Crystallization kinetic of fluoro-zirconate glasses by non-isothermal analysis

Fluoride glasses have been extensively studied due to their high transparency in the infrared wavelength. The crystallization kinetics of these systems has been studied using DTA and DSC techniques. Most of the experimental data is frequently investigated in terms of the Johnson-Mehl-Avrami (JMA) model in order to obtain kinetic parameters.In this work, DSC technique has been used to study the crystallization of fluorozirconate glass under non-isothermal conditions. It was found that JMA model was not fit to be applied directly to these systems, therefore, the method proposed by Malek has been applied and the Sestak-Berggren (SB) model seems to be adequate to describe the crystallization process.

Electric characterization of a hybrid composite based on POMA/P(VDF- TrFE)/Zn2SiO4 : Mn using impedance spectroscopy

Understanding the microscopic origin of the dielectric properties of disordered materials has been a challenge for many years, especially in the case of samples with more than one phase. For polar dielectrics, for instance, the Lepienski approach has indicated that the random free energy barrier model of Dyre must be extended. Here we analyse the dielectric properties of a polymer blend made up with the semiconducting poly(o-methoxyaniline) and poly( vinylidene fluoride-trifluorethylene) POMA/P(VDF-TrFE), and of a hybrid composite of POMA/P(VDF-TrFE)/Zn2SiO4:Mn. For the blend, the Lepienski model, which takes into account the rotation or stretching of electric dipoles, provided excellent fitting to the ac impedance data. Because two phases had to be assumed for the hybrid composite, we had to extend the Lepienski model to fit the data, by incorporating a second transport mechanism. The two mechanisms were associated with the electronic transport in the polymeric matrix and with transport at the interfaces between Zn2SiO4: Mn microparticles and the polymeric matrix, with the relative importance of the interfacial component increasing with the percentage of Zn2SiO4: Mn in the composite. The analysis of impedance data at various temperatures led to a prediction of the theoretical model of a change in morphology at 190 +/- 40 K, and this was confirmed experimentally with a differential scanning calorimetry experiment.

Spectroscopic studies of the Eu3+ and Er3+ ions in the fluorozirconate LaZr2F11 matrix

An investigation by optical spectroscopy of the Eu3 + and Er3 + active ions in the crystallized fluorozirconate matrix LaZr2F11 is presented. The D-5(1) --> F-7(0-5) emission lines of Eu3 + are used to extract the F-7(0-5) energy scheme and the observed extinctions permit the deduction of irreducible representations (IRREPS) associated with corresponding sub-levels in the D-2 symmetry. The crystal field analysis was carried out on a 387 x 387 basis set, comprising the F-7, D-5(1,2,3) F-5(1,2), (5)G(1,2,3) and P-3(1,2,3,4,5,6) terms of the Eu-3 (+) 4f(6) configuration. The deviation and rms are 6.8 and 7.9 cm (-1), respectively for 38 levels and ten parameters. The experimental crystal field parameters are in good agreement with the ab-initio ones. Moreover, the relative intensities of the D-5(0) --> F-7(2,3,4) emissions are well reproduced by an 'ab-initio' calculation, except for three lines. The Er3 + ions introduced in LaZr2F11, microcrystals also lie in an unique crystallographic site. A total of 31 energy levels were recorded and the crystal field analysis led to 6.6 and 7.8 cm (-1) for the deviation and rms, respectively, for nine variable parameters taken into account. The experimental CF parameters for Er3 + and Eu3 + are very similar, which seems to show that the host lattice contracts around the smaller Er3 + ion. The informations given by both Eu3 + and Eu3 + optical probes in LaZr2F11 are very consistent with the structure previously determined for the isotypic PrZr2F11 fluoride. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Electric measurements with constant current: A practical method for characterizing dielectric films

This article assesses the use of the constant current (CC) method for characterizing dielectric films. The method is based on charging the sample with a constant current (current stress) and measuring the corresponding voltage rise under the closed circuit condition. Our article shows that the CC method is an alternative to the constant voltage stressing method to study the electric properties of nonpolar, ferroelectric, and polar polymers. The method was tested by determining the dielectric constant of polytetrafluoroethylene, and investigating the electric conduction in poly(ethylene terephthalate). For the ferroelectric polymer poly(vinylidene fluoride), it is shown that hysteresis loops and the dependence of the ferroelectric polarization on the electric field can be obtained. (C) 2001 American Institute of Physics.

