Tuning the Eu luminescence in glass materials synthesized in air by adjusting glass compositions

The doped Eu3+ ions can be partly reduced to Eu2+ in a series of MO-B2O3: Eu (M=Ba, Sr, Ca) glasses synthesized in air atmosphere, but not in the 12CaO-7Al(2)O(3): Eu glass. The different redox-behavior of Eu ions in these two glass systems is attributed to the different host optical basicity. It is found that a lower valence state of Eu2+ is more favorable in acidic glasses, which have lower optical basicities. A notion of the critical value of optical basicity is introduced empirically, which can be used as a guide for the selection of glass composition suitable to incorporate Eu2+ for luminescence. (C) 2006 Elsevier B.V. All rights reserved.

Effect of ternary phosphate-based glass compositions on osteoblast and osteoblast-like prolferation, differentiation and death in vitro

There is currently a need to expand the range of graft materials available to orthopaedic surgeons. This study investigated the effect of ternary phosphate based glass (PBG) compositions on the behaviour of osteoblast and osteoblast-like cells. PBGs of the formula in mol% P2O5 (50)-CaO (50-X)-Na2O (X), where X was either 2, 4, 6, 8 or 10 were produced and their influence on the proliferation, differentiation and death in vitro of adult human bone marrow stromal cells (hBMSCs) and human fetal osteoblast 1.19 (HFOB 1.19) cells were assessed. Tissue culture plastic (TCP) and hydroxyapatite (HA) were used as controls. Exposure to PBGs in culture inhibited cell adhesion, proliferation and increased cell death in both cell types studied. There was no significant difference in %cell death between the PBGs which was significantly greater than the controls. However, compared to other PBGs, a greater number of cells was found on the 48 mol% CaO which may have been due to either increased adherence, proliferation or both. This composition was capable of supporting osteogenic proliferation and early differentiation and supports the notion that chemical modification of the glass could to lead to a more biologically compatible substrate with the potential to support osteogenic grafting. Realisation of this potential should lead to the development of novel grafting strategies for the treatment of problematic bone defects.

Surface reactivity enhancement of silica-based glass-ceramic scaffolds

A paradigm shift is taking place from using transplanting tissue and synthetic implants to a tissue engineering approach that aims to regenerate damaged tissues by combining cells from the body with highly porous scaffold biomaterials, which act as templates, guiding the growth of new tissue. The central focus of this thesis was to produce porous glass and glass-ceramic scaffolds that exhibits a bioactive and biocompatible behaviour with specific surface reactivity in synthetic physiological fluids and cell-scaffold interactions, enhanced by composition and thermal treatments applied. Understanding the sintering behaviour and the interaction between the densification and crystallization processes of glass powders was essential for assessing the ideal sintering conditions for obtaining a glass scaffolds for tissue engineering applications. Our main goal was to carry out a comprehensive study of the bioactive glass sintering, identifying the powder size and sintering variables effect, for future design of sintered glass scaffolds with competent microstructures. The developed scaffolds prepared by the salt sintering method using a 3CaO.P2O5 - SiO2 - MgO glass system, with additions of Na2O with a salt, NaCl, exhibit high porosity, interconnectivity, pore size distribution and mechanical strength suitable for bone repair applications. The replacement of 6 % MgO by Na2O in the glass network allowed to tailor the dissolution rate and bioactivity of the glass scaffolds. Regarding the biological assessment, the incorporation of sodium to the composition resulted in an inibition cell response for small periods. Nevertheless it was demonstrated that for 21 days the cells response recovered and are similar for both glass compositions. The in vitro behaviour of the glass scaffolds was tested by introducing scaffolds to simulated body fluid for 21 days. Energy-dispersive Xray spectroscopy and SEM analyses proved the existence of CaP crystals for both compositions. Crystallization forming whitlockite was observed to affect the dissolution behaviour in simulated body fluid. By performing different heat treatments, it was possible to control the bioactivity and biocompatability of the glass scaffolds by means of a controlled crystallization. To recover and tune the bioactivity of the glass-ceramic with 82 % crystalline phase, different methods have been applied including functionalization using 3- aminopropyl-triethoxysilane (APTES). The glass ceramic modified surface exhibited an accelerated crystalline hydroxyapatite layer formation upon immersion in SBF after 21 days while the as prepared glass-ceramic had no detected formation of calcium phosphate up to 5 months. A sufficient mechanical support for bone tissue regeneration that biodegrade later at a tailorable rate was achievable with the glass–ceramic scaffold. Considering the biological assessment, scaffolds demonstrated an inductive effect on the proliferation of cells. The cells showed a normal morphology and high growth rate when compared to standard culture plates. This study opens up new possibilities for using 3CaO.P2O5–SiO2–MgO glass to manufacture various structures, while tailoring their bioactivity by controlling the content of the crystalline phase. Additionally, the in vitro behaviour of these structures suggests the high potential of these materials to be used in the field of tissue regeneration.

