Determination of diffusion coefficient of titanium ion in TiO2---SiO2 wet gel prepared from metal alkoxides during leaching

It was found that the radial gradient refractive index (r-GRIN) glass rod could be produced by the leaching of wet gel prepared by a sol-gel method from metal alkoxides and heat-treatment of the gel. The concentration gradient of the doped component resulting from its diffusion in the wet gel was studied. In order to estimate the exact diffusion coefficient of the titanium ion in the binary TiO₂---SiO₂ wet gel, its value was measured by using two methods. The observed diffusion coefficient by colorimetric analysis was about 1.1 × 10⁻⁶ cm²/s, while the value obtained from analysis of EPMA was about 1.2 × 10⁻⁶ cm²/s, and both values were nearly equal to each other. The activation energy of titanium ion diffusion in the wet gel was estimated to be about 11 kcal/mol.     

Sol-gel preparation and optical properties of SiO2-Ta2O5 glass

Tantalum-doped silica glass was fabricated by the sol-gel process in order to obtain a glass with a high refractive index for optical use. A crack-free, clear glass rod was successfully prepared from a low-density gel and used as the core material for fabricating optical fibers. Transmission loss in the fabricated fibers was high, in the range of 10³-10⁴ dB/km, which may be caused by coloration due to the multivalency of tantalum; however, the loss was reduced by nearly one order of magnitude by heat treatment at 800 °C, that is, to 75 dB/km at a wavelength of 0.8 μm.     

Low temperature synthesis of non-crystalline solids of the system SrO-SiO2

Non-crystalline solids within the liquid-liquid immiscibility region in the system SrO-SiO₂ have been prepared from a gel obtained by the hydrolysis of silicon tetramethoxide with an aqueous solution of strontium nitrate. The gel which was porous and translucent at room temperature increased in transparency with heating due to the collapse of micropores until it became completely clear. The gel became opaque again due to the precipitation of α-quartz at higher temperatures. The critical temperatures below which clear solids were obtained fell on a line connecting the glass transition temperatures of vitreous silica and those of SrO-SiO₂ glasses prepared by melting. The density and refractive index of the pore-free, clear glassy solid, changed continuously with the SrO content along lines connecting those of vitreous silica and SrO- SiO₂ glasses of high SrO content prepared by melting. The maximum amount Sr²⁺ which could be introduced using an aqueous solution as the starting material corresponded to a composition of 10 SrO · 90 SiO₂ by weight.     

Colloidal sol/gel processing of ultra-low expansion TiO2/SiO2 glasses

A series of titania-silica glasses with 0–9% TiO₂ were fabricated using a sol/gel process. The sol was prepared by dispersing colloidal silica fume in an aqueous solution of titania which was synthesized through the acid-catalyzed hydrolysis of titanium isopropoxide. The sols gelled in 2–4 days, and then were dried for 6–8 days. The dry gels were sintered at 1450–1500°C to produce clear, dense, microstructure-free glasses. The gels underwent a total shrinkage of 50% to yield glass rods about 50 mm long and 5 mm in diameter, or glass discs about 4 cm in diameter and 5 mm thick. The drying step was most critical in the production of crack-free specimens.

In the gel, the transmission electron microscope (TEM) revealed the presence of 1–5 nm rutile microcrystallites uniformly distributed within a network of colloidal silica particles. After sintering to 1450–1500°C, though, a dense, transparent, microstructure-free glass was created. Fourier transform infrared spectroscopy (FTIR) verified the formation of an amorphous solid-solution of titania and silica after sintering.

The thermal expansion of the glasses was measured using a differential dilatometer. The average linear coefficients of thermal expansion (CTE @ 25–675°C) varied between +5 × 10⁻⁷ and −0.2 × 10⁻⁷°C⁻¹ in the range 0 to 9% TiO₂. The glass with 7.2% TiO₂ exhibited a zero thermal expansion coefficient at 150–210°C. The hysteresis in CTE on heating and cooling was of the order of 0.01–0.02 ppm.     

Thin SiO2---TiO2---ZrO2 films from alkoxide solutions

Different solutions containing alkoxides of silicon, titanium, and zirconium have been prepared. Some of their properties like the time dependent viscosity and the gelling time have been measured and are reported here for different H₂O, HCl, ethanol and/or formamide contents. Microscope slides have been dip coated in these solutions. After baking, film thickness and chemical durability have been determined.

In order to get good SiO₂---TiO₂---ZrO₂ glass coatings, the withdrawal speed should not exceed 5 cm/min unless the viscosities of the solutions are reduced by the addition of ethanol. By such a dilution, the film thickness could also be reduced, while the addition of formamide caused a delayed increase of the viscosity and increased gelling times. For this reason, solutions containing formamide can be used for longer periods. The chemical durability of the substrates against boiling NaOH solution is enhanced by the SiO₂---TiO₂---ZrO₂ glass coatings.     

