Attenuated Toatal Reflectance Fourier-Transform Infrared Spectra of a Hydrated Sodium Soilicate Glass

Attenuated total reflectance Fouriertransform infrared (ATR-FTIR) spectra were measured in the region from 4300 to 400 cm⁻¹ for a hydrated Na₂O–SiO₂ glass containing 35 wt% water. The Si–OH bending vibration mode was observed. It was found that the incorporated water, molecular water as well as hydroxyls, affected the Si–O vibrations. The effect of incorporated water upon the glass structure is discussed.     

Diffusion of Alkali Ions in Vitreous Silica

The diffusion of Cs⁺, Rb⁺, and K⁺ ions was measured in three grades of vitreous SiO₂ by the radiotracer-sectioning technique or Rutherford, backscattering spectroscopy. The values of the diffusion coefficient, D , at 1000°C decrease strongly with increasing ionic radius, changing by about two and one-half orders of magnitude per row of the periodic table. The difference between D_Cs and D_Rb is largely in the preexponential factor D_o in the Arrhenius expression rather than in the activation enthalpy Q . The values of D are much smaller than the tracer D values for the alkali metal ion in homogeneous Rb or Cs silicate glasses. Residual metallic impurities in the SiO₂ decrease both Q and D_o for the diffusion of Rb. The results are analyzed in terms of the interstitial structure of vitreous SiO₂.     

Chemical Interactions Promoting the ZrO2 Tetragonal Stabilization in ZrO2–SiO2 Binary Oxides

Metastable tetragonal ZrO₂ phase has been observed in ZrO₂–SiO₂ binary oxides prepared by the sol–gel method. There are many studies concerning the causes of ZrO₂ tetragonal stabilization in binary oxides such as Y₃O₂–ZrO₂, MgO–ZrO₂, or CaO–ZrO₂. In these binary oxides, oxygen vacancies cause changes or defects in the ZrO₂ lattice parameters, which are responsible for tetragonal stabilization. Since oxygen vacancies are not expected in ZrO₂–SiO₂ binary oxides, tetragonal stabilization should just be due to the difficulty of zirconia particles growing in the silica matrix. Furthermore, changes in the tetragonal ZrO₂ crystalline lattice parameters of these binary oxides have recently been reported in a previous paper. The changes of the zirconia crystalline lattice parameters must result from the chemical interactions at the silica–zirconia interface (e.g., formation of Si–O–Zr bonds or Si–O⁻ groups). In this paper, FT-IR and ²⁹Si NMR spectroscopy have been used to elucidate whether the presence of Si–O–Zr or Si–O⁻ is responsible for tetragonal phase stabilization. Moreover, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy have also been used to study the crystalline characteristics of the samples.     

Formation and Properties of Ln-Si-O-N Glasses (Ln = Lanthanides or Y)

Homogeneous Y-Si-O-N glasses containing 15 or 20 eq% nitrogen (N) were prepared from compositions with Y/Si ratios in the vicinity of that of the lowest eutectic point on the Y₂O₃–SiO₂ phase diagram. The liquidus on the phase diagram shifted toward lower temperatures by incorporation of N. The density, the elastic moduli, and the glass transition temperature of the Y-Si-O-N glasses increased with incorporation of N. This is due to the closer packing of atoms in the glasses by the substitution of N, which is in three-fold coordination with Si, for O which is in two-fold coordination, and the stronger covalent nature of the Si–N bond compared with the Si–O bond. The coefficient of thermal expansion of the Y-Si-O-N glasses increased with increasing Y content, because the discontinuity of the glass network developed with increasing nonbridging anions by the introduction of Y. In contrast, the glass transition temperature and the elastic moduli increased with Y content due to the high coordination of Y for O, and the relatively high cationic field strength of Y. Furthermore, the effect of cationic field strength on properties of Ln-Si-O-N glasses (Ln = lanthanides or Y) is discussed.     

Structural Equilibria in Silicate Glass Melts Investigated by Raman Spectroscopy

Structural equilibria of alkali silicate glasses and melts are investigated based on the Q ⁿ fractions ( n =number of bridging oxygen in SiO₄ tetrahedron) obtained from high-temperature Raman spectra. A mathematical treatment of the entropy of mixing, Δ S _mix, of structural groups of Q ⁿ is conducted and applied to the investigation of phase transformation and phase separation. Characteristics of Q ⁿ traces and the counter-map of Δ S _mix on Q ⁿ diagram are found to possess useful information to understand their mechanisms. An extended Q ⁿ diagram is also proposed to understand the melt structure and properties for the wide composition range.     

