β-Eucryptite by a Sol-Gel Route

-Eucryptite solid solution (LAS) Li2O : Al 2O3 : 3SiO2(113) was prepared via a sol-gel route. Complex solutions of lithium or aluminum salts in ethanol/water mixtures were catalysed by inorganic acids (catalyst/alkoxide ratio 0.1). Different ratios of H2SO4 catalyst were also used.TGA showed that the maximum % yield of LAS 113 occurred using H2SO4 catalyst. Above 400°C exothermic peaks occurred in DSC followed by the glass transition. XRD and IR showed a high crystallinity of -eucryptite solid solution using all acids at the 0.1 ratio with the highest crystallinity for the 0.05 H2SO4 ratio. SEM revealed similar grain sizes in spite of higher acid concentrations. XRD data indicated a change to a tetragonal modification with higher catalyst ratio.     

External polyacrylate-coating as alternative material for preparation of photopolymerized sol-gel monolithic column

Photopolymerized sol-gel monolithic columns for use in capillary electrochromatography were prepared in 125 microm i.d. polyacrylate-coated fused-silica capillaries. The polyacrylate-coating, unlike the polyimide one, is transparent to the radiation used (approximately 370 nm), and thus, no coating removal is necessary. This is a very important particularity since intrinsic capillary column characteristics, such as flexibility and mechanical resistance, are unchanged. A mixture containing metacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photoinitiator was irradiated at 370 nm for 20 min inside the capillaries to prepare the columns through sol-gel approach. The versatility and viability of the use of polyacrilate as a new capillary external coating were shown through preparation of two columns under different conditions, which were tested in electrochromatography for separation of standard mixture containing thiourea (marker compound), propylbenzene, phenanthrene and pyrene.     

Erbium and ytterbium co-doped SiO<Subscript>2</Subscript>:GeO<Subscript>2</Subscript> planar waveguide prepared by the sol–gel route using an alternative precursor

The sol–gel method combined with a spin-coating technique has been successfully applied for the preparation of rare-earth doped silica:germania films used for the fabrication of erbium-doped waveguide amplifiers (EDWA), presenting several advantages over other methods for the preparation of thin films. As with other methods, the sol–gel route also shows some drawbacks, such as cracks related to the thickness of silica films and high hydrolysis rate of certain precursors such as germanium alkoxides. This article describes the preparation and optical characterization of erbium and ytterbium co-doped SiO₂:GeO₂ crack-free thick films prepared by the sol–gel route combined with a spin-coating technique using a chemically stable non-aqueous germanium oxide solution as an alternative precursor. The non-crystalline films obtained are planar waveguides exhibiting a single mode at 1,550 nm with an average thickness of 3.9 μm presenting low percentages of porosity evaluated by the Lorentz–Lorenz Effective Medium Approximation, and low stress, according to the refractive index values measured in both transversal electric and magnetic polarizations. Weakly confining core layers (0.3% < Δn < 0.75%) were obtained according to the refractive index difference between the core and buffer layers, suggesting that low-loss coupling EDWA may be obtained. The life time of the erbium ⁴I_13/2 metastable state was measured as a function of erbium concentration in different systems and based on these values it is possible to infer that the hydroxyl group was reduced and the formation of rare-earth clusters was avoided.     

Synthesis and characterization of microcrystalline cellulose produced from bacterial cellulose

In this study, microcrystalline cellulose (MCC) was prepared from the acid hydrolysis of bacterial cellulose (BC) produced in culture medium of static Acetobacter xylinum. The MCC-BC produced an average particle size between 70 and 90 μm and a degree of polymerization (DP) of 250. The characterization of samples was performed by thermogravimetric analysis, X-ray diffraction, and scanning electron microscopy (SEM). The MCC shows a lower thermal stability than the pristine cellulose, which was expected due to the decrease in the DP during the hydrolysis process. In addition, from X-ray diffractograms, we observed a change in the crystalline structure. The images of SEM for the BC and MCC show clear differences with modifications of BC fiber structure and production of particles with characteristics similar to commercial MCC.     