Diopside-fluorapatite-wollastonite based bioactive glasses and glass-ceramics

Bioactive glasses and glass–ceramics are a class of biomaterials which elicit special response on their surface when in contact with biological fluids, leading to strong bonding to living tissue. This particular trait along with good sintering ability and high mechanical strength make them ideal materials for scaffold fabrication. The work presented in this thesis is directed towards understanding the composition-structure-property relationships in potentially bioactive glasses designed in CaOMgOP2O5SiO2F system, in some cases with added Na2O. The main emphasis has been on unearthing the influence of glass composition on molecular structure, sintering ability and bioactivity of phosphosilicate glasses. The parent glass compositions have been designed in the primary crystallization field of the pseudo-ternary system of diopside (CaO•MgO•2SiO2) – fluorapatite (9CaO•3P2O5•CaF2) – wollastonite (CaO•SiO2), followed by studying the impact of compositional variations on the structure-property relationships and sintering ability of these glasses. All the glasses investigated in this work have been synthesized via melt-quenching route and have been characterized for their molecular structure, sintering ability, chemical degradation and bioactivity using wide array of experimental tools and techniques. It has been shown that in all investigated glass compositions the silicate network was mainly dominated by Q2 units while phosphate in all the glasses was found to be coordinated in orthophosphate environment. The glass compositions designed in alkali-free region of diopside – fluorapatite system demonstrated excellent sintering ability and good bioactivity in order to qualify them as potential materials for scaffold fabrication while alkali-rich bioactive glasses not only hinder the densification during sintering but also induce cytotoxicity in vitro, thus, are not ideal candidates for in vitro tissue engineering. One of our bioglass compositions with low sodium content has been tested successfully both in vivo and in preliminary clinical trials. But this work needs to be continued and deepened. The dispersing of fine glass particles in aqueous media or in other suitable solvents, and the study of the most important factors that affect the rheology of the suspensions are essential steps to enable the manufacture of porous structures with tailor-made hierarchical pores by advanced processing techniques such as Robocasting.

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

Undoped and calcium doped borate glass system for thermoluminescent dosimeter

Borate glasses present an absorption coefficient very close to that of human tissue. This fact makes some borates ideal materials to develop medical and environmental dosimeters. Glass compositions with calcium tetraborate (CaB4O7) and calcium metaborate (CaB2O4), such as the xCaB(4)O(7) - (100-x)CaB2O4 System (0 <= x <= 100 wt%) were obtained by the traditional melting/quenching method. A phenomenon widely known as the 'boron anomaly' was observed in our thermal analysis measurements, as indicated by the increase of T, and the appearance of a maximum value in the composition with 40 wt% of CaB2O4. The Dy doped and Li co-doped 80CaB(4)O(7)-20CaB(2)O(4) (Wt%) glass samples were studied by the thermoluminescence technique. The addition of Dy improved the signal sensitivity in about three times with respect to the undoped glass sample. The addition of Li as a co-dopant in this glass caused a shift to a lower temperature of about 20 degrees C in the main glow peak. The structural analysis of the 80CaB(4)O(7)-20CaB(2)O(4) (wt%) undoped and doped samples were studied through infrared absorption. We have noted an increase in the coordination number of the boron atoms from 3 to 4, i.e., the conversion of the BO3 triangular structural units into BO4 tetrahedra. (c) 2006 Elsevier 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.

Study of the glass transition temperature of as-s glasses for the fabrication of chalcogenide optical fibers

Values of glass transition temperature (Tg) and of linear expansion coefficient (α) for Asx S100-x glasses were measured in the range of concentrations 35 × 42. Because of the importance of the glass formation region 35 × 42 for the optical fibers elaboration, special attention was made on high-pure Asx S100-x glasses. For the glass in the range of 35 × 38, we measure Tg with the interval of x equal to 1 at.% of arsenic. We also measured the Tg values with the interval of x equal to 0.5 at.% of As. We obtained nonlinear behavior of Tg, reflecting the change in molecular composition of As-S glass in the glass composition range studied. The control of such parameters is important to produce optical fibers with specific numerical aperture. © 2013 The American Ceramic Society and Wiley Periodicals, Inc.

