Picosecond nonlinearity of GeO2-Bi2O3-PbO-TiO2 glasses at 532 and 1,064 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of Ag nanoparticles on the radiative properties of tellurite glasses doped with Er3+, Yb3+ and Tm3+ ions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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.

Characteristics of PbO-BiO1.5-GaO1.5 glasses melted in SnO2 crucibles

PbO-BiO 1.5-GaO 1.5-based glasses are good candidates for optical applications, because of some of their interesting characteristics, such as high refraction indices and high transmission in the ultraviolet (UV), visible (VIS), and infrared (IR) regions. A limited stage in the processing of these glasses is the corrosion that is caused by the melt in all currently used conventional crucibles, such as noble metals (platinum or gold) and Al 2O 3. The absorption of crucible material by the glass composition may reduce the transmission level, the cutoff in the UV-VIS, and IR regions, and the thermal stability. In this study, a SnO 2 crucible has been tested for PbO-BiO 1.5-GaO 1.5 molten glass. Optical and thermal analyses show, in some cases, advantages over the use of platinum and Al 2O 3 crucibles. A visible cutoff value of 474 nm has been measured, and a longer melting time (850°C for 4 h) results in a significant reduction of the O-H absorption band at 3.2 μm.

IR-visible upconversion and thermal effects in Pr3+/Yb3+-codoped Ga2O3 : La2S3 chalcogenide glasses

IR-visible upconversion fluorescence spectroscopy and thermal effects in pr(3+)/Yb3+-codoped Ga2O3:La2S3 chalcogenide glasses excited at 1.064 mum is reported. Intense visible upconversion emission in the wavelength region of 480-680 nm peaked around 500, 550, 620 and 660 nm is observed. Upconversion excitation of the Pr3+ excited-state visible emitting levels is achieved by st combination of phonon-assisted absorption, energy-transfer and phonon-assisted excited-state absorption processes. A threefold upconversion emission enhancement induced by thermal effects when the codoped sample was heated in the temperature range of 20-200 degreesC is demonstrated. The thermal-induced enhancement is attributed to a multiphonon-assisted anti-Stokes process which takes place in the excitation of the ytterbium and excited-state absorption of the praseodymium. The thermal effect is modelled by conventional rate equations considering temperature-dependent effective absorption cross-sections for the F-2(7/2)-F-2(5/2) ytterbium transition and (1)G(4)-P-3(0) praseadymium excited-state absorption, and it is shown to agree very well with experimental results. Frequency upconversion in singly Pr3+-doped samples pumped at 836 nm and 1.064 mum in a two-beam configuration is also examined.

Incorporation of PbF2 into Heavy Metal Oxide Borate Glasses. Structural Studies by Solid State NMR

A series of heavy metal oxide (HMO) glasses with composition 26.66B(2)O(3)-16GeO(2)-4 Bi2O3-(53.33-x)PbO-xPbF2 (0 <= x <= 40) were prepared and characterized with respect to their bulk (glass transition and crystallization temperatures, densities, molar volumes) and spectroscopic properties. Homogeneous glasses are formed up to x = 30, while crystallization of beta-PbF2 takes place at higher contents. Substitution of PbO by PbF2 shifts the optical band gap toward higher energies, thereby extending the UV transmission window significantly toward higher frequencies. Raman and infrared absorption spectra can be interpreted in conjunction with published reference data. Using B-11 and F-19 high-resolution solid state NMR as well as B-11/F-19 double resonance methodologies, we develop a quantitative structural description of this material. The fraction of four-coordinate boron is found to be moderately higher compared to that in glasses with the same PbO/B2O3 ratios, suggesting some participation of PbF2 in the network transformation process. This suggestion is confirmed by the F-19 NMR spectra. While the majority of the fluoride ions is present as ionic fluoride, similar to 20% of the fluorine inventory acts as a network modifier, resulting in the formation of four-coordinate BO3/2F- units. These units can be identified by F-19{B-11} rotational echo double resonance and B-11{F-19} cross-polarization magic angle spinning (CPMAS) data. These results provide the first unambiguous evidence of B-F bonding in a PbF2-modified glass system. The majority of the fluoride ions are found in a lead-dominated environment. F-19-F-19 homonuclear dipolar second moments measured by spin echo decay spectroscopy are quantitatively consistent with a model in which these ions are randomly distributed within the network modifier subdomain consisting of PbO, Bi2O3, and PbF2. This model, which implies both the features of atomic scale mixing with the network former borate species and some degree of fluoride ion clustering is consistent with all of the experimental data obtained on these glasses.

Frequency upconversion properties of Tm3+ doped TeO2-ZnO glasses containing silver nanoparticles

Frequency upconversion (UC) properties of Tm3+ doped TeO2-ZnO glasses containing silver nanoparticles (NPs) were investigated. Infrared-to-visible and infrared-to-infrared UC processes associated to the Tm3+ ions were studied by exciting the samples with a cw 1050 nm ytterbium laser. The luminescence intensity as a function of laser intensity was also measured using a pulsed 1047 nm Nd3+:YVO laser in order to determine the number of photons participating in the UC processes. Enhancement of the UC signals for samples heat-treated during various time intervals is attributed to the growth of the local field in the vicinity of the NPs. PL enhancement by one-order of magnitude was observed in the whole spectrum of the samples heat-treated during 48 h. On the other hand PL quenching was observed for the samples heat-treated more than 48 h. (c) 2011 Elsevier B.V. All rights reserved.

