Rayleigh and Brillouin Scattering in K2O–SiO2 Glasses

The intensity and spectral distribution of light scattered by K₂O-SiO₂ glasses (K₂O content up to 40 mol%) were measured. The transverse and longitudinal sound-wave velocities and the photoelastic constants were evaluated from the results. The total intensity of the scattering (and therefore the attenuation caused by it) exhibited a minimum at a concentration of ∼25 mol% K₂O. For this composition the attenuation is ∼2/2 of that in pure SiO₂. This behavior results from the existence of anomalously small concentration fluctuations in the melt of K₂O·3SiO₂ glass. A qualitative explanation of this result, involving low-temperature immiscibility regions, is presented.     

Equilibrium Compressibilities and Density Fluctuations in K2O–SiO2 Glasses

The density fluctuations contributing to light scattering in a glass are governed by the flctive temperature of the glass and the equilibrium compressibility of the melt. Using ultrasonic velocity data for K₂O–SiO₂ melts, these compressibilities were evaluated, and the magnitude of the density fluctuations were calculated. In this system, the mean–square amplitude of the fluctuations reaches a minimum value (about half that of pure SiO₂) for a composition of ∼20 mol% K₂O. By extrapolating the equilibrium compressibilities to zero K₂O content, the density fluctuations can be calculated for pure SiO₂ glass; this calculation agrees well with the result obtained from light–scattering measurements.     

Optimization of the Thermodynamic Properties and Phase Diagrams of the Na2O–SiO2 and K2O–SiO2 Systems

Available thermodynamic and phase diagram data have been evaluated for all phases in the Na₂O-SiO₂ and K₂O-SiO₂ systems at 1 bar pressure from 298 K to above the liq-uidus temperatures. All reliable thermodynamic and phase diagram data have been simultaneously optimized in order to obtain one set of model equations for the Gibbs energies of all phases as functions of temperature and composition. The thermodynamic properties and phase diagrams calculated from these parameters are self-consistent. The modified quasi-chemical model was used to represent the Gibbs energies of the molten slag phases.     

Spectroscopic Properties of Er3+-Doped Na2O–La2O3–Al2O3–SiO2 Glasses

Er³⁺-doped sodium lanthanum aluminosilicate glasses with compositions of (90− x )(0.7SiO₂·0.3Al₂O₃)· x Na₂O·8.2La₂O₃· 0.6Er₂O₃·0.2Yb₂O₃·1Sb₂O₃ (in mol%) ( x = 12, 20, 24, 40, 60 mol%) were prepared and their spectroscopic properties were investigated. Judd–Ofelt analysis was used to calculate spectroscopic properties of all glasses. The Judd–Ofelt intensity parameter Ω _t ( t = 2, 4, 6) decreases with increasing Na₂O. Ω₂ decreases rapidly with increasing Na₂O while Ω₄ and Ω₆ decrease slowly. Both the fluorescent lifetime and the radiative transition rate increase with increasing Na₂O. Fluorescence spectra of the ⁴ I _13/2 to ⁴ I _15/2 transition have been measured and the change with Na₂O content is discussed. It is found that the full width at half-maximum decreases with increasing Na₂O.     

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.     

Indentation Creep of Na2O · 3SiO2 Glasses with Various Water Contents

Time-dependent deformation behavior induced by an indentation, called indentation creep, was investigated for Na₂O · 3SiO₂ glasses with various water contents by measuring the indentation depth as a function of time using a conical indenter. It was found that the indentation creep behavior of the glasses could be best explained as steady-state inhomogeneous (non-Newtonian viscous) flow. Water in the glasses appeared to reduce the stress (or yield stress) needed to cause this flow. Crack initiation of the glasses was promoted by water through this inhomogeneous flow.     

Factors Affecting the Preparation of Sr2Fe2−xMoxO6

Samples of Sr₂Fe_{2− x} Mo _x O₆were prepared by solid-state reaction in air and 5%H₂–95%N₂. X-ray diffractometry was used to identify the phases and evaluate the lattice parameters. It is found that molybdenum ions can dissolve in the SrFeO₃ even if the sample is heated in air but the solubility is limited. The solubility can be enhanced by heating the sample in low oxygen partial pressure, which is attributed to the larger ionic radii of Fe³⁺ and Mo⁵⁺ than that of Fe⁴⁺. The degradation of Sr₂Fe_{2− x} Mo _x O₆in water and air is also reported.     