Gel synthesis of glass powders in the BaO---Al2O3---SiO2 system

Homogeneous glass powders were prepared from multicomponent silicate gels in the BaO---Al₂O₃---SiO₂ system. Gels synthesized from TEOS, Al-sec-butoxide, and Ba-acetate were characterized by TGA, DSC, and single-point BET analysis. Amorphous oxide powders of controlled composition were obtained through an appropriate drying and heat treatment schedule. Inclusion-free clear oxynitride glasses were also prepared by co-melting gel synthesized oxide powders with silicon nitride powders.     

Glass formation, physico-chemical properties, and structure of glasses based on Ga2S3-GeS2-Sb2S3 system

We prepared sulfide glasses based on a Ga₂S₃-GeS₂-Sb₂S₃ system and investigated the compositional dependences of their physico-chemical properties and structure. Additivities were observed for density and refractive index; i.e., these properties were presented by the summation of the contribution from each component. With the increase of Sb₂S₃ content, the density, refractive index, and thermal expansion coefficient increased while the glass transition and softening temperatures decreased, and the short-wavelength absorption edge shifted to the longer wavelength side. These variations are expected from the incorporation of a heavy element (Sb) into the glasses. On the other hand, the replacement of GeS₂ by Ga₂S₃ increased the density and refractive index, and shifted the short-wavelength absorption edge to the longer wavelength side. These variations were explained by the increase of the number densities of the cations with the replacement and the formation of metal-metal bonds. The latter was confirmed from the Raman spectra. We also investigated the effects of Ag₂S incorporation on the optical properties. The incorporation of Ag₂S increased the density and refractive index whereas the position of the short-wavelength absorption edge varied little. These results show the possibility of fabricating an optical waveguide by Ag incorporation into the glasses.     

Some characteristics of glass in the Al2O3---B2O3---SiO2 system from the gel

The colorless and transparent glasses in the Al₂O₃---B₂O₃---SiO₃ system with high B₂O₃ and SiO₂ content were prepared from gels at low temperature. Their IR spectra not only revealed the evolution of the gel to glass conversion, but also showed that the formation of mixed bonds in the glasses obtained did not show any effect due to the B₂O₃ content. The accuracy of the glass composition is dependent upon the SiO₂/B₂O₃ molar ratio. The higher the ratio, the less the deviation of the analyzed compositions of the resulting glasses from their original calculated values. It is obvious that the higher the ratio, the lower the thermal expansion coefficient and the higher the transformation temperature of the glass, and the temperature at which the thermal contraction reaches an equilibrium is higher.     

Viscosity matching of new PbF2–InF3–GaF3 based fluoride glasses and ZBLAN for high NA optical fiber

New multicomponent PbF₂–InF₃–GaF₃ bulk glasses have been investigated. They show lower phonon energy (540 cm⁻¹) in comparison with 580 cm⁻¹ for ZBLAN. Large PbF₂ concentration provided glasses with high refractive index up to 1.582 and the viscosity curves revealed an excellent thermal compatibility with ZBLAYN glass. A multimode fiber with a numerical aperture of 0.51, a loss of 0.85 dB/m at 1.3 μm was fabricated using the rotational casting method.     

Ionic conduction in As2S3---Ag2S, GeS2---GeS---Ag2S and P2S5---Ag2S glasses

The glass-forming region in the system P---S---Ag was determined and density, thermal expansion, dc conductivity and the transport number of Ag ions were measured for P₂S₅---Ag₂S glasses found in the P---S---Ag system. The results for the transport number measurement show that P₂S₅---Ag₂S glasses are purely ionic conductors owing to the Ag ion migration, like most of the As₂S₃---Ag₂S and GeS₂---GeS---Ag₂S glasses reported previously. Glass structure and ionic conduction processes in As₂S₃---Ag₂S, GeS₂---GeS---Ag₂S and P₂S₅---Ag₂S glasses are discussed, based on their ionic conductivity and density data. The structural concept of -Ag₂S was applied to these glasses, which suggests that the Ag ions in the glasses are distributed in the available Ag ion sites in the non-conducting framework composed of both S anions and As, Ge or P cations. In each system the ionic conductivity increases linearly with increasing Ag⁺/total cation (%) in glass composition, the determining factor being the activation energy for ionic conduction alone. Thus, the activation energy in these glasses depends predominantly upon the molar ratio of Ag ions to total cation in the glass, irrespective of the kind of system. Small differences in the activation energy among the three systems can be interpreted as arising from differences in the field strength of As, Ge and P cations.     

