Crystallization of monoclinic WO3 in tungstate fluorophosphate glasses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Luminescence quenching by iron in barium aluminoborate glasses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Local order around tungsten atoms in tungstate fluorophosphate glasses by X-ray absorption spectroscopy

X-ray absorption spectroscopy was used to study the local environment of tungsten atoms in NaPO3-BaF2,-WO3 glasses and the results were compared with crystalline references Na2WO4 and WO3. XANES measurements at the W-L-1 edge allowed to determine a distorted octahedral environment of tungsten atoms in these glasses similar to the local order of tungsten in monoclinic WO3. Extended X-ray absorption fine structure (EXAFS) has been used as a local probe to monitor the effect of WO3 concentration on the tungsten environment. Based on an analysis of the EXAFS data, we proposed a three-shell model of oxygen atoms around tungsten as in monoclinic WO3. With increasing WO3 concentration, it was found that R-2 decreases from 1.96 to 1.92 angstrom whereas R-3 increases from 2.07 to 2.12 angstrom. (c) 2005 Elsevier B.V. All rights reserved.

CRYSTALLINE FRAGMENTS IN GLASSES

The nature of tetrahedral molecular fragments is investigated in SiSe2 glasses using the molecular-dynamics method. The glass consists of both edge-sharing (ES) and corner-sharing tetrahedra. The ES tetrahedra are the building blocks of chain-like-molecular fragments. The two-edge-sharing tetrahedra are the nucleus, and corner-sharing configurations provide connecting hinges between fragments. Statistics of rings and fragments reveals that threefold and eightfold rings are most abundant, chainlike fragments that are typically 10-15 angstrom long occur mostly in eightfold rings, and the longest fragments occur in elevenfold rings.

Influence of Ga incorporation on photoinduced phenomena in Ge-S based glasses

To study the influence of Ga addition on photoinduced effect, GaGeS glasses with constant atomic ratio S/Ge = 2.6 have been prepared. Using Raman spectroscopy, we have reported the effect of Ga on the structural behavior of these glasses. An increase of the glass transition temperature T(g), the linear refractive index and the density have been observed with increasing gallium content. The photoinduced phenomena have been examined through the influence of time exposure and power density, when exposed to above light bandgap (3.53 eV). The correlation between photoinduced phenomena and Ga content in such glasses are shown hereby. (C) 2009 Elsevier B.V. All rights reserved.

Time-resolved Z-scan and thermal lens measurements in Er+3 and Nd+3 doped fluoroindate glasses

In rare earth ion doped solids, a resonant non-linear refractive index, n2, appears when the laser pumps one of the ion excited states and the refractive index change is proportional to the excited state population. In these solids there are usually thermal and non-thermal lensing effects, where the non-thermal one is due to the polarizability difference, Δα, between excited and ground states of the ions. We have used the time resolved Z-scan and a mode-mismatched thermal lens technique with an Ar+ ion laser in Er+3 (20ZnF2-20SrF2-2NaF-16BaF2-6GaF3-(36 - x)InF3-xErF3, with x= 1, 2, 3 and 4 mol%) and Nd+3 (20SrF2-16BaF2-20ZnF2-2GdF3-2NaF-(40 - x)InF3-xNdF3, with x = 0.1, 0.25, 0.5-1 mol%) doped fluoroindate glasses. In both samples we found that the non-linear refraction is due to the thermal effect, while the non-thermal effect is negligible. This result indicates that in fluoride glasses Δα is very small (less than 10-26 cm3). We also measured the imaginary part of the non-linear refractive index (n″2) due to absorption saturation.

Frequency upconversion in rare-earth doped fluoroindate glasses

We present recent results on frequency upconversion (UPC) obtained in fluoroindate glasses (FIG) doped with Ho3+, Tm3+ and Nd3+ ions and codoped with Pr3+/Nd3+ and Yb3+/Tb3+ ions. The results for the Ho3+-doped samples show strong evidence of energy transfer (ET) between Ho3+ ions resonantly excited at 640 nm. The origin of the blue-green upconverted fluorescence observed was identified and the dynamics of the signals revealed the pathways involved in the UPC process. In the case of Tm3+-doped FIG, the samples were resonantly excited at 650 nm and the main mechanism that contributes for the red-to-blue upconversion is excited-state absorption (ESA). The FIG samples codoped with Pr3+/Nd3+ were excited at 588 nm in resonance with transitions starting from the ground state of the Nd 3+ and the Pr3+ ions. It was observed that the presence of Nd3+ ions enhanced the Pr3+ emission at 480 nm by two orders of magnitude. Multiphonon (MP)-assisted upconversion is also discussed for Nd3+-doped FIG pumped at 866 nm. Emission at 750 nm with a peculiar linear dependence with the laser intensity was observed and explained. A rate-equation model that includes MP absorption via thermally coupled electronic excited states of Nd3+ was developed and describes well the experimental results. The role played by effective phonon modes is clearly demonstrated. MP-assisted UPC process was also studied in Yb3+/ Tb3+-codoped FIG samples excited at 1064 nm, which is off-resonance with electronic transitions starting from the ground state. It was determined that the mechanism leading to Tb3+ emission in the blue is due to ET from a pair of excited Yb3+ ions followed by ESA in the Tb 3+ ions. © 2002 Académie des sciences/Éditions scientifiques et médicales Elsevier SAS.

