Vidros e vitrocerâmicas em sistemas oxifluoretos

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

Estudos estruturais em vidros e vitrocerâmicas contendo 'PBF IND.2'-'CDF IND.2

Pós-graduação em Química - IQ

EStudo fundamental da interação de nanopartículas metálicas com íons terras raras em vidros e vitrocerâmicas para aplicações na região do infravermelho

Pós-graduação em Química - IQ

In vitro evaluation of Biosilicate® dissolution on dentin surface: a SEM analysis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Preparação de vidros e vitrocerâmicas de óxidos de metais pesados contendo prata: propriedades ópticas, estruturais e eletroquímicas

Silver containing heavy metal oxide glasses and glass ceramics of the system WO3-SbPO4-PbO-AgCl with different AgCl contents have been prepared and their thermal, structural and optical properties characterized. Glass ceramics containing metallic silver nanoparticles have been prepared by annealing glass samples at temperatures above the glass transition and analyzed by transmission electron microscopy and energy dispersive X-ray microanalysis. The presence of the metallic clusters has been also confirmed by the observation of a surface plasmon resonimce band in the visible range. Cyclic voltammetric measurements indicated the presence of metallic silver into the glasses, even before to perform the thermal treatment.

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.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Osteoconductivity of modified fluorcanasite glass-ceramics for bone tissue augmentation and repair

Modified fluorcanasite glasses were fabricated by either altering the molar ratios of Na(2)O and CaO or by adding P(2)O(5) to the parent stoichiometric glass compositions. Glasses were converted to glass-ceramics by a controlled two-stage heat treatment process. Rods (2 mm x 4 mm) were produced using the conventional lost-wax casting technique. Osteoconductive 45S5 bioglass was used as a reference material. Biocompatibility and osteoconductivity were investigated by implantation into healing defects (2 mm) in the midshaft of rabbit femora. Tissue response was investigated using conventional histology and scanning electron microscopy. Histological and histomorphometric evaluation of specimens after 12 weeks implantation showed significantly more bone contact with the surface of 45S5 bioglass implants when compared with other test materials. When the bone contact for each material was compared between experimental time points, the Glass-Ceramic 2 (CaO rich) group showed significant difference (p = 0.027) at 4 weeks, but no direct contact at 12 weeks. Histology and backscattered electron photomicrographs showed that modified fluorcanasite glass-ceramic implants had greater osteoconductivity than the parent stoichiometric composition. Of the new materials, fluorcanasite glass-ceramic implants modified by the addition of P(2)O(5) showed the greatest stimulation of new mineralized bone tissue formation adjacent to the implants after 4 and 12 weeks implantation. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 94A: 760-768, 2010

Er3+ and Eu3+ containing transparent glass ceramics in the system PbGeO3-PbF2-CdF2

Glasses with composition 60PbGeO(3)-10PbF(2)-30CdF(2) (mol%) have been obtained in the bulk form with a high stability against crystallization. After doping them with 0.5 mol% of Er3+ or Eu3+ and appropriate heat treatment transparent glass ceramics could be obtained. Electronic spectroscopy, X-ray diffraction and transmission electron microscopy measurements have been made. beta-PbF2: Er3+/Eu3+ Single crystals, 5-10 nm in size, are detected in the otherwise transparent composite medium, the size of the particles and absence of clustering allowing for the increased transparency of the final materials. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Osteoconductivity of modified fluorcanasite glass-ceramics for bone tissue augmentation and repair

Modified fluorcanasite glasses were fabricated by either altering the molar ratios of Na 2O and CaO or by adding P 2O 5 to the parent stoichiometric glass compositions. Glasses were converted to glass-ceramics by a controlled two-stage heat treatment process. Rods (2 mm x 4 mm) were produced using the conventional lost-wax casting technique. Osteoconductive 45S5 bioglass was used as a reference material. Biocompatibility and osteoconductivity were investigated by implantation into healing defects (2 mm) in the midshaft of rabbit femora. Tissue response was investigated using conventional histology and scanning electron microscopy. Histological and histomorphometric evaluation of specimens after 12 weeks implantation showed significantly more bone contact with the surface of 45S5 bioglass implants when compared with other test materials. When the bone contact for each material was compared between experimental time points, the Glass-Ceramic 2 (CaO rich) group showed significant difference (p = 0.027) at 4 weeks, but no direct contact at 12 weeks. Histology and backscattered electron photomicrographs showed that modified fluorcanasite glass-ceramic implants had greater osteoconductivity than the parent stoichiometric composition. Of the new materials, fluorcanasite glass-ceramic implants modified by the addition of P 2O 5 showed the greatest stimulation of new mineralized bone tissue formation adjacent to the implants after 4 and 12 weeks implantation. © 2010 Wiley Periodicals, Inc.