Fabrication of fluorine-doped silica glasses by the sol-gel method

Fluorine-doped silica glasses are produced by the sol-gel method for optical fiber preforms. In order to dope fluorine into silica glass, fluorinated silicon alkoxide, Si(OC₂H₅)₃F, is titrated into SiO₂ sol solutions. The fluorine content in silica glass depends on: the fluorine concentration in the gel, the specific surface area of SiO₂ particles and the heating rate in the sintering process. Fluorine-doped silica glass with a maximum relative refractive index difference of −0.93% is obtained. Using this technique, optical fibers with a triangular refractive index profile are fabricated with a minimum optical loss of 1.6 dB/km at 1.69 μm wavelength.     

Crystallization behavior and hydrophilic performances of V2O5–TiO2 films prepared by sol–gel dip-coating

Homogeneous and transparent V₂O₅–TiO₂ composite nanometer thin films were prepared on glass substrates by sol–gel processing and dip-coating technique. The films as well as the dried powder of bulk gel were characterized by different techniques like X-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM), atomic force microscope (AFM) and thermogravimetry–differential thermal analysis (TG–DTA). The hydrophilicity of the films was determined by measuring the water contact angles on the films. The results showed that the dopant of V₂O₅ on TiO₂ thin films could produce a visible-light response to the films, and the introduction of V₂O₅ could suppress the structural phase transition and crystal growth of TiO₂ crystal. Finally, the relationship between crystalline size and hydrophilicity under sunlight was investigated in this article.     

A SAXS study of V2O5·nH2O sols and gels

Small-angle X-ray scattering (SAXS) measurements on V₂O₅·nH₂O sols and gels, prepared by dissolving V₂O₅ glass into water at room temperature, show that there are V₂O₅ polymeric fibers entangled like random coils in the sol of n 5000, while the deviation from the random coil behavior occurs in the dilute sol of n 6000.

A Bragg peak appears at the scattering vector h 0.02 Å⁻¹ to be superimposed on an asymptotic h⁻²-course in the SAXS curve of the concentrated sol of n 680. This means that the spatial correlation between V₂O₅ polymeric fibers takes place even in the fluid state.

V₂O₅·nH₂O sols completely lose fluidity at n 250 to transfer to the gel state, where V₂O₅ polymeric fibers begin to pile up in the parallel with a substrate surface. Such a layer structure is preserved up to the gel of n 4. However, V₂O₅ polymeric fibers are randomly oriented within each layer.     

Characteristics of ZnO–B2O3–CaO–Na2O–P2O5 glass powders prepared by spray pyrolysis

Fine-sized ZnO–B₂O₃–CaO–Na₂O–P₂O₅ glass powders with spherical shape were directly prepared by high temperature spray pyrolysis. The ZnO–B₂O₃–CaO–Na₂O–P₂O₅ powders prepared by spray pyrolysis at temperatures above 1200 °C had broad peaks at around 30° in the XRD patterns. The glass transition temperatures (T_g) of the glass powders obtained by spray pyrolysis at preparation temperatures between 900 °C and 1400 °C were near 480 °C regardless of the preparation temperatures. The dielectric layers formed from the glass powders prepared by spray pyrolysis at preparation temperatures above 1300 °C had clean surface and dense inner structure at the firing temperature of 580 °C. The transmittance of the dielectric layer formed from the glass powders obtained by spray pyrolysis at preparation temperature of 1400 °C was 90% at the firing temperature of 580 °C, in which the thickness of the dielectric layer was 13 μm. The UV cutoff edges gradually shift towards longer wavelength with increasing the preparation temperature of glass powders and the firing temperature of dielectric layers.     

Characterization and chemical durability of 70Ph2SiO·30TiO2 coating prepared by the sol-gel process

70Ph₂SiO·30TiO₂ coatings on slide glass and phosphate glass substrates have been prepared by the sol-gel process. Experimental results on the characterization and chemical durability of the coatings are presented. It is shown that the coatings heated at 150°C have reasonably good acid and water resistance while their alkali durability is very poor. The XPS results are used to verify the different corrosion behaviors of the coating in pure water and 1N HC1 solutions. The chemical durability of phosphate glass can be significantly improved by this coating.     