Effects of Glass Additions on (Zr,Sn)TiO4 for Microwave Applications

The effects of glass additions on the properties of (Zr,Sn)TiO₄ as a microwave dielectric material were investigated. The (Zr,Sn)TiO₄ ceramics with no glass addition sintered at 1360°C gave Q = 4900 and K = 37 at 7.9 GH_z. Several glasses, including SiO₂, B₂O₃, 5ZnO–2B₂O₃, and nine commercial glasses, were tested during this study. Among these glasses, (Zr,Sn)TiO₄ sintered with ZnO-B₂O₃–SiO₂ (Corning 7574) showed more than 20% higher density than that of pure (Zr,Sn)TiO₄ sintered at the same temperature. A 5-wt% addition of SiO₂, to (Zr,Sn)TiO₄, when sintered at 1200°C, gave the best Q : Q = 2700 at 9 GHz. Results of XRD analysis and scanning electron microscopy and the effect of glass content are also presented.     

Relationship Between Structure and Glass Transition Temperature in Low-silica Calcium Aluminosilicate Glasses: the Origin of the Anomaly at Low Silica Content

The anomalous behavior of the glass transition temperature ( T _g) in low silica calcium aluminosilicate glasses has been related to the structural modifications observed by neutron and X-ray diffraction. The diffraction data indicate that Al and Si are in tetrahedral sites and that Ca atoms are in distorted octahedral sites. By subtracting the correlation functions for glasses at constant SiO₂ or constant Al₂O₃ content, we have shown that Si and Al atoms are introduced in a different way within the glass structure. Si is present in various Q ⁿ sites, while Al resides in Q³ and Q⁴ sites for glasses with high CaO content and enters fully polymerized Q⁴ sites with increasing SiO₂ or Al₂O₃ content. The higher proportion of Al in Q³ positions at high CaO content yields a depolymerization of the network. The lower connectivity will contribute to a decrease of the viscosity, which may be at the origin of the decrease of T _g for glasses at low silica content.     

Properties and Network Constitution of rf-Sputtered Amorphous Films in the System Silicon Dioxide–Aluminum Orthophosphate

Amorphous films in the system SiO₂–AlPO₄ were prepared by means of the rf-sputtering method, and their physical properties, such as density, refractive index, and temperature coefficient of Young's modulus, and infrared spectra were measured. Also, the K α X-ray emission spectra of silicon and aluminum were measured in order to investigate the coordination state of these cations in the amorphous films. The density and the refractive index were close to those of amorphous SiO₂ and AlPO₄ and the compositional dependence showed a small deviation from linearity. The temperature coefficients of Young's modulus were positive for all of the samples. The infrared absorption spectra of all of the samples were similar to those of SiO₂ glass and amorphous AlPO₄ film, and there was no evidence of the presence of P═O bonds. The coordination states of silicon and aluminum ions in the present amorphous films were the same as those in fused silica and AlPO₄ crystal, respectively. The results of the properties, infrared absorption spectra, and X-ray emission spectra suggest that SiO₄ tetrahedrons and AlO₄–PO₄ connecting tetrahedral dimers constitute the network of the present amorphous films. A small deviation of the physical properties from an additive rule was thought to result from the difference in the bond character between the newly formed Si–O–Al and Si–O–P bonds and the bonds in the end members, Si–O–Si and Al–O–P.     

Glass Formation in the System SiO2–PbO Containing Transition-Metal Oxides

Glass-forming regions, valence states, and viscosities in SiO₂–PbO systems containing various transition-metal oxides as a third component were investigated. The glasses were prepared by melting in an open atmosphere. The glass-forming regions ranged as follows: MnO≡ZnO > FeO_1.5>NiO. The ratios Fe²⁺/(Fe²⁺+ Fe³⁺) and Mn³⁺/ (Mn³⁺+ Mn²⁺) in the glasses were determined by chemical analysis. The Fe²⁺/ (Fe²⁺+ Fe³⁺) ratio in SiO₂–PbO–FeO_1.5 glasses ranged from 0.016 to 0.050. The Mn³⁺/ (Mn³⁺+ Mn²⁺) ratio in SiO₂–PbO–MnO glasses ranged from 0.056 to 0.30. The fraction of manganese (III) ions in the glasses varies considerably with the glass composition. The effects of transitionmetal oxides on the viscosity are discussed.     

Elastic Properties and Molar Volume of Rare-Earth Aluminosilicate Glasses

The elastic properties, molar volume, and glass transition temperature ( T _g) of rare-earth-containing aluminosilicate glasses were investigated in the compositions of SiO₂–LnAlO₃ and SiO₂–Ln_3/4Al_5/4O₃, where Ln is Y, La, Nd, Eu, or Yb. The molar volume decreased with decreased ionic size of the Ln³⁺ ion, and T _g and elastic moduli increased in the same order. The Yb-containing glasses showed the highest Young's modulus among all the oxide glasses, even higher than the highest value ever known for glass containing Y₂O₃, as expected from the smaller ionic radius of Yb³⁺ than that of Y³⁺. The bulk modulus was found to be almost proportional to the inverse four-thirds power of the molar volume of glasses in each composition, indicating that Ln³⁺ ions can substitute for each other without changing the glass structure except for the size of the local structure around themselves. From the comparison of these properties, the structural role of rare-earth ions in these glasses is discussed.     

