NMR techniques. New five- and six-coordinated aluminum environments have been observed and characterized by advanced solid-state NMR techniques probing (27)Al-(1)H and (27)Al-(31)P internuclear dipole couplings. The fractional area of these new Al sites is correlated with the combined fractional area of two new Q(3Al)((0)) and Q(2Al)((0)) phosphate species observed in the (31)P MAS NMR spectra. Based on this correlation as well as detailed composition dependent studies, we suggest that the new signals arise from the breakage of Al-O-P linkages associated with the insertion process. (C) 2010 Elsevier B.V. All rights reserved.

Study on the observation of Eu(2+) and Eu(3+) valence states in low silica calcium aluminosilicate glasses

The optical, magnetic and structural properties of Eu doped low silica calcium aluminosilicate glasses were investigated. The optical absorption coefficient presented two bands at 39 246 and 29 416 cm(-1), which were assigned respectively to the 4f(7) ((8)S(7/2)) -> 4f(6) (4F(J)) 5d (T(2g)), and 4f(7) ((8)S(7/2)) -> 4f(6) (4F(J)) 5d (E(g)) transitions of Eu(2+). The fluorescence measured at 300 K on a sample doped with 0.5 wt% of Eu(2)O(3) exhibited a broad band centered at 17 350 cm(-1), which is attributed to the 4f(6)5d -> 4f(7) transition of Eu(2+), whereas the additional peaks are due to the (5)D(0) -> (7)F(J) (J = 1, 2, 4) transitions of Eu(3+). From magnetization and XANES data it was possible to evaluate the fractions of Eu(2+) and Eu(3+) for the sample doped with 0.5 and 5.0 wt% of Eu(2)O(3), the values of which were approximately 30 and 70%, respectively.

Lead and aluminum bonding in Pb-Al metaphosphate glasses

The bonding properties of cations in phosphate glasses determine many short- and medium-range structural features in the glass network, hence influencing bulk properties. In this work, Pb-Al-metaphosphate glasses (1 - x)Pb-(PO(3))(2)center dot xAI(PO(3))(3) with 0 <= - x <= 1 were analyzed to determine the effect of the substitution of Pb by Al on the glass structure in the metaphosphate composition. The glass transition temperature and density were measured as a function of the Al concentration. The vibrational and structural properties were probed by Raman spectroscopy and nuclear magnetic resonance of (31)P, (27)Al, and (207)Pb. Aluminum incorporates homogeneously in the glass creating a stiffer and less packed network. The average coordination number for Al decreases from 5.9 to 5.0 as x increases from 0.1 to 1, indicating more covalent Al-O bonds. The coordination number of Pb in these glasses is greater than 8, showing an increasing ionic behavior for compositions richer in Al. A quantitative analysis of the phosphate speciation shows definite trends in the bonding of AlO(n) groups and phosphate tetrahedra. In glasses with x < 0.48, phosphate groups share preferentially only one nonbridging O corner with an AlO(n) coordination polyhedron. For x > 0.48 more than one nonbridging O can be linked to AlO(n) polyhedra. There is no corner sharing of O between AlO(n) and PbO(n) polyhedra nor between AlO(n) themselves throughout the compositional range. The PbO(n) coordination polyhedra show considerable nonbridging O sharing, with each O participating in the coordination sphere of at least two Pb. The bonding preferences determined for Al are consistent with the behavior observed in Na-Al and Ca-Al metaphosphates, indicating this may be a general behavior for ternary phosphate glasses.

An Information Theory framework for two-stage binary image operator design

The design of translation invariant and locally defined binary image operators over large windows is made difficult by decreased statistical precision and increased training time. We present a complete framework for the application of stacked design, a recently proposed technique to create two-stage operators that circumvents that difficulty. We propose a novel algorithm, based on Information Theory, to find groups of pixels that should be used together to predict the Output Value. We employ this algorithm to automate the process of creating a set of first-level operators that are later combined in a global operator. We also propose a principled way to guide this combination, by using feature selection and model comparison. Experimental results Show that the proposed framework leads to better results than single stage design. (C) 2009 Elsevier B.V. All rights reserved.

Multilevel Training of Binary Morphological Operators

The design of binary morphological operators that are translation-invariant and locally defined by a finite neighborhood window corresponds to the problem of designing Boolean functions. As in any supervised classification problem, morphological operators designed from a training sample also suffer from overfitting. Large neighborhood tends to lead to performance degradation of the designed operator. This work proposes a multilevel design approach to deal with the issue of designing large neighborhood-based operators. The main idea is inspired by stacked generalization (a multilevel classifier design approach) and consists of, at each training level, combining the outcomes of the previous level operators. The final operator is a multilevel operator that ultimately depends on a larger neighborhood than of the individual operators that have been combined. Experimental results show that two-level operators obtained by combining operators designed on subwindows of a large window consistently outperform the single-level operators designed on the full window. They also show that iterating two-level operators is an effective multilevel approach to obtain better results.

Perfect Simulation of a Coupling Achieving the (d)over-bar-distance Between Ordered Pairs of Binary Chains of Infinite Order

We explicitly construct a stationary coupling attaining Ornstein`s (d) over bar -distance between ordered pairs of binary chains of infinite order. Our main tool is a representation of the transition probabilities of the coupled bivariate chain of infinite order as a countable mixture of Markov transition probabilities of increasing order. Under suitable conditions on the loss of memory of the chains, this representation implies that the coupled chain can be represented as a concatenation of i.i.d. sequences of bivariate finite random strings of symbols. The perfect simulation algorithm is based on the fact that we can identify the first regeneration point to the left of the origin almost surely.

Framework for Skew-Probit Links in Binary Regression

We review several asymmetrical links for binary regression models and present a unified approach for two skew-probit links proposed in the literature. Moreover, under skew-probit link, conditions for the existence of the ML estimators and the posterior distribution under improper priors are established. The framework proposed here considers two sets of latent variables which are helpful to implement the Bayesian MCMC approach. A simulation study to criteria for models comparison is conducted and two applications are made. Using different Bayesian criteria we show that, for these data sets, the skew-probit links are better than alternative links proposed in the literature.

Automorphism Groups of Generalized (Binary) Icosahedral, Tetrahedral and Octahedral Groups

Let G be any of the (binary) icosahedral, generalized octahedral (tetrahedral) groups or their quotients by the center. We calculate the automorphism group Aut(G).

ON SPECIALITY OF BINARY-LIE ALGEBRAS

In the present work, binary-Lie, assocyclic, and binary (-1,1) algebras are studied. We prove that, for every assocyclic algebra A, the algebra A(-) is binary-Lie. We find a simple non-Malcev binary-Lie superalgebra T that cannot be embedded in A(-s) for an assocyclic superalgebra A. We use the Grassmann envelope of T to prove the similar result for algebras. This solve negatively a problem by Filippov (see [1, Problem 2.108]). Finally, we prove that the superalgebra T is isomorphic to the commutator superalgebra A(-s) for a simple binary (-1,1) superalgebra A.