Transmission enhancement in chalco-halide glasses for multiband applications

The potential of clear Ga2S3-GeS2-CsCl based sulfide glasses transparent up to 11.5 μm to be used as new optical material for multispectral applications has been investigated. The addition of large amount of chlorine ions – above 40 mol.% of CsCl – into the chalcogenide vitreous network in order to produce colorless glasses results in a drastic increase of their water contamination. We report for the first time, to the best of our knowledge, the purification of cesium chloride CsCl by dynamic distillations under vacuum in order to reduce water and hydroxyl group contamination before complete melting of the glass. Besides, sulfur purification by dynamic and static distillations was also performed in the implemented method. The obtained glasses were then characterized by UV-visible and infrared (FTIR) spectroscopies, by electron probe microanalysis (EPMA), thermal analysis (DSC), and their refractive indices in the visible and near infrared ranges were also measured. A large improvement of the glass transmission spectrum has been achieved with an estimated reduction of about 45 times of the OH and H2O content and 60 times of the SH content. The glass thermal molding ability and chemical durability with and without protective coating have been tested to probe their potential for fabrication of complex optics.

Raman spectroscopy analysis of structural photoinduced changes in GeS(2) + Ga(2)O(3) thin films

Photoexpansion and photobleaching effects have been observed in amorphous GeS(2) + Ga(2)O(3) (GGSO) thin films, when their surfaces were exposed to UV light. The photoinduced changes on the surface of the samples are indications that the structure has been changed as a result of photoexcitation. In this paper, micro-Raman, energy dispersive X-ray analysis (EDX) and backscattering electrons (BSE) microscopy were the techniques used to identify the origin of these effects. Raman spectra revealed that these phenomena are a consequence of the Ge-S bonds` breakdown and the formation of new Ge-O bonds, with an increase of the modes associated with Ge-O-Ge bonds and mixed oxysulphide tetrahedral units (S-Ge-O). The chemical composition measured by EDX and BSE microscopy images indicated that the irradiated area is oxygen rich. So, the present paper provides fundamental insights into the influence of the oxygen within the glass matrix on the considered photoinduced effects. (C) 2010 Elsevier B.V. All rights reserved.

Microstructured chalcogenide optical fibers from As2S3 glass: towards new IR broadband sources

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

Formation, thermal, optical and physical properties of GeS2-Ga2S3-AgCl novel chalcohalide glasses

Novel GeS2-Ga2S3-AgCl chalcohalide glasses had been prepared by melt-quenching technique, and the glass-forming region was determined by XRD, which indicated that the maximum of dissolvable AgCl was up to 65 mol%. Thermal and optical properties of the glasses were studied by differential scanning calorimetry (DSC) and Visible-IR transmission, which showed that most of GeS2-Ga2S3-AgCl glasses had strong glass-forming ability and broad region of transmission (about 0.45-12.5 mu m). With the addition of AgCl, the glass transition temperature, Tg decreases distinctly, and the short-wavelength cut-off edge (lambda(vis)) of the glasses also shifts to the long wavelength gradually. However, the glass-forming ability of the glass has a complicated evolutional trend depended on the compositional change. In addition, the values of the Vickers microhardness, H (v) , which decrease with the addition of AgCl, are high enough for the practical applications. These excellent properties of GeS2-Ga2S3-AgCl glasses make them potentially applied in the optoelectronic field, such as all-optical switch, etc.

Novel erbium-doped TeO2-based oxysulfide glasses: thermal and spectroscopic properties

Er3+-doped TeO2-based oxysulfide glasses have been prepared in argon atmosphere in carbon crucibles. The thermal analysis and spectroscopic properties of Er (3+) have been considered in terms of sulfide influence. As a function of composition, we have principally measured optical absorption, spontaneous emission and lifetime measurements. Judd-Ofelt theory was introduced to calculate bandwidth and emission cross-section. The results show the product FVMM x sigma(c) increase from 476.8 8 to 635.04 10(-21) cm(2) nm evidently with the addition of 10 mol% PbS into tellurite glass, which indicates a perfect effect on spectra property of Er3+ ions. (C) 2004 Elsevier B.V. All rights reserved.