Effect of Cervitec (R) on mutans streptococci in plaque and on caries formation on occlusal fissures of erupting permanent molars

The aim of this study was to evaluate the effect of Cervitec(R) on the abundance of mutans streptococci (MS) in occlusal dental plaque and on 2-year caries increment of partly erupting first permanent molars. Sixteen healthy schoolchildren aged 6-8 years, with at least 2 sound contralateral partly erupted permanent molars, received diet counselling and daily parental supervised toothbrushing with a fluoride dentifrice. Stimulated saliva samples were collected at baseline and after 1 year to evaluate MS levels. In a split-mouth design, Cervitec varnish was applied to one of the teeth at baseline and after 3 and 6 months, while the other tooth in the same jaw was a control. At the 9-month follow-up the teeth were in occlusal contact. At this time, varnish was not applied. At 3 and 6 months after the first application of varnish a significant suppression of MS was observed in plaque. Caries investigations, performed at baseline and every 3 months during the 2 years after the start of the study, showed that all the teeth treated with the varnish were free of caries after 2 years, whereas 8/16 control teeth developed incipient caries. In conclusion, our results suggest that treatment with Cervitec reduces MS in plaque on erupting permanent molars and can lead to a significant decrease in caries incidence. Copyright (C) 2002 S. Karger AG, Basel.

Synthesis and structural investigations on TeO2-PbF2-CdF2 glasses and transparent glass-ceramics

New glasses have been prepared in the oxifluoride mixed system TeO2-PbF2-CdF2. Starting from pure TeO2 the addition of the fluorides leads to a decrease in the glasses characteristic temperatures. Also from Raman scattering results a structural evolution was observed where the number of structural units described as [TeO3] trigonal pyramids and [TeO3+1] polyhedra increases at the expense of the [TeO4] trigonal bipyramids supposed to exist in the TeO2, rich samples. Transparent glass ceramics were obtained from the glass with composition 80TeO(2)-10PbF(2)-10CdF(2), (mol%) with the PbTe3O7 crystalline phase being identified by X-ray diffraction and EXAFS measurements performed at the Te K, Cd K and Pb L-III edges. Also from Exafs measurements it is proposed that cadmium ions are preferentially surrounded by oxygen atoms although they were in a fluoride anion environment in the starting material. (C) 2002 Published by Elsevier B.V. Ltd.

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.

CONTROL OF ADIPOSE-TISSUE LIPOLYSIS IN ECTOTHERM VERTEBRATES

Lipolytic activity of fish (Hoplias malabaricus), toad (Bufo paracnemis), and snake (Philodryas patagoniensis) adipose tissue was investigated in vivo and in vitro. Catecholamines or glucagon did not affect the release of free fatty acids (FFA) by incubated fish and toad adipose tissue. Catecholamines also failed to activate snake adipose tissue lipolysis, which even decreased in the presence of epinephrine. However, glucagon stimulated both the lipolytic activity of reptilian tissue in vitro and the mobilization of FFA to plasma when administered to snakes in vivo. The release of FFA from incubated fish, amphibian, and reptilian adipose tissue increased markedly in the presence of cAMP or xanthine derivatives, inhibitors of phosphodiesterase. Forskolin or fluoride, activators of specific components of the adenylate cyclase system, strongly stimulated toad adipose tissue lipolysis. The data suggest that adipocyte triacylglycerol lipase of ectotherm vertebrates is activated by a cAMP-mediated phosphorylation and that the organization of the membrane-bound adenylate cyclase system is similar to that of mammals.

Molecular dynamics simulation on devitrification: Isothermal devitrification and thermodynamics of PbF2 glasses

The vitrification and devitrification features of lead fluoride are investigated by means of molecular dynamic simulations. The influence of heating rate on the devitrification temperature as well as the dependence of the glass properties on its thermal history, i.e., the cooling rate employed, is identified. As expected, different glasses are obtained when the cooling rates differ. Diffusion coefficient analysis during heating of glass and crystal, indicates that the presence of defects on the glassy matrix favors the transition processes from the ionic to a superionic state, with high mobility of fluorine atoms, responsible for the high anionic conduction of lead fluoride. Nonisothermal and isothermal devitrification processes are simulated in glasses obtained at different cooling rates and structural organizations occurring during the heat treatments are clearly observed. When a fast cooling rate is employed during the glass formation, the devitrification of a single crystal (limited by the cell dimensions) is observed, while the glass obtained with slower cooling rate, allowing relaxations and organization of various regions on the glass bulk during the cooling process, devitrifies in more than one crystalline plane. (C) 2004 American Institute of Physics.

Effect of low contents of a polyaniline derivative on the crystallization and electrical properties of blends with PVDF

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

Quantitative analysis of mineral content in enamel using laboratory microtomography and microhardness analysis. - art. no. 631823

This study evaluates laboratory microtomography and microhardness analysis for quantifying the mineral content of bovine enamel. Fifty enamel blocks were submitted individually for 5 days to a pH-cycling model at 37 degrees C and remained in the remineralizing solution for 2 days. The blocks were treated twice daily for 1 min with NaF dentifrices (Placebo, 275, 550, 1,100 mu g F/g and Crest (R)) diluted in deionized water. Surface microhardness changes (%SMH) and mineral loss (Delta Z) were then calculated. Laboratory microtomography was also used to measure total mineral lost (LMM). Pearson's correlation (p < 0.05) was used to determine the relationship between different methods of analysis and dose-response between treatments. Dentifrice fluoride concentration and %SMH and Delta Z were correlated (p < 0.05). There was a positive relationship (p < 0.05) when comparing LMM vs. Delta Z; a negative relationship (p < 0.05) was found for %SMH vs. LMM and %SMH vs. Delta Z. Therefore, both mineral quantification techniques provide adequate precision for studying the bovine enamel-pH-cycling demineralization/remineralization model.