White Light and Multicolor Emission Tuning in Triply Doped Yb3+/Tm3+/Er3+ Novel Fluoro-phosphate Transparent Glass-ceramics

New Yb3+, Er3+ and Tm3+ doped fluoro-phosphate glasses belonging to the system NaPO3–YF3–BaF2–CaF2 and containing up to 10 wt% of rare-earth ion fluorides were prepared and characterized by differential scanning calorimetry, absorption spectroscopy and up-conversion emission spectroscopy under excitation with a 975 nm laser diode. Transparent and homogeneous glass-ceramics have been reproducibly obtained with a view to manage the red, green and blue emission bands and generate white light. X-ray diffraction as well as electron microscopy techniques have confirmed the formation of fluorite-type cubic nanocrystals at the beginning of the crystallization process while complex nanocrystalline phases are formed after a longer heat-treatment. The prepared glass-ceramics exhibit high optical transparency even after 170 h of thermal treatment. An improvement of up-conversion emission intensity – from 10 to 160 times larger – was measured in the glass-ceramics when compared to the parent glass, suggesting an important incorporation of the rare-earth ions into the crystalline phase(s). The involved mechanisms and lifetime were described in detail as a function of heat-treatment time. Finally, a large range of designable color rendering (from orange to turquoise through white) can be observed in these materials by controlling the laser excitation power and the crystallization rate.

Mechanical properties and porosity of dental glass-ceramics hot-pressed at different temperatures

The objective of this work was to evaluate biaxial-flexural-strength (σf), Vickers hardness (HV), fracture toughness (K Ic), Young's modulus (E), Poisson's ratio (ν) and porosity (P) of two commercial glass-ceramics, Empress (E1) and Empress 2 (E2), as a function of the hot-pressing temperature. Ten disks were hot-pressed at 1065, 1070, 1075 and 1080 °C for E1; and at 910, 915, 920 and 925 °C for E2. The porosity was measured by an image analyzer software and s f was determined using the piston-on-three-balls method. K Ic and HV were determined by an indentation method. Elastic constants were determined by the pulse-echo method. For E1 samples treated at different temperatures, there were no statistical differences among the values of all evaluated properties. For E2 samples treated at different temperatures, there were no statistical differences among the values of σf, E, and ν, however HV and K Ic were significantly higher for 910 and 915 °C, respectively. Regarding P, the mean value obtained for E2 for 925 °C was significantly higher compared to other temperatures.

Internal Residual Stresses in Sintered and Commercial Low Expansion Li(2)O-Al(2)O(3)-SiO(2) Glass-Ceramics

We performed Synchrotron X-ray diffraction (XRD) analyses of internal residual stresses in monolithic samples of a newly developed Li(2)O-Al(2)O(3)-SiO(2) (LAS) glass-ceramic produced by sintering and in a commercial LAS glass-ceramic, CERAN (R), produced by the traditional crystal nucleation and growth treatments. The elastic constants were measured by instrumented indentation and a pulse-echo technique. The thermal expansion coefficient of virgilite was determined by high temperature XRD and dilatometry. The c-axis contracts with the increasing temperature whereas the a-axis does not vary significantly. Microcracking of the microstructure affects the thermal expansion coefficients measured by dilatometry and thermal expansion hysteresis is observed for the sintered glass-ceramic as well as for CERAN (R). The measured internal stress is quite low for both glass-ceramics and can be explained by theoretical modeling if the high volume fraction of the crystalline phase (virgilite) is considered. Using a modified Green model, the calculated critical (glass) island diameter for spontaneous cracking agreed with experimental observations. The experimental data collected also allowed the calculation of the critical crystal grain diameters for grain-boundary microcracking due to the anisotropy of thermal expansion of virgilite and for microcracking in the residual glass phase surrounding the virgilite particles. All these parameters are important for the successful microstructural design of sintered glass-ceramics.

Subcritical crack growth in porcelains, glass-ceramics, and glass-infiltrated alumina composite for dental restorations

The objective was to compare fracture toughness (K(Ic)), stress corrosion susceptibility coefficient (n), and stress intensity factor threshold for crack propagation (K(I0)) of two porcelains [VM7/Vita (V) and d.Sign/Ivoclar (D)], two glass-ceramics [Empress/Ivolcar (E1) and Empress2/Ivlocar (E2)] and a glass-infiltrated alumina composite [In-Ceram Alumina/Vita (IC)]. Disks were constructed according to each manufacturer`s processing method, and polished before induction of cracks by a Vickers indenter. Crack lengths were measured under optical microscopy at times between 0.1 and 100 h. Specimens were stored in artificial saliva at 37A degrees C during the whole experiment. K(Ic) and n were determined using indentation fracture method. K(I0) was determined by plotting log crack velocity versus log K(I). Microstructure characterization was carried out under SEM, EDS, X-ray diffraction and X-ray fluorescence. IC and E2 presented higher K(Ic) and K(I0) compared to E1, V, and D. IC presented the highest n value, followed by E2, D, E1, and V in a decreasing order. V and D presented similar K(Ic), but porcelain V showed higher K(I0) and lower n compared to D. Microstructure features (volume fraction, size, aspect ratio of crystalline phases and chemical composition of glassy matrix) determined K(Ic). The increase of K(Ic) value favored the increases of n and K(I0).