Down-conversion process in Tb3+-Yb3+ co-doped Calibo glasses

The down-conversion process in Tb3+-Yb3+ co-doped Calibo glasses was studied. The emission, excitation and time-resolved measurements indicated the existence of an energy conversion through the excitation of Tb3+ ions to near-infrared emission by Yb3+ ions. The emission intensity dependence on excitation power confirms that the one-photon process is responsible for the Yb3+ emission. An enhanced Yb3+ emission was observed with Yb3+ doping and an optimal energy transfer efficiency of 32% was obtained before reaching near-infrared emission quenching. The mechanism of the non-resonant energy transfer from Tb3+ to Yb3+ is discussed in terms of the Tb3+-Yb3+ cross-relaxation and multiphonon decay processes. (C) 2012 Elsevier B.V. All rights reserved.

Spectroscopic investigation and heat generation of Yb3+/Ho3+ codoped aluminosilicate glasses looking for the emission at 2 μm

Energy transfer (ET) and heat generation processes in Yb3+/Ho3+-codoped low-silica calcium aluminosilicate glasses were investigated using thermal lens (TL) and photoluminescence measurements looking for the emission around 2.0 μm. Stepwise ET processes from Yb3+ to Ho3+, upon excitation at 0.976 μm, produced highly efficient emission in the mid-infrared range at around 2.0 μm, with high fluorescence quantum efficiency (η1 ∼ 0.85 and independent of Ho3+ concentration) and relatively very low thermal loading (<0.4) for concentration up to 1.5% of Ho2O3. An equation was deduced for the description of the TL results that provided the absolute value of η1 and the number of emitted photons at 2.0 μm per absorbed pump photon by the Yb3+ ions, the latter reaching 60% for the highest Ho3+ concentration. These results suggest that the studied codoped system would be a promising candidate for the construction of photonic devices, especially for medical applications.

(Table 1) H2O and CO2 contents in submarine basaltic glasses from Ontong Java Plateau

The Ontong Java Plateau in the western Pacific is anomalous compared to other oceanic large igneous provinces in that it appears to have never formed a large subaerial plateau. Paleoeruption depths (at 122 Ma) estimated from dissolved H2O and CO2 in submarine basaltic glass pillow rims vary from ~1100 m below sea level (mbsl) on the central part of the plateau to 2200-3000 mbsl on the northeastern edge. Our results suggest maximum initial uplift for the plateau of 2500-3600 m above the surrounding seafloor and 1500+/-400 m of postemplacement subsidence since 122 Ma. Our estimates of uplift and subsidence for the plateau are significantly less than predictions from thermal models of oceanic lithosphere, and thus our results are inconsistent with formation of the plateau by a high-temperature mantle plume. Two controversial possibilities to explain the anomalous uplift and subsidence are that the plateau (1) formed as a result of a giant bolide impact, or (2) formed from a mantle plume but has a lower crust of dense garnet granulite and/or eclogite; neither of these possibilities is fully consistent with all available geological, geophysical, and geochemical data. The origin of the largest magmatic event on Earth in the past 200 m.y. thus remains an enigma.

Chemical and isotopic compositions of basaltic glasses and crusts from the Mid-Atlantic Ridge rift valley

Data presented in the paper suggest significant differences between thermodynamic conditions, under which magmatic complexes were formed in MAR at 29°-34°N and 12°-18°N. Melts occurring at 29°-34°N were derived by melting of a mantle source with homogeneous distribution of volatile components and arrived at the surface without significant fractionation, likely, due to their rapid ascent. The MAR segments between 12° and 18°N combine contrasting geodynamic environments of magmatism, which predetermined development of a large plume region with widespread mixing of melting products of geochemically distinct mantle sources. At the same time, this region is characterized by conditions favorable for origin of localized zones of anomalous plume magmatism. These sporadic magmatic sources were spatially restricted to MAR fragments with the Hess crust, whose compositional and mechanical properties were, perhaps, favorable for focusing and localization of plume magmatism. The plume source between 12° and 18°N beneath MAR may be geochemically heterogeneous.

The in-vitro bioactivity of mesoporous bioactive glasses

Ordered mesoporous bioactive glasses (MBGs) with different compositions were prepared by using nonionic block copolymer surfactants as structure-directing agents through an evaporation-induced self-assembly process. Their in-vitro bioactivities were studied in detail by electron microscopy, Fourier-transform infrared spectroscopy, and inductively coupled plasma (ICP) atomic emission spectroscopy. The ICP element analysis results were further calculated in terms of the total consumption of Ca and P, Delta[Ca]/Delta[P] ratios, and ionic activity product (IP) of hydroxyapatite. Through the above analysis, it is clear that MBGs show a different structure-bioactivity correlation compared to conventional sol-gel-derivcd BGs. The in vitro bioactivity of MBGs is dependent on the Si/Ca ratio in the network when the other material parameters such as the mesostructure and texture properties (pore size, pore volume) are controlled. MBG 80S15C with relatively lower calcium content exhibits the best in vitro bioactivity, in contrast to conventional sol-gel-derived BGs where usually higher calcium percentage BGs (e.g. 60S35C) show better bioactivity. Calcination temperature is another important factor that influences the in vitro bioactivity. According to our results, MBGs calcined at 973 K may possess the best in vitro bioactivity. The influences of the composition and calcination temperature upon bioactivity are explained in terms of the unique structures of MBGs. (c) 2006 Elsevier Ltd. All rights reserved.