High Verdet constant Ga : S : La : O chalcogenide glasses for magneto-optical devices

The magneto-optical rotation at room temperature was measured for three Ga:S:La:O chalcogenide glasses at several laser lines in the visible. The first sample was a binary system constituted by 70 mol % Ga2S3 and 30 mol % La2O3, whereas in the second and third ones the lanthanum oxide was partially substituted by lanthanum sulfide, keeping the amount of gallium sulfide fixed. A pulsed magnetic field between 50 and 80 kG was used for the Faraday rotation measurements. The Verdet constant for one of the ternary samples was found to be as high as 0.205 min G(-1) cm(-1) at 543 nm, indicating that these chalcogenide glasses are very promising for magneto-optical applications. The data for each sample were fitted using the expected analytical expression for the magneto-optical dispersion. Measurements of the refractive index of the glasses at 632.8 nm are also reported. Data on the magneto-optical properties of two high Verdet constant, heavy-metal oxide diamagnetic glasses are also included for comparison. (C) 1999 Society of Photo-Optical Instrumentation Engineers. [S0091-3286(99)00102-6].

Nonlinear refractive index measurements in antimony-sulfide glass films using a single beam nonlinear image technique

The nonlinear refractive index, n(2), of films based on the new glass system Sb(2)O(3)-Sb(2)S(3) was measured at 1064 nm with laser pulses of 15 ps, using a single-beam nonlinear image technique in presence of a phase object. The films were prepared from bulk glasses by RF-sputtering. A large value of n(2) = 3 x 10-(15) m(2)/W, which is three orders of magnitude larger than for CS(2), was determined. The result shows the strong potential of antimony-sulfide glass films for integrated nonlinear optics. (c) 2005 Elsevier B.V. All rights reserved.

Chemical composition of basalts and basaltic glasses from the Sierra Leone Fracture Zone region

Major and trace element (including REE) geochemistry of basalts and chilled basaltic glasses from the MAR axial zone in the vicinity of the Sierra Leone FZ (5-7°10'N) has been studied. Associations of basalts of various compositions with particular ocean-floor geological structural features have been analyzed as well. Three basaltic varieties have been discriminated. Almost ubiquitous are high-Mg basalts (Variety 1) that are derivatives of N-MORB tholeiitic melts and that are produced in the axial zone of spreading. Variety 2 is alkaline basalts widespread on the southwestern flank of the MAR crest zone in the Sierra Leone region, likely generated through deep mantle melting under plume impact. Variety 3 is basalts derivative from T- and P-MORB-like tholeiitic melts and originating through addition of deeper mantle material to depleted upper mantle melts. Magma generation parameters, as calculated from chilled glass compositions, are different for depleted tholeiites (44-55 km, 1320-1370°C) and enriched tholeiites (45-78 km, 1330-1450°C). Mantle plume impact is shown to affect not only tholeiitic basalt compositions but also magma generation conditions in the axial spreading zone, resulting in higher Ti and Na concentrations in melts parental to rift-related basalts occurring near the plume. T- and P-MORBs are also developed near areas where mantle plumes are localized. High-Mg basalts are shown to come in several types with distinctive Ti and Na contents. Nearly every single MAR segment (bounded by sinistral strike slips and the Bogdanov Fracture Zone) is featured by its own basalt type suggesting that it has formed above an asthenospheric diapir with its unique magma generation conditions. These conditions are time variable. Likely causes of temporal and spatial instability of the mantle upwelling beneath this portion of the MAR are singular tectonic processes and plume activity. In sulfide-bearing rift morphostructures (so-called "Ore area'' and the Markov Basin), basalts make up highly evolved suites generated through olivine and plagioclase fractionation, which is suggestive of relatively long-lived magma chambers beneath the sulfide-bearing rift morphostructures. Functioning of these chambers is a combined effect of singular geodynamic regime and plume activity. In these chambers melts undergo deep differentiation leading to progressively increasing concentration of sulfide phase, eventually to be supplied to the hydrothermal plumbing system.