Coordination of Zinc(II) in ZnO–K2O–SiO2 Glasses by X-ray Diffraction

The radial distribution functions of ZnO–K₂O–SiO₂ glasses with 7 and 10 wt% ZnO are compared with that of the corresponding K₂O–SiO₂ matrix leading to "difference distribution curves'representative of the zinc structural arrangement. Analysis of the curves indicates that Zn²⁺ ions are prevalent (65% to 80%) in the glasses in tetracoordinated form.     

Direct Measurement of Relative Partial Molar Enthalpy of SiO2 in SiO2–M2O (M=Li, Na, K, Cs) Binary and SiO2–CaO–Al2O3 Ternary Melts

The relative partial molar enthalpies, Δ _SiO2, of SiO₂ in SiO₂–M₂O (M = Li, Na, K and Cs) binary and SiO₂–CaO–Al₂O₃ternary melts were directly measured by drop-solution calorimetry at 1465 K and 1663 K. Δ _SiO2 changes from exothermic to endothermic as silica content increases, confirming the tendency toward immisciblity seen from activity measurements. It is concluded that Δ _SiO2 is negative due to acid-base reactions and charge-coupled substitutions when the melt is composed of fewer Q ⁴ and more Q ³ and Q ² species, but positive due to structural strain when the melt is composed of mostly Q ⁴ species. The Δ _SiO2 obtained by calorimetry is a useful measure of basicity, when comparing different alkali and alkaline earth oxides.     

Proton Conductivity in Zr4+-Ion-Doped P2O5–SiO2 Porous Glasses

The effect of zirconium ions on glass structure and proton conductivity was investigated for sol-gel-derived P₂O₅–SiO₂ glasses. Porous glasses were prepared through hydrolysis of PO(OCH₃)₃, Zr(OC₄H₉)₄, and Si(OC₂H₅)₄. Chemical bonding of the P⁵⁺ ions was characterized using ³¹P-NMR spectra. The phosphorous ions, occurring as PO(OH)₃ in the ZrO₂-free glass, were polymerized with one or two bridging oxygen ions per PO₄ unit with increased ZrO₂ content. The chemical stability of these glasses was increased significantly on the addition of ZrO₂, but the conductivity gradually decreased from 26 to 12 mS/cm at room temperature for 10P₂O₅·7ZrO₂·83SiO₂ glass. A fuel cell was constructed using 10P₂O₅·5ZrO₂·85SiO₂ glass as the electrolyte; a power of ∼4.5 mW/cm² was attained.     

Reduction of Eu3+ to Eu2+ in Aluminoborosilicate Glasses Prepared in Air

Eu₂O₃-doped aluminoborosilicate glasses were prepared in air at high temperature. Luminescence measurements were used to investigate a valence change from Eu³⁺ to Eu²⁺ ions in the aluminoborosilicate glasses. The results showed that the doped Eu³⁺ ions were partially reduced to Eu²⁺ in the Eu₂O₃:RO–Al₂O₃–B₂O₃–SiO₂ (RO=CaO, SrO, BaO, Li₂O) glasses, but not in the Eu₂O₃:RO–Al₂O₃–B₂O₃–SiO₂ (RO=Na₂O, K₂O) glasses. The changes of Eu reduction with different RO components were discussed with the variation of optical basicity of RO and with different valency of R cations. The effects of co-doping BaO and ZnO in aluminoborosilicate glasses on Eu reduction were also investigated and discussed.     

Novel Processing for Mesoporous Silica Films with One-Dimensional Through Channels Normal to the Substrate Surface

Mesoporous silica films with one-dimensional through channels perpendicular to the substrate surface have been fabricated successfully by a novel process, which was a combination of eutectic decomposition of amorphous films and subsequent chemical etching. In the case of the Fe–Si–O system, amorphous precursor films annealed under oxidizing conditions were decomposed to a regular array of needlelike hematite (Fe₂O₃) crystals with a diameter of ∼4 nm surrounded by an amorphous silica matrix. Then, hematite crystals were preferentially removed by chemical etching. The pore surface areas of the remaining mesoporous SiO₂ films were found to be more than 1000 m²/g by an isothermal N₂ gas adsorption and desorption measurement.     

