A Pb MAS-NMR study of Pb-containing glasses

²⁰⁷Pb magic angle spinning (MAS)-NMR spectra have been obtained for various Pb-containing crystalline compounds and high lead glasses. The isotropic chemical shifts were determined for the crystalline samples. The more ionic lead atoms with a coordination number larger than six had relatively small chemical shifts between 0 and 2382 ppm with respect to crystalline Pb(NO₃)₂. On the other hand, the covalent lead atoms with PbO₃ trigonal and PbO₄ square pyramidal configurations gave a multiplet line profile with shifts ranging from about 3000 to 6000 ppm. The lead atoms with different local environments in PbSiO₃ (alamosite) and H-Pb₂SiO₄, for instance, could be clearly distinguished from each other on the basis of the isotropic chemical shift. The NMR spectra for the high lead glasses of composition 67PbO·33SiO₂, 80PbO·20B₂O₃ and 70PbO· 30GaO_1.5 were found to exhibit an extremely broad peak with a shift ranging from about 3000 to 6000 ppm. This shift indicates that, in these glasses, neither such highly ionic lead atoms as found in symmetrical PbO₆ octahedra nor such highly covalent ones as found in PbO₄ square pyramids in the PbO crystal are predominant, but instead PbO₃ trigonal or PbO₄ square pyramids, with two or three other neighboring oxygens at larger distances as found in H-Pb₂SiO₄ or PbSiO₃, are the major lead-oxygen configuration.     

Rheology of sols and fiber drawing

The investigations on the viscosity of the metal alkoxide solutions in the course of hydrolysis and condensation reactions leading to the gelation of sols have been reviewed. All the solutions which gel finally show a continuous increase in viscosity with time until they gel at a certain viscosity higher than about 100 P which is dependent on the composition of the starting solution. When a metal alkoxide solution is catalyzed with an acid and its water content is small at less than 4 or 5 in the water to alkoxide mol ratio, the solution exhibits spinnability at viscosities above about 10 P and becomes drawable into gel fibers, whereas no spinnability appears when a solution contains a large amount of water or is catalyzed with an alkali like ammonia.

The investigations on the relation between the reduced viscosity and the concentration or the relation between the intrinsic viscosity and the number-averaged molecular weight have made it clear that the spinnable silicon alkoxide solutions have long-shaped siloxane particles and non-spinnable solutions have round particles.

It has been established that spinnable solutions exhibit Newtonian flow behavior up to high viscosities, where fibers can be drawn, while non-spinnable solutions exhibit marked structural viscosity and, sometimes, thixotropy. Similar behavior is confirmed in the alumina solutions prepared from inorganic salts. It has been reported that the viscosity measurements provide information on the rate of the reaction leading to gelation. It is also known that the viscosity of the alkoxide solution controls the thickness of the thin coating film made by the dip-coating technique using an alkoxide solution.     

Sintering of silica gel derived from the alkoxysilane solution containing N,N-dimethylformamide

The sintering of three kinds of dried gels with different microstructures prepared from the tetramethoxysilane (TMOS) solutions containing N,N-dimethylformamide (DMF) with varying [H₂O]/[TMOS] mole ratios and different catalysts was investigated by measuring the pore size distribution, the Vickers hardness, the linear shrinkage and the apparent density of the gels heated to various temperatures. The marked shrinkage of the pores started at temperatures above 900 °C. The temperature required for the conversion of a gel to a pore-free silica glass depended on the average size of the pores contained in the dried gels; the average pore sizes of about 50 Å, 75 Å and 100 Å corresponded to 1040 °C, 1060°C and 1080°C, respectively. The Vickers hardness, the linear shrinkage and the density of the gel showed a corresponding change with a change in heating temperature.     

