Glass-Forming Systems Involving GeO2 with Bi2O3, Ti2O, and PbO

The previously studied system GeO₂-Bi₂O₃-TI₂O was extended with the addition of PbO using air- and water-quenched melted samples. Large areas of glass formation were found in the systems GeO₂–Bi₂O₃–PbO and GeO₂–PbO–Tl₂O at all but the lowest GeO₂ contents. Glasses were examined by powder X-ray diffraction, differential thermal analysis, thermomechanical analysis, and Archimedes'technique to obtain glass transition and crystallization exotherm temperatures, thermal expansion coefficients, and densities, which are presented in diagrams for the GeO₂-PbO binary and for the two ternary systems. Based on calculated values of λ₀, the wavelength for zero material dispersion, compositions in this system may be useful for construction of ultralow-loss optical waveguides in the μm region.     

Free Volume of Network-Forming Oxide Glasses in the Systems P2O5-(GeO2,TeO2,Sb2O3,V2O5)

The free-volume fraction (V_f) defined by Simha and Boyer was measured for network-forming oxide glasses in the systems P₂O₅-(GeO₂, TeO₂,Sb₂O₃.V₂O₅). The V_f values varied from 0.06 to 0.25. The systems P₂O₅-TeO₂: and P₂O₅-Sb₂O₃ have V_f∼0.1, which is near the magnitude of the free-volume fraction for normal metaphosphate glasses and many organic high polymers.     

Structure of Glasses and Melts in the Na2O·GeO2·B2O3 System

Density and viscosity results are presented for ternary Na₂O·GeO₂·B₂O₃ melts (∼600° to 1300°C) and glasses containing as much as 35 mole % Na₂O. Synthetic partial molar volume models indicate a fairly broad stability region for BO₄ tetrahedra in the B₂O₃-rich melts. Similar models for GeO₂-rich melts reveal a more limited stability region for GeO₆ octahedra. The expansion coefficient contours and viscosity isotherms confirm the volume-based conclusions for the liquid state. The high-temperature volume models were used to develop glass volume models that agree to within several percent of experiment. It has been concluded that the melts and glasses possess similar structures. The relatively greater compositional stability of GeO₆ octahedra in the presence of B₂O₃ (compared to Al₂O₃) can be related to the smaller average number of oxygens around boron (III), at a fixed O/Ge ratio, compared to aluminum (III). Evidence is presented for a slight decrease of the thermal stability of GeO₆ octahedra in the GeO₂-rich melts above about 1000°C.     

Depolymerization of GeO2 and B2O3-GeO2 Network Glasses by Sb2O3

Binary Sb₂O₃-GeO₂ glasses containing 45 mol% Sb₂O₃ and ternary Sb₂O₃-B₂O₃-GeO₂ glasses containing 50 mol% GeO₂ were prepared. Their densities (volumes), refractive indices, and infrared spectra were determined, and their colors and high-temperature viscosities were estimated visually. Small amounts of Sb₂O₃ (∼10 mol%) appear to perturb neither the Ge-O-Ge network nor those B-O-Ge networks with small B/Ge ratios (∼0.2). The B-O-Ge networks with larger B/Ge ratios (∼1.0) depolymerize in the presence of even less Sb₂O₃. Amounts of Sb₂O₃ >10 mol% appear to depolymerize the Ge-O-Ge and Ge-O-B networks progressively, possibly with the formation of chains. A structurally sensitive ir isofrequency contour technique developed for ternary glass systems was applied successfully to these Sb₂O₃-B₂O₃-GeO₂ glasses. These contours can thus readily detect significant network depolymerization in the absence of the usual network modifiers.     

Glass Formation in the System GeO2-Bi2O3-Tl2O

The occurrence of glass in the three binary and one ternary oxide systems containing Ge, Bi, and Tl was studied by air- and water-quenching melted samples. Bulk glass occurred widely in these systems and was obtained with as little as 10 mol% GeO₂, combined with 68 mol% BiO_1.5 and 22 mol% TIO_0.5. Some glass occurred in all compositions except those with the highest Bi₂O₃ or TI₂O contents. Glass specimens were studied by differential thermal analysis to yield glass transition and crystallization exotherm temperatures; the thermal expansion coefficients and densities were also measured. Diagrams are presented to show the variation of these properties as well as λ₀, the wavelength for zero material dispersion, in the binary and ternary systems. Based on these data, it is demonstrated that ultralow-loss optical waveguides can be constructed in the 3-3.5-μm regionb.     

Internal Friction of Network-Forming Oxide Glasses in the System P2O5-(GeO2, TeO2, Sb2O3, V2O5)

The internal friction of only network-forming oxide glasses containing a P₂O₅ component, i.e., in the systems P₂O₅-GeO₂, P₂O₅-TeO₂, P₂O₅-Sb₂O₃, and P₂O₅-V₂O₅, was measured as a function of temperature by a free torsional vibration method. P₂O₅-TeO₂ and P₂O₅-Sb₂O₃ glasses exhibited clearly high-temperature peaks in a plot of internal friction vs temperature in spite of the absence of nonbridging oxygens and network modifiers. Therefore, we conclude that the high-temperature peaks appeared when strong and weak parts coexisted in the network structure.     