Quantification of Short and Medium Range Order in Mixed Network Former Glasses of the System GeO2-NaPO3: A Combined NMR and X-ray Photoelectron Spectroscopy Study

Glasses in the system xGeO(2)-(1-x)NaPO3 (0 <= x <= 0.50) were prepared by conventional melting quenching and characterized by thermal analysis, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and P-31 nuclear magnetic resonance (MAS NMR) techniques. The deconvolution of the latter spectra was aided by homonuclear J-resolved and refocused INADEQUATE techniques. The combined analyses of P-31 MAS NMR and O-1s XPS lineshapes, taking charge and mass balance considerations into account, yield the detailed quantitative speciations of the phosphorus, germanium, and oxygen atoms and their respective connectivities. An internally consistent description is possible without invoking the formation of higher-coordinated germanium species in these glasses, in agreement with experimental evidence in the literature. The structure can be regarded, to a first approximation, as a network consisting of P-(2) and P-(3) tetrahedra linked via four-coordinate germanium. As implied by the appearance of P-(3) units, there is a moderate extent of network modifier sharing between phosphate and germanate network formers, as expressed by the formal melt reaction P-(2) + Ge-(4) -> P-(3) + Ge-(3). The equilibrium constant of this reaction is estimated as K = 0.52 +/- 0.11, indicating a preferential attraction of network modifier by the phosphorus component. These conclusions are qualitatively supported by Raman spectroscopy as well as P-31{Na-23} and P-31{Na-23} rotational echo double resonance (REDOR) NMR results. The combined interpretation of O-1s XPS and P-31 MAS NMR spectra shows further that there are clear deviations from a random connectivity scenario: heteroatomic P-O-Ge linkages are favored over homoatomic P-O-P and Ge-O-Ge linkages.

Near-infrared quantum cutting through a three-step energy transfer process in Nd3+-Yb3+ co-doped fluoroindogallate glasses

The Nd3+-Yb3+ couple was investigated in fluoroindogallate glasses using optical spectroscopy to elucidate the energy transfer mechanisms involved in the downconversion (DC) process. Upon excitation of a Nd3+ ion by an ultraviolet photon, DC through a three-step energy transfer process occurs, in which the energy of the ultraviolet photon absorbed by the Nd3+ ion is converted into three infrared photons emitted by Yb3+ ions, i.e. quantum cutting (QC). In addition, with excitation in the visible, our results confirm that the DC process occurs through a one-step energy transfer process, in which the energy of a visible photon absorbed by the Nd3+ ion is converted into only one infrared photon emitted by an Yb3+ ion. Time-resolved measurements enabled the estimation of the efficiencies of the cross-relaxation processes between Nd3+ and Yb3+ ions.

Linking origin of the electric field-assisted beta-PbF2 crystallization in lead oxyfluoroborate glasses below T (g) to simultaneous cathode/anode-compensated electrochemical reactions

Full validation of the electrochemical mechanisms so far postulated as driving force of electric field-assisted non-spontaneous crystallization development in given glasses has suffered experimental restrictions. In this work, we looked into origin of this phenomenon in lead oxyfluoroborate glasses, resulting in beta-PbF2 growth even below the corresponding glass transition temperatures, through achieving a systematic study of not only Pt,Ag/Glass/Ag,Pt- but also Pt,Ag/Glass/YSZ:PbF2/Ag,Pt-type cells, where YSZ:PbF2 represents a two-phase system (formed by Y2O3-doped ZrO2 and PbF2). It is demonstrated that crystallization induction in these glasses involves Pb2+ ions reduction at the cathode, the phenomenon being, however, confirmed only when the F- ions were simultaneously also able to reach the anode for oxidation, after assuring either a direct glass-anode contact or percolation pathways for free fluoride migration across the YSZ:PbF2 mixtures. A further support of this account is that the electrochemically induced beta-PbF2 phase crystallizes showing ramified-like microstructure morphology that arises, accordingly, from development of electroconvective diffusion processes under electric field action.

