Lead-cadmium oxyfluoride glasses and glass-ceramics

Glasses and glass-ceramics have been obtained in oxyfluoride systems involving lead and cadmium fluorides and one of the well-known glass former oxides SiO2, B2O3 and TeO2. Vitreous domains were established and a wide range of compositions including high heavy metal contents lead to stable glasses. Amorphous structures have been studied by short-range order spectroscopy techniques (Raman scattering and x-ray absorption) and molecular basic structures have been identified. Besides the usual oxides, the role of glass former could also be proposed for cadmium ions. Special attention has been paid for crystallization process. Cubic lead fluoride, cubic lead tellurite, tetragonal tellurium oxide and a solid solution of the type Pb1-xCdxF2 are obtained as crystallization products depending on the composition and temperature of heat treatments. Pb1-xCdxF2 solid solutions are well known superionic materials and obtaining this solid solution as a crystal phase could be very interesting for applications concerning ionic electrical conduction properties. The addition of rare earth ions led to the control of the crystallization process. In the presence of the nucleating ion only the cubic form beta-PbF2 was identified. Rare earth ions are present in the crystal phase and crystal-like spectroscopic properties were observed suggesting interesting applications for these perfectly transparent glass ceramics in photonics.

Structural and spectroscopic study of oxyfluoride glasses and glass-ceramics using europium ion as a structural probe

Transparent oxyfluoride glasses and beta-PbF(2) nanocrystals containing glass-ceramics were prepared with varying Eu(3+) content (0.3, 0.4, 0.5 and 0.6%). The effect of Eu(3+) content on the preparation of glass-ceramics was investigated. From differential scanning calorimetry, the T(x)-T(g)(T(x)-temperature of the onset of crystallization; T(g)-glass transition temperature) parameter for glasses has shown slight variation, and an exothermic peak near T(g) called the ceramization temperature (T(c)) has been observed. Heat treatments were performed at this temperature to obtain transparent glass-ceramics containing beta-PbF(2) nanocrystals, identified by x-ray diffraction. Heat treatments for different periods of time were performed and were observed to be very important in the control of the crystal size and of the crystallization rate. Based upon the absorption spectra, the scattering level due to the presence of beta-PbF(2) nanocrystals in the glass-ceramics was observed to be similar to that for the mother glasses. Detailed analysis of emission spectra and decay time measurements led to the identification of Eu(3+) ions as the beta-PbF(2) crystalline phase. Excitation spectra at 70 K show the interaction of Eu(3+) ions with the fluorogermanate network.

Local order around rare earth ions during the devitrification of oxyfluoride glasses

Erbium L-3-edge extended x-ray absorption fine structure (EXAFS) measurements were performed on rare earth doped fluorosilicate and fluoroborate glasses and glass ceramics. The well known nucleating effects of erbium ions for the crystallization of cubic lead fluoride (based on x-ray diffraction measurements) and the fact that the rare earth ions are present in the crystalline phase (as indicated by Er3+ emission spectra) seem in contradiction with the present EXAFS analysis, which indicates a lack of medium range structural ordering around the Er3+ ions and suggests that the lead fluoride crystallization does not occur in the nearest neighbor distance of the rare earth ion. Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er3+ ions were performed, and results indicate that Er3+ ions lower the devitrification temperature of PbF2, in good agreement with the experimental results. The genuine role of Er3+ ions in the devitrification process of PbF2 has been investigated. Although Er3+ ions could indeed act as seeds for crystallization, as experiments suggest, molecular dynamics simulation results corroborate the experimental EXAFS observation that the devitrification does not occur at its nearest neighbor distance. (c) 2008 American Institute of Physics.

Study of fluorine losses in oxyfluoride glasses

Glasses in PbGeO3-PbF-CdF2 and GeO2-PbO-PbF2-CdF2 systems were studied and the fluorine losses during synthesis were investigated. Samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction, Fourier transform infrared spectroscopy (FTIR) and Raman scattering spectroscopy. The use of stoichiometric germanate glass, PbGeO3, instead of introducing individual oxides (GeO2 + PbO) lead to decreasing fluorine losses, as detected by a fluorine ion selective electrode. The main structural features obtained from vibrational spectroscopy could be described by a metagermanate basic structure permeating fluorine rich regions. (c) 2005 Elsevier B.V. All rights reserved.

Sol-gel Eu3+/Tm3+ doped transparent glass-ceramic waveguides

Eu3+ and Tm3+ doped lanthanum fluoride and lanthanum oxyfluoride are obtained from Eu3+, Tm3+ containing lanthanum fluoracetate solutions. The nature of the crystal phase obtained could be controlled by the temperature of heat treatment. Spectral characteristics of Eu3+ doped crystal phases were sufficiently different to allow utilization of Eu3+ as structural probes. Tm3+ emission at the technologically important spectral region of 1450nm could be observed for the fluoride and oxyfluoride crystal phases. The large bandwidth obtained (around 120nm) suggests potential applications in optical amplification. SiO2-LaF3-LaOF composite materials were also prepared. It is observed that for heat treatments above 800degreesC, fluorine loss, probably in the form of SiF4 hinder the observation of Tm3+ emission. Eu3+ spectroscopic characteristics clearly show the evolution of a fluoride like environment to an amorphous oxide one as the temperature of heat treatment increased. Thin films obtained by dip-coating on V-SiO2 substrates and treated at 300degreesC, 500degreesC and 800degreesC display guided modes in the visible and infrared regions. Optical characteristics (refractive index and films thickness) were obtained at 543.5, 632.8 and 1550nm. Attenuation as low as 1.8dB/cm was measured at 632.8nm. (C) 2004 Published by Elsevier B.V.