The role of glass modifiers in the solubility of Tm3+ ions in As2S3 glasses

Au cours des années une variété des compositions de verre chalcogénure a été étudiée en tant qu’une matrice hôte pour les ions Terres Rares (TR). Pourtant, l’obtention d’une matrice de verre avec une haute solubilité des ions TR et la fabrication d’une fibre chalcogénure dopée au TR avec une bonne qualité optique reste toujours un grand défi. La présente thèse de doctorat se concentre sur l’étude de nouveaux systèmes vitreux comme des matrices hôtes pour le dopage des ions TR, ce qui a permis d’obtenir des fibres optiques dopées au TR qui sont transparents dans l’IR proche et moyenne. Les systèmes vitreux étudiés ont été basés sur le verre de sulfure d’arsenic (As2S3) co-dopé aux ions de Tm3+ et aux différents modificateurs du verre. Premièrement, l’addition de Gallium (Ga), comme un co-dopant, a été examinée et son influence sur les propriétés d’émission des ions de Tm a été explorée. Avec l’incorporation de Ga, la matrice d’As2S3 dopée au Tm a montré trois bandes d’émission à 1.2 μm (1H5→3H6), 1.4 μm (3H4→3F4) et 1.8 μm (3F4→3H6), sous l’excitation des longueurs d’onde de 698 nm et 800 nm. Les concentrations de Tm et de Ga ont été optimisées afin d’obtenir le meilleur rendement possible de photoluminescence. À partir de la composition optimale, la fibre Ga-As-S dopée au Tm3+ a été étirée et ses propriétés de luminescence ont été étudiées. Un mécanisme de formation structurale a été proposé pour ce système vitreux par la caractérisation structurale des verres Ga-As-S dopés au Tm3+, en utilisant la spectroscopie Raman et l’analyse de spectrométrie d’absorption des rayons X (EXAFS) à seuil K d’As, seuil K de Ga et seuil L3 de Tm et il a été corrélé avec les caractéristiques de luminescence de Tm. Dans la deuxième partie, la modification des verres As2S3 dopés au Tm3+, avec l’incorporation d’halogénures (Iode (I2)), a été étudiée en tant qu’une méthode pour l’adaptation des paramètres du procédé de purification afin d’obtenir une matrice de verre de haute pureté par distillation chimique. Les trois bandes d’émission susmentionnées ont été aussi bien observées pour ce système sous l’excitation à 800 nm. Les propriétés optiques, thermiques et structurelles de ces systèmes vitreux ont été caractérisées expérimentalement en fonction de la concentration d’I2 et de Tm dans le verre, où l’attention a été concentrée sur deux aspects principaux: l’influence de la concentration d’I2 sur l’intensité d’émission de Tm et les mécanismes responsables pour l’augmentation de la solubilité des ions de Tm dans la matrice d’As2S3 avec l’addition I2.

The Cougar Point tuff: Implications for thermochemical zonation and longevity of high-temperature, large-volume silicic magmas of the Miocene Yellowstone hotspot

The 12.7-10.5 Ma Cougar Point Tuff in southern Idaho, USA, consists of 10 large-volume (>10²-10³ km³ each), high-temperature (800-1000 °C), rhyolitic ash-flow tuffs erupted from the Bruneau-Jarbidge volcanic center of the Yellowstone hotspot. These tuffs provide evidence for compositional and thermal zonation in pre-eruptive rhyolite magma, and suggest the presence of a long-lived reservoir that was tapped by numerous large explosive eruptions. Pyroxene compositions exhibit discrete compositional modes with respect to Fe and Mg that define a linear spectrum punctuated by conspicuous gaps. Airfall glass compositions also cluster into modes, and the presence of multiple modes indicates tapping of different magma volumes during early phases of eruption. Equilibrium assemblages of pigeonite and augite are used to reconstruct compositional and thermal gradients in the pre-eruptive reservoir. The recurrence of identical compositional modes and of mineral pairs equilibrated at high temperatures in successive eruptive units is consistent with the persistence of their respective liquids in the magma reservoir. Recurrence intervals of identical modes range from 0.3 to 0.9 Myr and suggest possible magma residence times of similar duration. Eruption ages, magma temperatures, Nd isotopes, and pyroxene and glass compositions are consistent with a long-lived, dynamically evolving magma reservoir that was chemically and thermally zoned and composed of multiple discrete magma volumes.

Characterization studies of AgI---Ag2O---MoO3 glasses

Glass formation has been investigated in the system AgI---Ag2O---MoO3. X-ray absorption edge chemical shifts, infrared spectra and heat capacities of the various glass compositions have been measured. The probable anion structures in the oxygen excess and deficient regions have been discussed