Study on the initial stages of water corrosion of fluorozirconate glasses

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, ZBLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)) was investigated using X-ray photoelectron spectroscopy (XPS), grazing-incidence small angle X-ray scattering (GISAXS), X-ray reflectivity (XRR) and scanning electron microscopy (SEM). After a short exposure period (25 min) of the glass surface to deionized water the XPS data indicate an increase of the oxygen content accompanied by a decrease of fluorine concentration. The analysis of the chemical bonding structure identified the predominant surface reaction products as zirconium hydroxyfluoride and oxyfluoride species. The second most abundant glass component, bariumfluoride, remains almost unaffected by oxygen, while sodium fluoride is completely removed from the attacked surface region. The detected structural and compositional changes are related to the selective dissolution of the glass components leading to the formation of a new surface phase. This process is accompanied by a visible surface roughening caused by reprecipitated species, observed by SEM. The modification of the glass surface is responsible for an increase of the GISAXS intensity. The scattering was attributed to nanovoids formed at the surface region of the glass with an average size of 2.4 +/- 0.05 nm. (C) 2004 Elsevier B.V. All rights reserved.

Effect of rinsing with water immediately after APF gel application on enamel demineralization in situ

This double-blind crossover in situ study evaluated the effect of rinsing with water immediately after the application of acidulated phosphate fluoride (APF) on enamel demineralization. APF application was followed by: no rinsing or consuming of liquids or solids for the next 30 min; immediately washing with water jet or drinking of a glass of water. All treatments showed a statistically significant decrease in enamel mineral loss compared to the control (p < 0.05), but the differences among treatments were not significant (p > 0.05). The data suggest that the recommendation of asking patients to refrain from drinking water following professional APF application does not seem to have an influence on the anticaries effect of fluoride. Copyright (C) 2005 S. Karger AG, Basel.

Effect of commercial mouthwashes on the corrosion resistance of Ti-10Mo experimental alloy

The purpose of this work was to evaluate the effect of three commercial mouthwashes on the corrosion resistance of Ti-10Mo experimental alloy. Experiments were made at 37.0 +/- 0.5 degrees C in a conventional three-compartment double wall glass cell containing commercial mouthwashes. Three mouthwashes with different active ingredients were tested: ( I) 0.05% sodium fluoride + 0.03% triclosan; (II) 0.5 g/l cetylpyridinium chloride + 0.05% sodium fluoride; (III) 0.12% chlorohexidine digluconate. The assessment of the individual effect of active ingredients was studied by using 0.05% sodium fluoride. Commercially pure titanium (CP Ti) was used as control. Microstructures from Ti-10Mo experimental alloy and CP Ti were also evaluated using optical microscopy. Ti-10Mo as-cast alloy shows the typical rapidly cooled dendrites microstructure (beta phase) while CP Ti has exhibited a metastable martensitic microstructure. Electrochemical behavior of dental materials here studied was more affected by mouthwash type than by Ti alloy composition or microstructure. In both alloys passivation phenomenon was observed. This process may be mainly related to Ti oxides or other Ti species present in spontaneously formed film. Small differences in passive current densities values may be connected with changes in film porosity and thickness. Protective characteristics of this passive film are lower in 0.05% sodium fluoride + 0.03% triclosan mouthwash than in the other two mouthwashes tested.

Electroluminescence of zinc oxide thin-films prepared via polymeric precursor and via sol-gel methods

Zinc oxide (ZnO) is an electroluminescent (EL) material that can emit light in different regions of electromagnetic spectrum when electrically excited. Since ZnO is chemically stable, inexpensive and environmentally friendly material, its EL property can be useful to construct solid-state lamps for illumination or as UV emitter. We present here two wet chemical methods to prepare ZnO thin-films: the Pechini method and the sol-gel method, with both methods resulting in crystalline and transparent films with transmittance > 85% at 550 nm. These films were used to make thin-film electroluminescent devices (TFELD) using two different insulator layers: lithium fluoride (LiF) or silica (SiO2). All the devices exhibit at least two wide emission bands in the visible range centered at 420 nm and at 380 nm attributed to the electronic defects in the ZnO optical band gap. Besides these two bands, the device using SiO2 and ZnO film obtained via sol-gel exhibits an additional band in the UV range centered at 350 nm which can be attributed to excitonic emission. These emission bands of ZnO can transfer their energy when a proper dopant is present. For the devices produced the voltage-current characteristics were measured in a specific range of applied voltage. (C) 2007 Elsevier B.V. All rights reserved.