X-ray reflectivity of zirconia based sol-gel coatings on borosilicate glasses

In this work the technique of X-ray reflectometry was applied to study zirconiumsulfate films deposited by sol-gel dip-coating process on a borosilicate glass surface. The influence of withdrawal speed and temperature of thermal treatment on the film structure are analyzed. The thermal evolution of the density and thickness of the film was compared with these properties measured for a monolithic xerogel by helium picnometry and thermomechanical analysis. The fitting of experimental curves by classical reflectivity model showed the presence of an additional layer at the top surface of the coating. Layer thickness increases with increase of withdrawal speed in agreement with the Landau-Levich model. The apparent and real densities are similar for coatings fired below 400 degrees C, which shows that the films are free of pores. The shrinkage during firing is anisotropic, occurring essentially perpendicular to the coating surface. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Structural studies on TeO2-PbO glasses

Binary tellurite-based glasses in the TeO2-PbO system were prepared and its structure investigated by means of Raman Scattering and X-ray Absorption Spectroscopy. Both spectroscopies indicate strong modifications of the first coordination shell around tellurium atoms when the PbO content increases revealing for lead its glassy network modifier role. Also, Pb L-3-edge EXAFS measurements reveal this structural role played by lead atoms, but the presence of a medium range order contribution indicates that lead also participates to the glassy network formation. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Spectroscopic properties of lead fluoroborate glasses doped with ytterbium

A new lead fluoroborate glass (PbO-PbF2-B2O3) doped with ytterbium (Yb:PbFB) is presented. Samples with different concentrations of Yb3+ were produced and had their emission cross-sections, fluorescence lifetimes and minimum pump intensities determined. They have high refractive index of 2.2 and a density of 4.4 g/cm(3). For a doping level of 1.153x10(20) ions/cm(3), the fluorescence lifetime, after excitation at 968 nm, is 0.81 ms, which is comparable to Yb:tellurite laser glass. Also, an emission band at 1022 nm is measured with emission cross-section of approximately 1.07x10(-20) cm(2) and fluorescence effective linewidth of 60 nm, which is comparable to Yb:phosphate laser glass. (C) 2001 Optical Society of America.

Dynamics of Tm-Ho energy transfer and deactivation of the F-3(4) low level of thulium in fluorozirconate glasses

The mechanism involved in the Tm3+ (F-3(4))-->Ho3+ (I-5(7)) energy transfer and Tm3+ (H-3(4), H-3(6))-->Tm3+ (F-3(4), F-3(4)) cross relaxation as a function of the donor and acceptor concentrations was investigated in Tm-Ho-codoped fluorozirconate glasses. The experimental transfer rates were determined for the Tm-->Ho energy transfer from the best fit of the acceptor luminescence decay using an expression which takes into account the Inokuti-Hirayama model and localized donor-to-acceptor interaction solution. The original acceptor solution derived from the Inokuti-Hirayama model fits well the acceptor luminescence transient only for low-concentrated systems. The results showed that a fast excitation diffusion that occurs in a very short time (t<Tm cross relaxation and Tm-->Ho energy transfer ions from H-3(4) and F-3(4) thulium states, respectively. (C) 2004 American Institute of Physics.

1.5 mu m emission and infrared-to-visible frequency upconversion in Er+3/Yb+3-doped phosphoniobate glasses

Sodium phosphoniobate glasses with the composition (mol%) 75NaPO(3)-25Nb(2)O(5) and containing 2 mol% Yb3+ and x mol% Er3+ (0.01 <= x <= 2) were prepared using the conventional melting/casting process. Er3+ emission at 1.5 mu m and infrared-to-visible upconversion emission, upon excitation at 976 nm, are evaluated as a function of the Er3+ concentration. For the lowest Er3+ content, 1.5 mu m emission quantum efficiency was 90%. Increasing the Er3+ concentration up to 2 mol%, the emission quantum efficiency was observed to decrease to 37% due to concentration quenching. The green and red upconversion emission intensity ratio was studied as a function of Yb3+ co-doping and the Er3+-Er3+ energy transfer processes. (c) 2006 Elsevier B.V. All rights reserved.