Influence of Water Content and Temperature on Molecular Mobility and Intracellular Glasses in Seeds and Pollen1

Although the occurrence of intracellular glasses in seeds and pollen has been established, physical properties such as rotational correlation times and viscosity have not been studied extensively. Using electron paramagnetic resonance spectroscopy, we examined changes in the molecular mobility of the hydrophilic nitroxide spin probe 3-carboxy-proxyl during melting of intracellular glasses in axes of pea (Pisum sativum L.) seeds and cattail (Typha latifolia L.) pollen. The rotational correlation time of the spin probe in intracellular glasses of both organisms was approximately 10−3 s. Using the distance between the outer extrema of the electron paramagnetic resonance spectrum (2Azz) as a measure of molecular mobility, we found a sharp increase in mobility at a definite temperature during heating. This temperature increased with decreasing water content of the samples. Differential scanning calorimetry data on these samples indicated that this sharp increase corresponded to melting of the glassy matrix. Molecular mobility was found to be inversely correlated with storage stability. With decreasing water content, the molecular mobility reached a minimum, and increased again at very low water content. Minimum mobility and maximum storage stability occurred at a similar water content. This correlation suggests that storage stability might be at least partially controlled by molecular mobility. At low temperatures, when storage longevity cannot be determined on a realistic time scale, 2Azz measurements can provide an estimate of the optimum storage conditions.

(Table 1) Rare earth element contents in basalts and glasses of DSDP Legs 45 and 51

Rare-earth element (REE) distributions in altered basalts and glasses collected during some Legs of the Deep Sea Drilling Project show that a fractionation of these elements occurs during submarine weathering. When the alteration is well-marked, the REE distribution in altered glasses shows an enrichment in light rare-earths relative to the fresh glass. In particular, Ce is selectively enriched in palagonitized glasses that comprise, besides polymetallic nodules, another phase liable to explain the Ce depletion in seawater. Taking in account these processes of submarine weathering of the oceanic crust, a geochemical balance of Ce between authigenic phases of the marine environment is attempted.

Uranium glass in museum collections

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Conservação e Restauro Área de especialização – Vidro

Glassiness in a model without energy barriers

We propose a microscopic model without energy barriers in order to explain some generic features observed in structural glasses. The statics can be exactly solved while the dynamics has been clarified using Monte Carlo calculations. Although the model has no thermodynamic transition, it captures some of the essential features of real glasses, i.e., extremely slow relaxation, time dependent hysteresis effects, anomalous increase of the relaxation time, and aging. This suggests that the effect of entropy barriers can be an important ingredient to account for the behavior observed in real glasses.

Hydrogen and oxygen isotope behaviors during variable degrees of upper mantle melting: Example from the basaltic glasses from Macquarie Island

We present measurements of hydrogen and oxygen isotopes in MORB glasses from Macquarie Island (SW. Pacific Ocean) coupled with determination of bulk H2O content by two independent techniques: total dehydration and FTIR. The incompatible trace elements in these glasses vary by a factor of 12 to 17, with K2O varying from 0.1 to 1.7 wt.%; these ranges reflect a variable degree of closed-system mantle melting, estimated from 1 to 15%. Water concentrations determined by the two techniques match well, yielding a range from 0.25 to 1.49 wt.% which correlates positively with all of the measured incompatible trace elements, suggesting that water is un-degassed, and behaves conservatively during mantle melting. Also, the agreement between the FTIR-determined and extracted water contents gives us confidence that the measured isotopic values of hydrogen reflect that of the mantle. Comparison of the range of water content with that of other incompatible trace elements allows estimation of the water partition coefficient in lherzolite, 0.0208 (ranging from 0.017 to 0.023), and the water content in the source, 386 ppm (ranging from 370 to 440 ppm). We observe a fairly narrow range in delta D and delta O-18 values of -75.5 +/- 4.5 parts per thousand and 5.50 +/- 0 .05 parts per thousand respectively, that can be explained by partial melting of normal lherzolitic mantle. The measured delta D and delta O-18 values of Macquarie Island glasses that range from nepheline- to hypersthene-normative, and from MORB to EMORB in composition, are identical to those in average global MORB. The observed lack of variation of delta D and delta O-18 with 1 to 15% degree of mantle melting is consistent with a bulk melting model of delta D and delta O-18 fractionation, in which water is rapidly scavenged into the first partial melt. The narrow ranges of delta D and delta O-18 in normal mantle are mostly due to the buffering effect of clino- and orthopyroxenes in the residual assemblage; additionally, fast ``wet'' diffusion of oxygen and hydrogen isotopes through the melting regions may further smooth isotopic differences. (C) 2012 Elsevier B.V. All rights reserved.