Ion-implanted treatment of (Ba,Sr)TiO3 films for DRAM applications

The effects of ion implantation on the properties of spin-on sol–gel Ba_0.7Sr_0.3TiO₃ (BST) thin films were studied by implanted Ar⁺, N⁺, and F⁺ doses. The F⁺-implanted BST samples present leakage current density <10⁻⁶ A/cm² at 2.5 V and dielectric constant 450. The leakage current of F⁺-implanted BST samples was reduced about one order of magnitude as compared with that of samples with implanted Ar⁺, N⁺ or without implantation. The thickness shrinkage from 135 to 115 nm was observed in F⁺-implanted BST films (before annealing treatment) and a respective increase in the refractive index from 1.84 to 2.05 was measured. After annealing the implanted samples, the changes of thickness and refractive index depend on the concentration of implanted dose. Based on an infrared transmission study of the samples we suggest that the ion-implanted samples with smaller dose (5×10¹⁴ cm⁻²) have fewer −OH contaminants than the non-implanted or implanted samples with the larger doses (1×10¹⁵ cm⁻²). Based on the results presented, we conclude that suitable ion implantation densifies the spin-on sol–gel BST films and reduces the −OH contaminants in the films.     

Glass formation through hydrolysis of Si(OC2H5)4 with NH4OH and HCl solution

Monolithic silica glass was obtained by heating the gels prepared by hydrolyzing Si(OC₂H₅)₄ with NH₄OH and HCl solution. The effect of the condition of hydrolysis of Si(OC₂H₅)₄ on glass formation was examined by measuring the bulk density, the infrared spectra and the thermal shrinkage of the gel on heating. The gel prepared by hydrolysis with NH₄OH solution consisted of numerous spherical particles, the bulk density being about 0.8. This gel abruptly shrank at about 1050°C, being converted to the pore free material similar to fused silica. The conversion of the gel to glass followed the sintering model in which the viscous flow controlled the sintering process. The viscosity and the activation energy for viscous flow were calculated on the basis of the Frenkel equation. On the other hand, the spherical particles were not observed in the gel prepared by hydrolysis with HCl solution. The bulk density of the gel was about 1.8. This gel was converted to glass at about 700°C, which was lower than the temperature of glass formation for the gel obtained by hydrolysis with NH₄OH solution.     

A study of alkali resistance of CaO---Al2O3---SiO2 glasses

The alkali resistance and structure of CaO---Al₂O₃---SiO₂ glasses are studied in this paper. The change of coordination number of aluminum ions in the glasses, caused by corrosion from the cement extract aqueous solution, was determined by means of X-ray fluorescence spectra and infrared absorption spectra. The interrelationship between glass compositions, structure, and alkali resistance is discussed.     

Migration of Cu ions in Cu2O---Al2O3---SiO2 glasses on heating in air

The behavior of copper ions in the Cu₂O·Al₂O₃·4SiO₂ (in moles) glass on heating in air at temperatures up to 500°C was studied. When the glass, in which about 90% of Cu was present as Cu⁺ ions, was heated in air above 300°C, a CuO layer was formed on the surface. The amount of CuO was increased with heating temperature and time, corresponding to the decrease in weight of the glass. Furthermore, the fraction of Cu²⁺ ions in the glass increased. These observations suggest that oxygens do not diffuse into the glass, but Cu⁺ ions migrate to the surface from the interior to balance the surplus positive charge produced by the oxidation of Cu⁺ to Cu²⁺ ions inside the glass. The following reaction scheme for the formation of the CuO layer was proposed; 2Cu⁺(interior) + ₂¹O₂(surface) → Cu²⁺(interior) + CuO(surface).     

Synthesis of Y2O3:Eu phosphors by bicontinuous cubic phase process

A novel approach for preparation of red-emitting europium-doped yttrium oxide phosphor (Y₂O₃:Eu) by using the bicontinuous cubic phase (BCP) process was reported in this paper. The BCP system was composed of anionic surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and aqueous yttrium nitrate/europium nitrate solution. Energy dispersive spectrometer analysis revealed the homogeneous precipitation occurred in the BCP structure. Thermogravimetric analysis measurements indicated the precursor powder was europium-doped yttrium hydroxide, Y_1−xEu_x(OH)₃. Scanning electron microscopy micrographs showed the precursor powder had a primary size about 30 nm and narrow size distribution. After heat treatment in furnace above 700 °C for 4 h, high crystallinity Y₂O₃:Eu phosphors was obtained. However, the primary size of particles grew to 50–200 nm and the dense agglomerates with a size below 1 μm were formed. X-ray diffraction patterns indicated the crystal structure of precursor powders and Y₂O₃:Eu phosphors were amorphous and body-centered cubic structure, respectively. The photoluminescence analysis showed that the obtained Y₂O₃:Eu phosphor had a strong red emitting at 612 nm and the quenching started at a Eu concentration of 10 mol%. This study indicated that the BCP process could be used to prepare the highly efficient oxide-based phosphors.