Evaluation of glass ionomer cements properties obtained from niobium silicate glasses prepared by chemical process

Glass ionomer cements (GICs) are glass and polymer composite materials. These materials currently find use in the dental field. The purpose of this work is to obtain systems based on composition 4.5SiO(2)-3Al(2)O(3)-XNb2O5-2CaO to be used in Dentistry. The systems were prepared by chemical route at 700 degrees C. The results obtained by XRD and DTA showed that all systems prepared are glasses. The structures of the obtained glasses were compared to commercial material using Al-27 and Si-29 MAS NMR. The analysis of MAS NMR spectra indicated that the systems developed and commercial material are formed by SiO4 and AlO4 linked tetrahedra. The properties of glass ionomer cements based on the glasses prepared with several niobium contents were studied. Setting and working times of the cement pastes, microhardness and diametral tensile strength were evaluated for the experimental GICs and commercial luting cements. It was concluded that setting time of the cement pastes increased with increasing niobium content of the glasses (X). The properties to the GICs such as setting time and microhardness were influenced by niobium content. (c) 2005 Elsevier B.V. All rights reserved.

New tungstate fluorophosphate glasses

\A new class of tungstate fluorophosphate glasses was identified in the NaPO3-BaF2-WO3 ternary system. The variation of several physical properties was determined with respect to chemical composition. Characteristic temperatures, density and refractive index increase as tungsten oxide content increases. The optical transmission range and specially the energy bandgap depend of the WO3 amount. No crystallization could be observed for the Most WO3 concentrated vitreous samples (greater than or equal to20% molar). Color and optical properties of the glasses depend of the melting time because of the presence of reduced tungsten species like W5+ and W4+. In addition, photodarkening is observed in tungsten rich glass samples under UV laser illumination and this phenomenon can be reversible by heat treatment near the glass transition temperature. (C) 2004 Published by Elsevier B.V.

Fluoride dose response in pH-cycling models using bovine enamel

The aim of this study was to establish methodologies for verification of the fluoride solution dose-response relationship using bovine enamel and pH-cycling models. Six models of the cariogenic challenge were performed, varying the time of demineralization and pH, time of remineralization, composition of de- and remineralization solutions, frequency and time of application of treatment solutions and pH-cycling duration. For the evaluation of the fluoride effect on caries dynamics, two proposed models provided for improvement in standardization of methods leading to a higher level of precision, demonstrating a dose response between treatments with regard to surface microhardness and Delta Z. For the evaluation of the fluoride effect on enamel remineralization, the addition of fluoride to the de- and remineralization solutions and the reduction of frequency and time of application of fluoride solutions led to a more suitable pH-cycling model. Copyright (C) 2005 S. Karger AG, Basel.

Physical properties of silicate glasses doped with SnO2

The presence of tin in the network of silicate glasses produces changes in several of their physico-chemical properties. Glasses with the composition (mol%) 22Na(2)O (.) 8CaO (.) 70SiO(2) containing up to 5 wt% of SnO2 were analyzed under several experimental techniques. Dilatometric measurements showed an increase of the glass transition temperature with increasing tin content, while the average thermal expansion coefficient is reduced. Vickers microhardness, density, and refractive index also increase with the tin content. Diffuse reflectance spectra in the infrared (DRIFT) showed that the presence of tin, even at low concentrations, is responsible for some structural changes since there is an increase of the bridging oxygen concentration. The doped glasses present a brown color and optical absorption spectra measurements are interpreted as being due to precipitation of tin in the form of colloidal particles during cooling of the melted glass. In the Na+ <-> K+ ion exchange process the presence of tin in the glass network hinders the diffusion of these ions. The diffusion coefficients of those ions were calculated by the Boltzmann-Matano technique, after concentration profiles obtained by EDS measurements. All results obtained present evidences that Sn4+ cation acts as a glass network former. (c) 2005 Elsevier B.V. All rights reserved.

Morphology of poly(vinylidene fluoride) and poly(o-metoxyaniline) blends

Blends of poly(o-methoxyaniline) - POMA - and poly(vinylidene fluoride) - PVDF - of various compositions were prepared from organic solvent solutions. Flexible, free-standing and stretchable films were obtained by casting, which were characterized by conductivity measurements, electron microscopy and differential scanning calorimetry. As expected, the blends conductivity increases with increasing contents of the conducting polymer. The onset of the conductivity at low contents of conducting polymer indicates a low percolation threshold for the blends. Despite the presence of the conductive host, the blends displayed the crystalline spherulitic morphology and the beta-phase characteristic of pure PVDF. This morphology appears to be destroyed, however, if the film is stretched by zone-drawing.