Corrosion of Lead Glasses in Acid Media: I, Leaching Kinetics

The leaching kinetics of lead glasses (25 to 35 mol% PbO-75 to 65 mol% SiO₂; some with K₂O and A1₂O₃, additions) were determined in 10% acetic acid. Except for a ternary glass (SiO₂-PbO-K₂O) which had a linear dependence on time, all compositions exhibited a linear dependence on the square root of time for the amount of Pb and K removed. Increasing the SiO₂: PbO ratio or the Al₂O₃ content improved the durability whereas adding K₂O to a binary PbO-Si0₂ glass greatly increased the corrosion rate. Activation energies for the rates of Pb and K removal were determined for three compositions and it was deduced that the diffusion of H⁺ controlled the leaching for binary and 4-component glasses whereas dissolution of the silica network was rate-controlling for the ternary.     

Crystallization and Chemical Strengthening of Stuffed β-Quartz Glass-Ceramics

Metastable solid solutions with the β-quartz structure can be crystallized from most glasses in the system SiO₂-Mg(AlO₂)₂-LiAlO₂ as well as from many containing the additional components Zn(AlO₂)₂ Al(AlO₂)₃, Li₂ZnO₂, and Li₂BeO₂. Internal nucleation is afforded by additions of ZrO₂ or TiO₂. Either transparent or opaque crystalline materials can be formed from glasses containing about 70% SiO₂. The transparency is due to a combination of low birefringence in the major stuffed β-quartz phase and minute crystal size. Thermal expansions vary from -20 to +50 × 10⁻⁷/°C. Thermal stability is highly variable. Breakdown products include spinel, cordierite, β-spodumene, willemite, mullite, and cristobalite. Magnesian compositions can be strengthened by a 2Li⁺⇌ Mg²⁺ ionexchange reaction. Abraded flexural strengths range from 30,000 to 160,000 psi.     

Preparation of Cerium-Activated Silica Glasses: Phosphorus and Aluminum Codoping Effects on Absorption and Fluorescence Properties

Cerium-activated silica (SiO₂) glasses were prepared by plasma torch chemical vapor deposition (CVD). In Ce-doped SiO₂ glasses, most Ce exists as Ce⁴⁺ ions; the remaining small amount of Ce³⁺ ions exhibits a broad fluorescence spectrum with a large Stokes shift, ∼9600 cm^-1, from the excitation spectrum peak of 324 nm. Aluminum and phosphorus codoping considerably increases the Ce³⁺ ratio and shifts the peaks of both spectra to shorter wavelengths. P codoping is the more effective way to achieve this result and in some cases produces an absorption spectrum similar to that of a Ce-doped phosphate glass. These findings are consistent with the solvatiorn shell model for codoping, as previously proposed. To codope P, a soot remelting method was devised to deal with the highly volatile P₂O₅.     

Structure of Liquid Al6Si2O13 (3:2 Mullite)

We report the first measurements of the structure factor, S ( Q ), and the pair distribution function, G ( r ), of Al₆Si₂O₁₃ (3:2 mullite) in the normal and supercooled liquid states in the temperature range 1776–2203 K. Measurements are obtained by synchrotron X-ray scattering on levitated, laser-heated liquid specimens. The S ( Q ) shows a prepeak at 2.0 Å⁻¹ followed by a main peak at 4.5 Å⁻¹ and a weak feature at 8 Å⁻¹. The G ( r ) shows a strong (Si,Al)–O correlation at 1.80 Å at high temperature that moves to 1.72 Å as the liquid is supercooled. The second and third nearest neighbor peaks at 3.0 and 4.25 Å sharpen with supercooling. The short-range structure of the high-temperature liquid is similar to the corresponding glasses produced by rapid quenching. Supercooling causes an increase in the concentration of tetrahedral Si⁴⁺ ions, which is manifested by the large shift in the first peak to lower ionic distance, r , values in G ( r ). The increase in tetrahedrally coordinated Si⁴⁺ ions is offset by an increase in octahedral Al³⁺ ions. The clustering of the SiO₄⁴⁻ tetrahedral units results in increased viscosity of the liquid at temperatures below the melting point, which is consistent with Al₆Si₂O₁₃ being a fragile liquid.     

EPR of Vanadium(IV) in Lead Silicate Glass

EPR spectra of lead silicate glasses doped with small amounts of V₂O₅ were studied at −150°C to room temperature. Only the glasses with the higher SiO₂ contents produced EPR signals. The spin Hamiltonian parameters are characteristic of the V(IV) species in axial symmetry. The values of g, g ⊥, A, and B indicate that V(IV) is present as VO^2plus; in a tetragonally distorted octahedral site. This ion probably does not enter the SiO₂ network but rather behaves as a modifier cation.