Effect of Neodymium:Yttrium Aluminum Garnet Laser Irradiation on Crystallization in Li2O–Al2O3–SiO2 Glass

A 355-nm neodymium:yttrium aluminum garnet laser, produced by a harmonic generator, was used for the nucleation process in photosensitive glass containing Ag⁺ and Ce³⁺ ions. The pulse width and frequency of the laser were 8 ns and 10 Hz, respectively. Heat treatment was conducted at 570°C for 1 h, following laser irradiation, to produce crystalline growth, after which a LiAlSi₃O₈ crystal phase appeared in the laser-irradiated Li₂O–Al₂O₃–SiO₂ glass. The present study compares the effect of laser-induced nucleation on glass crystallization with that of spontaneous nucleation by heat treatment.     

Dielectric Properties of Glasses in the System Nb2O5–Na2O–SiO2

The effect of niobia on the dielectric properties of glasses in the system Nb₂O₅–Na₂O–SiO₂ has been studied from 100 to 10¹⁰ cps. The dielectric constant is high even at frequencies up to 10¹⁰ cps. The Nb⁵⁺ ion, with its small ionic radius and high charge, reinforces the network and raises the dielectric constant.     

Effect of Molybdenum on the Structure and on the Crystallization of SiO2–Na2O–CaO–B2O3 Glasses

Crystallization of the poorly durable Na₂MoO₄ phase able to incorporate radioactive cesium must be avoided in SiO₂–Al₂O₃–B₂O₃–Na₂O–CaO glasses developed for the immobilization of Mo-rich nuclear wastes. Increasing amounts of B₂O₃ and MoO₃ were added to a SiO₂–Na₂O–CaO glass, and crystallization tendency was studied. Na₂MoO₄ crystallization tendency decreased with the increase of B₂O₃ concentration whereas the tendency of CaMoO₄ to crystallize increased due to preferential charge compensation of BO₄⁻ entities by Na⁺ ions. ²⁹Si MAS NMR showed that molybdenum acts as a reticulating agent in glass structure. Trivalent actinides surrogate (Nd³⁺) were shown to enter into CaMoO₄ crystals formed in glasses.     

Thermodynamic Assessment of the Miscibility Gaps and the Metastable Liquidi in the B2O3–RO Systems (R = Mg, Ca, Sr, and Ba)

In an attempt to understand the liquid–liquid phase separation in the B₂O₃–MgO, B₂O₃–CaO, B₂O₃–SrO, and B₂O₃–BaO systems, the liquid miscibility gaps were calculated using the optimized interaction parameters of liquid phases. The Gibbs energies of liquid phases were derived in the form of a subregular solution from an optimization procedure based on phase diagram data. In addition, metastable liquidus boundaries and spinodal curves were also assessed by using the Gibbs energies of liquid phases. The present results were compared and discussed with other experimental and assessed data available in the literature.     

Density Measurements of Glasses in the Series xNa2S + (1 −x)B2S3

Measurements of the densities of glasses in the series x Na₂S + (1 − x )B₂S₃ are reported for the first time. As has been found in the corresponding oxyborate series x Na₂O + (1 − x )B₂O₃, the addition of Na₂S to B₂S₃ causes the density to increase, from 1.80 g/mL for pure B₂S₃ to 1.99 g/mL at the limit of the low-alkali sulfide glass-forming range of x = 0.25. These data provide evidence for the formation of tetrahedral boron units (BS₄⁻) as alkali is added. Volumes for the trigonal BS₃ and tetrahedral BS₄⁻ groups of 57.55 and 51.79 ų, respectively, were determined. As has also been found in the oxyborates, the tetrahedral boron group occupies a smaller volume than the trigonal boron group and causes the increase in density with added Na₂S.     

Influence of TiO2 on Properties of Glasses in the System K2O–PbO–SiO2–TiO2 and Its Relation to Structure

By a progressive weight percent substitution of TiO₂ for SiO₂ at various rations of concentration of K₂O and PbO, the entire region of glass formation in the quaternary system K₂O–PbO–SiO₂–TiO₂ was covered with 51 glass compositions. The properties of these glasses were determined and studied with respect to the role of TiO₂ in the system. The results indicated that the dielectric constant increased progressively with increasing TiO₂ concentration whereas the dissipation factor showed an overall decrease, when measured at 1 Mc and 25°C. Density and the refractive index increased progressively with increasing TiO₂ concentration but deviated from the additive relation. Chemical durability, expansivity, and softening temperature vs. composition curves showed definite inflections. The effect of TiO₂ on oxygen packing indicated that Ti⁴⁺ strengthens the network in lower concentrations and weakens the network in higher concentrations in this system. It appears to be likely that Ti⁴⁺ changes its coordination number form 4 to 6.     