Frequency upconversion in rare-earth doped fluoroindate glasses

We present recent results on frequency upconversion (UPC) obtained in fluoroindate glasses (FIG) doped with Ho³⁺, Tm³⁺ and Nd³⁺ ions and codoped with Pr³⁺/Nd³⁺ and Yb³⁺/Tb³⁺ ions. The results for the Ho³⁺-doped samples show strong evidence of energy transfer (ET) between Ho³⁺ ions resonantly excited at 640 nm. The origin of the blue-green upconverted fluorescence observed was identified and the dynamics of the signals revealed the pathways involved in the UPC process. In the case of Tm³⁺-doped FIG, the samples were resonantly excited at 650 nm and the main mechanism that contributes for the red-to-blue upconversion is excited-state absorption (ESA). The FIG samples codoped with Pr³⁺/Nd³⁺ were excited at 588 nm in resonance with transitions starting from the ground state of the Nd³⁺ and the Pr³⁺ ions. It was observed that the presence of Nd³⁺ ions enhanced the Pr³⁺ emission at 480 nm by two orders of magnitude. Multiphonon (MP)-assisted upconversion is also discussed for Nd³⁺-doped FIG pumped at 866 nm. Emission at 750 nm with a peculiar linear dependence with the laser intensity was observed and explained. A rate-equation model that includes MP absorption via thermally coupled electronic excited states of Nd³⁺ was developed and describes well the experimental results. The role played by effective phonon modes is clearly demonstrated. MP-assisted UPC process was also studied in Yb³⁺/Tb³⁺-codoped FIG samples excited at 1064 nm, which is off-resonance with electronic transitions starting from the ground state. It was determined that the mechanism leading to Tb³⁺ emission in the blue is due to ET from a pair of excited Yb³⁺ ions followed by ESA in the Tb³⁺ ions.     

Photoinduced effect in Ga-Ge-S based thin films

Glassy films of Ga₁₀Ge₂₅S₆₅ with 4 μm thickness were deposited on quartz substrates by electron beam evaporation. Photoexpansion (PE) (photoinduced increase in volume) and photobleaching (PB) (blue shift of the bandgap) effects have been examined. The exposed areas have been analyzed using perfilometer and an expansion of 1.7 μm (ΔV/V ≈ 30%) is observed for composition Ga₁₀Ge₂₅S₆₅ exposed during 180 min and 3 mW/cm² power density. The optical absorption edge measured for the film Ge₂₅Ga₁₀S₆₅ above and below the bandgap show that the blue shift of the gap by below bandgap photon illumination is considerable higher (ΔE_g = 440 meV) than ΔE_g induced by above bandgap illumination (ΔE_g = 190 meV). The distribution of the refraction index profile showed a negative change of the refraction index in the irradiated samples (Δn = −0.6). The morphology was examined using a scanning electron microscopy (SEM). The chemical compositions measured using an energy dispersive analyzer (EDX) indicate an increase of the oxygen atoms into the irradiated area. Using a Lloyd's mirror setup for continuous wave holography it was possible to record holographic gratings using the photoinduced effects that occur in them. Diffraction efficiency up to 25% was achieved for the recorded gratings and atomic force microscopy images are presented.     

Redox behavior of molybdenum and tungsten in phosphate glasses

In this work, vitreous samples were prepared in the binary system (100 - x)NaPO3-xMO3 with M = Mo and W and x varying from 10 to 60. The transmittance properties in the UV, visible, and near-infrared were monitored as a function of MO3 concentration. In both cases, an increase in the amount of transition metal results in an intense and broad absorption band in the visible and near-infrared attributed to metal reduction under synthesis conditions. It was shown that this large absorption can be partially or totally removed using specific oxidizing agents or by improving synthesis parameters such as melting temperature or cooling rate of the melt. In addition, structural investigations by Raman and X-ray absorption spectroscopy suggest that reduction only occurs when the metal cation is in octahedral geometry and that the transmittance improvement is not related with any structural changes. These results were explained in terms of thermodynamic equilibrium of redox species in the melt and allowed to obtain for the first time transparent and chemically stable glasses containing high concentrations of MO3 with transition metals in octahedral geometry inside the glass network.     

Reaction of Dimethyl Acetylene-Dicarobxylate With Triazinone

Abstract

The addition of dimethyl acetylenedicarboxylate (DMAD) to 6-menthy-1, 2,4-triazlne-3(2H)thione-5(4H)-one afforded 2-methoxylcarboxy-7-methyl-1,3-thiazino[3,2-b][1,2,4]triazine-4,8-dione.     

A Relation Between Closure Operators on a Small Category and Its Category of Presheaves

In this paper we show that each factorization structure on a small category , satisfying certain conditions, yields a presheaf on and a morphism of presheaves . We then give connections, and set up one to one correspondences, between subclasses of the following classes: (a) closure operators on (b) subobjects of (c) morphisms from to (d) weak Lawvere–Tierney topologies (e) weak Grothendieck topologies (f) closure operators on .     

Bulk photochromism in a tungstate-phosphate glass: a new optical memory material?

In this work, we present a new photochromic tungstate based glass which have both absorption coefficient and refractive index modified under laser exposure. The photosensitive effect is superficial under ultraviolet (UV) irradiation but occurs in the entire volume of the glass under visible irradiation. The effect can be obtained in any specific point inside the volume using an infrared femtosecond laser. In addition, the photosensitive phenomenon can be erased by specific heat treatment. This glass can be useful to substitute actual data storage supports and is a promising material for 3-dimensional (3D) and holographic optical storage.