Conductivity and F-19 NMR in PbGeO3-PbF2-CdF2 glasses and glass-ceramics

The temperature dependence of the electrical conductivity and the F-19 nuclear magnetic resonance (NMR) of PbGeO3-PbF2CdF, glasses and glass ceramics are investigated. The measured conductivity values of the glasses are above 10(-5) Skin at 500 K, and increase with increasing lead fluoride content. Activation energies extracted from the conductivity data are in the range 0.59-0.73 eV. Results are consistent with the hypothesis that in these oxyfluoride glasses lead fluoride rich clusters are dispersed in a metagermanate based matrix providing increasing mobility pathways for conducting ions. The conductivity of a sample of the glass ceramic of composition (mol%) 60PbGeO(3-)20PbF(2)-20CdF(2) was found to be smaller than that in the corresponding glass, suggesting that there are poor ionic conducting regions in the interface between the nanometer sized crystals. The temperature dependence of the F-19 relaxation times, measured in the range 100-800 K, exhibit the qualitative features associated with high fluorine mobility in both, glass and glass ceramics materials. We suggest that de-convolution of the spin-lattice relaxation rates observed in the glass ceramics shows that the observed high temperature rate maximum is associated with the diffusional motions of the fluorine ions in beta-PbF2 crystals. (c) 2005 Elsevier B.V. All rights reserved.

Use of glass transition temperature for stabilization of board's cracks of Eucalyptus grandis

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

Crystallization of SiO2-CaO-Na2O Glass Using Sugarcane Bagasse Ash as Silica Source

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

Understanding the Crystallization Mechanism of a Wollastonite Base Glass Using Isoconversional, IKP Methods and Master Plots

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

Recycling of glass cullet as aggregate for clays used to produce roof tiles

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

Crystallization study of the (1-x)Sb2O3-(x)SbPO4 glass system

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Tunable visible photoluminescence of powdered silica glass

intense photoluminescence in the visible region was observed at room temperature in standard soda-lime-silica glass powder, mechanically milled in a high-energy attrition mill. The emission band maximum shows an interesting dependence on the exciting wavelength, suggesting the possibility to tune the PL emission. These findings indicate that the photoluminescence may be directly related to unsatisfied chemical bonds correlated with the high surface area. The Raman scattering and ultraviolet-visible optical reflectance measurements corroborate this assertion. Transmission electron microscopy measurements indicate that samples milled more than 10 h present the formation of nanocrystallites with about 10-20 nm. (C) 2007 Elsevier B.V. All rights reserved.

Processing and hygrothermal effects on viscoelastic behavior of glass fiber/epoxy composites

Fiber reinforced epoxy composites are used in a wide variety of applications in the aerospace field. These materials have high specific moduli, high specific strength and their properties can be tailored to application requirements. In order to screening optimum materials behavior, the effects of external environments on the mechanical properties during usage must be clearly understood. The environmental action, such as high moisture concentration, high temperatures, corrosive fluids or ultraviolet radiation (UV), can affect the performance of advanced composites during service. These factors can limit the applications of composites by deteriorating the mechanical properties over a period of time. Properties determination is attributed to the chemical and/or physical damages caused in the polymer matrix, loss of adhesion of fiber/resin interface, and/or reduction of fiber strength and stiffness. The dynamic elastic properties are important characteristics of glass fiber reinforced composites (GRFC). They control the damping behavior of composite structures and are also an ideal tool for monitoring the development of GFRC's mechanical properties during their processing or service. One of the most used tests is the vibration damping. In this work, the measurement consisted of recording the vibration decay of a rectangular plate excited by a controlled mechanism to identify the elastic and damping properties of the material under test. The frequency amplitude were measured by accelerometers and calculated by using a digital method. The present studies have been performed to explore relations between the dynamic mechanical properties, damping test and the influence of high moisture concentration of glass fiber reinforced composites (plain weave). The results show that the E' decreased with the increase in the exposed time for glass fiber/epoxy composites specimens exposed at 80 degrees C and 90% RH. The E' values found were: 26.7, 26.7, 25.4, 24.7 and 24.7 GPa for 0, 15, 30, 45 and 60 days of exposure, respectively. (c) 2005 Springer Science + Business Media, Inc.

Hygrothermal effects on damping behavior of metal/glass fiber/epoxy hybrid composites

Continuous fiber/metal laminates (FML) offer significant improvements over current available materials for aircraft structures due to their excellent fatigue endurance and low density. Glass fibers/epoxy laminae and aluminum foil (Glare) are commonly used to obtain these hybrid composites. The environmental factors can limit the applications of composites by deteriorating the mechanical properties during service. Usually, epoxy resins absorb moisture when exposed to humid environments and metals are prone to surface corrosion. Therefore, the combination of the two materials in Glare (polymeric composite and metal). can lead to differences that often turn out to be beneficial in terms of mechanical properties and resistance to environmental influences. In this work. The viscoelastic properties. such as storage modulus (E') and loss modulus (E'), were obtained for glass fiber/epoxy composite, aluminum 2024-T3 alloy and for a glass fiber/epoxy/aluminum laminate (Glare). It was found that the glass fiber/epoxy (G/E) composites decrease the E' modulus during hygrothermal conditioning up to saturation point (6 weeks). However, for Glare laminates the E' modulus remains unchanged (49GPa) during the cycle of hygrothermal conditioning. The outer aluminum sheets in the Glare laminate shield the G/E composite laminae from moisture absorption. which in turn prevent, in a certain extent, the material from hygrothermal degradation effects. (c) 2005 Elsevier B.V. All rights reserved.

Determination of Population Size of Glass-like Carbon Sampling Used in Weibull Analysis

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