Mesoporous bioactive glasses as drug delivery and bone tissue regeneration platforms

The use of mesoporous bioactive glasses (MBG) for drug delivery and bone tissue regeneration has grown significantly over the past 5 years. In this review, we highlight the recent advances made in the preparation of MBG particles, spheres, fibers and scaffolds. The advantages of MBG for drug delivery and bone scaffold applications are related to this material’s well-ordered mesopore channel structure, superior bioactivity, and the application for the delivery of both hydrophilic and hydrophobic drugs. A brief forward-looking perspective on the potential clinical applications of MBG in regenerative medicine is also discussed.

Preparation, characterisation and in vivo osteogenesis of mesoporous bioactive glasses

Bone defects, especially large bone defects, remain a major challenge in orthopaedic surgery. Autologous bone transplantation is considered the most effective treatment, but insufficient donor tissue, coupled with concerns about donor site morbidity, has hindered this approach in large-scale applications. Alternative approaches include implanting biomaterials such as bioactive glass (BG), which has been widely used for bone defect healing, due to having generally good biocompatibility, and can be gradually biodegraded during the process of new bone formation. Mesoporous bioactive glass (MBG) is a newly developed bioactive glass which has been proven to have enhanced in-vitro bioactivity; however the in-vivo osteogenesis has not been studied. A critical problem in using the bone tissue engineering approach to restore large bone defects is that the nutrient supply and cell viability at the centre of the scaffold is severely hampered since the diffusion distance of nutrients and oxygen for cell survival is limited to 150-200µm. Cobalt ions has been shown to mimic hypoxia, which plays a pivotal role in coupling angiogenesis with osteogenesis in-vivo by activating hypoxia inducing factor-1α (HIF-1α) transcription factor, subsequently initiating the expression of genes associated with tissue regeneration. Therefore, one aim of this study is to investigate the in-vivo osteogenesis of MBG by comparison with BG and β-TCP, which are widely used clinically. The other aim is to explore hypoxia-mimicking biomaterials by incorporating Cobalt into MBG and β-TCP. MBG and β-TCP incorporated with 5% cobalt (5Co-MBG and 5CCP) have also been studied in-vivo to determine whether the hypoxic effect has a beneficial effect on the bone formation. The composition and microstructure of synthesised materials (BG, MBG, 5Co-MBG, 5CCP) were characterised, along with the mesopore properties of the MBG materials. Dissolution and cytotoxicity of the Co-containing materials were also investigated. Femoral samples with defects harvested at 4 and 8 weeks were scanned using micro-CT followed by processing for histology (H&E staining) to determine bone formation. Histology of MBG showed a slower rate of bone formation at 4 weeks than BG, however at 8 weeks it could be clearly seen that MBG had more bone formation. The in-vivo results show that the osteogenesis of MBG reciprocates the enhanced performance shown in-vitro compared to BG. Dissolution study showed that Co ions can be efficiently released from MBG and β-TCP in a controllable way. Low amounts of Co incorporated into the MBG and β-TCP showed no significant cytotoxicity and the Co-MBG powders maintained a mesopore structure although not as highly ordered as pure MBG. Preliminary study has shown that Co incorporated samples showed little to no bone formation, instead incurring high lymphocyte activity. Further studies need to be done on Co incorporated materials to determine the cause for high lymphocyte activity in-vivo, which appear to hinder bone formation. In conclusion, this study demonstrated the osteogenic activity of MBG and provided some valuable information of tissue reaction to Co-incorporated MBG and TCP materials.