EU-3+ AND GD-3+ SPECTROSCOPY IN FLUOROINDATE GLASSES

Luminescence data for Eu3+ and Gd3+ in fluoroindate glasses are compared to those of a fluorozirconate glass. Emission is observed from Eu3+ 5D(J) (J = 0, 1, 2 and 3) and Gd3+ P-6(7/2) excited-state levels and the results put in evidence Eu-Eu and Gd-Eu energy transfer processes. Vibronic bands related to a 320 cm-1 vibrational mode could be observed for Eu3+ luminescent transitions with DELTAJ = 0, 1 and 2 and also for the P-6(7/2) --> S-8(7/2) transition of Gd3+. Lanthanide ion site symmetry is closer to an inversion center in fluoroindate glasses than it is in fluorozirconate.

Surface protection of fluoroindate glasses by sol-gel dip-coated SnO2 thin layers

SnO2 coatings were deposited by a sol-gel dip-coating process to shield fluoroindate glasses (40In-F-3:16BaF(2):20SrF(2):20ZnF(2):2NaF:2GaF(3)) against corrosion in aqueous environments. The effect of the number of coating applications and of the withdrawal speed on the thickness, density and roughness of tin oxide films was investigated by X-ray reflectivity. Film thickness increases both with the number of coating applications and the withdrawal speed. The aqueous leaching of uncoated and SnO2-coated fluoroindate glasses was studied by scanning electron microscopy (SEM) and infrared spectroscopy (FTIR), showing that the glass surface was protected against hydrolytic attack. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Raman scattering, differential scanning calorimetry and Nd3+ spectroscopy in alkali niobium tellurite glasses

Alkali niobium tellurite glasses have been prepared and some of their properties measured by differential scanning calorimetry and Raman scattering. The vitreous domain was established in the pseudo ternary phases diagram for the system TeO2-Nb2O5-(0.5K(2)O-0.5Li(2)O). Raman scattering shows that for samples in the TeO2 rich part of the phase diagram the vitreous structure is composed essentially of (TeO4) units connected by the vertices, as in the alpha-TeO2 crystal. The addition of alkali and niobium oxides causes depolymerization to occur with structures composed essentially of (TeO3) and (NbO6) units. Samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing up to 10% mol Nd3+. The addition of this oxide increases the rigidity of the vitreous network shifting characteristic temperatures to higher temperatures. For the 10% Nd3+ sample amorphous phase separation is assumed to exist from the observation of two glass transition temperatures. Spectroscopic properties such as Judd-Ofelt Omega(lambda) intensity parameters, radiative emission probabilities, and induced emission cross sections were calculated. From these results and also from the emission quenching observed as a function of Nd3+ concentration, we suggest that these glasses could be utilized in optical amplifying devices. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Efficient energy upconversion emission in Tm3+/Yb3+-codoped TeO2-based optical glasses excited at 1.064 mu m

Efficient energy upconversion of cw radiation at 1.064 mum into blue, red, and near infrared emission in Tm3+-doped Yb3+-sensitized 60TeO(2)-10GeO(2)-10K(2)O-10Li(2)O-10Nb(2)O(5) glasses is reported. Intense blue upconversion luminescence at 485 nm corresponding to the Tm3+ (1)G(4)--> H-3(6) transition with a measured absolute power of 0.1 muW for 800 mW excitation power at room temperature is observed. The experimental results also revealed a sevenfold enhancement in the upconversion efficiency when the sample was heated from room temperature to 235 degreesC yielding 0.7 muW of blue absolute fluorescence power for 800 mW pump power. High brightness emission around 800 nm (F-3(4)--> H-3(6)) in addition to a less intense 655 nm ((1)G(4)--> H-3(4) and F-3(2,3)--> H-3(6)) fluorescence is also recorded. The energy upconversion excitation mechanism for thulium emitting levels is assigned to multiphonon-assisted anti-Stokes excitation of the ytterbium-sensitizer followed by multiphonon-assisted sequential energy-transfer processes. (C) 2001 American Institute of Physics.