Effects of Alkaline-Earth-Metal Addition on the Sinterability and Microwave Characteristics of (Zr,Sn)TiO4 Dielectrics

The sinterability and microwave dielectric properties of (Zr_0.8Sn_0.2)TiO₄ with additions of 1 mol% of magnesium, calcium, strontium, or barium were examined. All the alkaline-earth metals were effective for densification, and the order of effectiveness was as follows: Mg < Ca < Sr < Ba. The dielectric constant and the temperature coefficient of the resonant frequency were not influenced very much by the additives; however, a strong deterioration of the quality factor ( Q ) did occur when magnesium was added. The presence of grain-boundary phases was confirmed via microstructural observation, using transmission electron microscopy. In addition, energy-dispersive X-ray analysis was performed to investigate the cause of the deterioration in the Q value.     

Mechanical Damping Spectrum for Mixed-Alkali R2 O·Al2 O3·6SiO2 Glasses

The internal friction of R₂O·Al₂O₃·6SiO₂ glasses was measured from-180° to 700°C at 0.4 Hz. Glasses containing Li₂O or Na₂O exhibited only the one internal friction peak characteristic of the stress-induced movement of the alkali ions. Substitution of a second alkali resulted in two significant changes in the internal friction: (1) a rapid reduction in the magnitude of the original alkali peak and (2) the appearance of a new internal friction peak whose magnitude was especially sensitive to the concentration of the second alkali. Each combination of two alkali ions resulted in a new peak, with peaks being observed for the combinations Li-Na, Na-K, and Li-K. A mechanical damping spectrum is predicted for aluminosilicate glasses containing more than two alkali ions.     

MgO–Na2O–P2O5-Based Sintering Additives for Tricalcium Phosphate Bioceramics

Effects of MgO–Na₂O–P₂O₅-based sintering additives on densification, microstructure, hardness, compression strength, and biodegradability of β-tricalcium phosphate (β-TCP) ceramics were studied. Three additive compositions were prepared and introduced into β-TCP. Uniaxially compacted ceramic structures, sintered at 1250°C in air, were characterized. Scanning electron microscopy was used to study the microstructure. The X-ray diffraction technique was used for phase analysis. Results showed that these additives modified the microstructure and improved the sintered density and mechanical properties. An increase of 9% in density, 40% in hardness and 38% in compression strength were achieved. Biodegradation analysis revealed that these additives could tailor the rate of resorption and hardness degradation of β-TCP.     

Dielectric Characteristics of Na2O · 3SiO2 Glasses with High Water Contents

Dielectric characteristics of Na₂O·3SiO₂ glasses with water contents up to ∼12 wt% were found to be drastically affected by incorporated water. The high-frequency dielectric constant increased with water content, while both the static dielectric constant and the low-frequency dielectric relaxation strength showed a pronounced minimum at a water content of ∼3 wt%.     

Reactions in the System Li2O–MgO–Al2O3–SiO2: I, The Cordierite-Spodumene Join

Phase equilibria along the nonbinary join between cordierite (2MgO · 2Al₂O₃· 5SiO₂) and spodumene (Li₂O · Al₂O₃· 4SiO₂) were investigated in the temperature range 800° to 1550°C. using the quench technique on fourteen compositions. The phase diagram at high temperatures is characterized by a very small region of solid solution on the cordierite side, appreciable solid solution on the spodumene side, and regions of three and four phases toward the center of the system, including liquid, α-cordierite, mullite, spinel, corundum, and β-spodumene and its solid solutions. The liquidus has a flat minimum between 40 and 50% cordierite at 1347°, and rises on one side to the congruent melting point of β-spodumene (1421°) and on the other side to the temperature of complete melting of cordierite (1530°). The lowest temperature at which liquid appears is 1325°. At low temperatures a complete series of metastable solid solutions exists between μ-cordierite and β-spodumene. The significance of the data in the preparation of thermal-shock-resisting bodies is discussed.     

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.     

Devitrification Kinetics and Mechanism of K2O–CaO–SrO–BaO–B2O3–SiO2 Glass-Ceramic

The devitrification kinetics and mechanism of a low-dielectric, low-temperature, cofirable K₂O–CaO–SrO–BaO–B₂O₃–SiO₂ glass-ceramic have been investigated. Crystalline phases including cristobalite (SiO₂) and pseudowollastonite ((Ca,Ba,Sr) SiO₃) are formed during firing. Activation energy analysis shows that the nucleation of the crystalline phases is controlled by phase separation of the glass. The crystallization kinetics of both cristobalite and pseudowollastonite obey Avrami-like behavior, and the results show an apparent activation energy close to that of the diffusion of alkaline and alkali ions in the glass, suggesting that diffusion is rate limiting. The above conclusion is further supported by analysis of measured growth rates.