Sensitized broadband near-infrared luminescence from bismuth-doped silicon-rich silica films

Developing Si compatible optical sources has attracted a great deal of attention owing to the potential for forming inexpensive, monolithic Si-based integrated devices. In this Letter, we show that ultra broadband near-IR (NIR) luminescence in the optical telecommunication window of silica optical fibers was obtained for Bi-doped silicon-rich silica films prepared by a co-sputtering method. Without excess Si, i.e., Bi-doped pure silica films, no luminescence was observed in the NIR range. A broad Bi-related NIR photoluminescence appears when excess Si was doped in the Bi-doped silica. The luminescence properties depended strongly on the amount of excess Si and the annealing temperature. Photoluminescence results suggest that excess Si acts as an agent to activate Bi NIR luminescence centers and also as an energy donor to transfer excitation energy to the centers. It is believed that this peculiar structure might find some important applications in Si photonics.     

A soluble hybrid material combining carbon nanohorns and C60

A soluble hybrid nanomaterial that combines fullerenes and carbon nanohorns (CNHs) has been prepared and fully characterized. Electrochemical investigations revealed that the CNHs modify the electron accepting ability of C(60) in the hybrid material.     

β-d-Xylosidase from Geobacillus thermoleovorans IT-08: Biochemical Characterization and Bioinformatics of the Enzyme

The gene encoding a thermostable β-d-xylosidase (GbtXyl43B) from Geobacillus thermoleovorans IT-08 was cloned in pET30a and expressed in Escherichia coli; additionally, characterization and kinetic analysis of GbtXyl43B were carried out. The gene product was purified to apparent homogeneity showing M _r of 72 by sodium dodecyl sulfate polyacrylamide gel electrophoresis. The enzyme exhibited an optimum temperature and pH of 60 °C and 6.0, respectively. In terms of stability, GbtXyl43B was stable at 60 °C at pH 6.0 for 1 h as well as at pH 6–8 at 4 °C for 24 h. The enzyme had a catalytic efficiency (k _cat/K _M) of 0.0048?±?0.0010 s^?1 mM^?1 on p-nitrophenyl-β-d-xylopyranoside substrate. Thin layer chromatography product analysis indicated that GbtXyl43B was exoglycosidase cleaving single xylose units from the nonreducing end of xylan. The activity of GbtXyl43B on insoluble xylan was eightfold higher than on soluble xylan. Bioinformatics analysis showed that GbtXyl43B belonging to glycoside hydrolase family 43 contained carbohydrate-binding module (CBM; residues 15 to 149 forming eight antiparallel β-strands) and catalytic module (residues 157 to 604 forming five-bladed β-propeller fold with predicted catalytic residues to be Asp287 and Glu476). CBM of GbtXyl43B dominated by the Phe residues which grip the carbohydrate is proposed as a novel CBM36 subfamily.     

57Fe-Mössbauer study of electrically conducting barium iron vanadate glass after heat treatment

Local structure and thermal durability of semiconducting xBaO·(90?? x)V₂O₅ · 10Fe₂O₃ glasses (x = 20, 30 and 40), NTA glass ^TM, before and after isothermal annealing were investigated by ⁵⁷Fe-Mössbauer spectroscopy and differential thermal analysis (DTA). An identical isomer shift ( $\mathit{\delta}$ ) of 0.39 ± 0.01 mm s^???1 and a systematic increase in the quadrupole splitting (Δ) were observed from 0.70 ± 0.02 to 0.80 ± 0.02 mm s^???1 with an increasing BaO content, showing an increase in the local distortion of Fe^IIIO₄ tetrahedra. From the slope of the straight line in the T _g–Δ plot of NTA glass ^TM, it proved that Fe^III plays a role of network former. Large Debye temperature (Θ _D) values of 1000 and 486 K were respectively obtained for 20BaO · 70V₂O₅ · 10Fe₂O₃ glass before and after isothermal annealing at 400°C for 60 min, respectively. This result also suggests that Fe^III atoms constitute the glass network composed of tetrahedral FeO₄, tetrahedral VO₄ and pyramidal VO₅ units. The electric conductivity of 20BaO · 70V₂O₅ · 10Fe₂O₃ glass increased from 1.6 × 10^???5 to 5.8 × 10^???2 S cm^???1 after isothermal annealing at 450°C for 2,000 min. These results suggest that the drastic increase in the electric conductivity caused by heat treatment is closely related to the structural relaxation of the glass network structure.