Polymer Mixtures in Na2O.Sb2O3.GeO2 Glasses

Ternary Na₂O.Sb₂O₃.GeO₂ glasses (with various [Na]/[Na + Sb] ratios) that contained ≥65 mol% GeO₂ were prepared. Their densities (volumes), refractive indices, and infrared spectra were determined and their colors noted. The ternary glasses with ≥88 mol% GeO₂ exhibit nearly additive volumes, refractivities, and frequencies for the main Ge-O vibration. Ternary glasses with lesser amounts of GeO₂ exhibit a variety of behaviors, depending on the [Na]/[Na + Sb] ratio. Small amounts of Sb₂O₃ cause significant volume and refraction deviations, as well as changes in ν_Ge-O, that can be associated with gradual elimination of GeO₆ octahedra. All the information supports a model for the glasses with 65 to 88 mol% GeO₂ that involves a degree of depolymerization that is greater when Na₂O and Sb₂O₃ are present together than when either is present alone.     

Properties and Structure of Glasses in the System Bi2O3-SiO2-GeO2

In the system Bi₂O₃-SiO₂-GeO₂, good glasses can be formed only from limited compositional regions consisting of 2 narrow strips along the lines x Bi₂O₃-(100-:t) GeO₂ ( x ≤40) and 40Bi₂O₃ y SiO₂ (60- y )GeO₂ (mol%); such glass is dark brown. Compositions from a large region (Bi₂O₃ content <40 mol%) showed immiscibility. In the binary system Bi₂O₃-GeO₂, density and refractive index vary linearly with composition (mol%). Negative deviations of molar volume from ideality suggest that the coordination of a significant number of Ge ions is changing from 4-fold to 6-fold. Thermal expansion and electrical resistivity data are also reported.     

Spectrum of Volume Relaxation Times in B2O3

Time-index of refraction isotherms were measured for B₂O₃ glass starting from both a high and a low temperature in the transformation region. The equilibrium index values at each temperature, obtained from both types of approach curve, were identical. As in the case of the density values, the equilibrium refractive index curve as a function of temperature for this glass is not a straight line. The two-relaxation-times (crossover) model was applied to B₂O₃ glass and fitted the data as well as it did in previous experiments with borosilicate crown and GeO₂ glasses. The reverse crossover which was predicted by the model was experimentally confirmed with the B₂O₃ glass. The spectrum of relaxation times narrowed with decreasing temperature, indicating approach to another region of single relaxation associated with the low-temperature Arrhenius region. The relaxation times for the low-temperature crossover agreed well with those from the high-temperature curves, indicating complete linearity in the experiments. The spectrum of relaxation times was slightly asymmetrical at constant pressure and very asymmetrical at constant volume.     

Defect Clustering and Color in Fe,Ti: α-Al2O3

A comprehensive theory is presented which successfully explains the polarization, isothermal, and isochronal behavior of the optical absorption bands responsible for the color in blue and blue-green sapphire (Fe,Ti: α-Al₂O₃). The experimental study on which this theory is based has conclusively shown that (Fe,Ti) and (Fe,Fe) vacancy-containing defect clusters are responsible for the optical properties of Fe,Ti: α-Al₂O₃ and H,Fe,Ti: α-Al₂O₃. The experimental results also prove that V‴ is the charge-compensating defect for Ti˙_Al in Fe, Ti and Ti: α-Al₂O₃ with an [Ti˙_Al] = 3[V‴] electroneutrality condition and that V¨_o provides the charge balance for Fe'_Al in Fe: α-Al₂O₃ with an [Fe'_Al] = 2[V¨_o]electroneutrality condition. Defect clusters were found to form via diffusion-limited solid-state reactions where the relative concentration of charged and neutral point defects depends on both the association energy and the diffusivity of the defects participating in the clustering reactions. In this paper, a model is presented which attempts to explain both the origin and the thermal behavior of the optical bands responsible for the color of Fe,Ti: α-Al₂O₃.     

Sintering, Crystallization, and Properties of B2O3/P2O5-Doped Li2O·Al2O3·4SiO2 Glass-Ceramics

Sintering, crystallization, microstructure, and thermal expansion of Li₂O·Al₂O₃·4SiO₂ glass-ceramics doped with B₂O₃, P₂O₅, or (B₂O₃+ P₂O₅) have been investigated. On heating the glass powder compacts, the glassy phase first crystallized into high-quartz s.s., which transformed into β-spodumene after the crystallization process was essentially complete. The effects of dopants on the crystallization of glass to high-quartz s.s. and the subsequent transformation of high-quartz s.s. to β-spodumene were discussed. The major densification occurred only in the early stage of sintering time due to the rapid crystallization. All dopants were found to promote the densification of the glass powders. The effect of doping on the densification can fairly well be explained by the crystallization tendency. All samples heated to 950°C exhibited a negative coefficient of thermal expansion ranging from about −4.7 × 10^-6 to −0.1 × 10^-6 K^-1. Codoping of B₂O₃ and P₂O₅ resulted in the highest densification and an extremely low coefficient of thermal expansion.     

Crystalline Phases and YAG Laser-Induced Crystallization in Sm2O3–Bi2O3–B2O3 Glasses

The glass formation region, crystalline phases, second harmonic (SH) generation, and Nd:yttrium aluminum garnet (YAG) laser-induced crystallization in the Sm₂O₃–Bi₂O₃–B₂O₃ system were clarified. The crystalline phases of Bi₄B₂O₉, Bi₃B₅O₁₂, BiBO₃, Sm _x Bi_{1− x} BO₃, and SmB₃O₆ were formed through the usual crystallization in an electric furnace. The crystallized glasses consisting of BiBO₃ and Sm _x Bi_{1− x} BO₃ showed SH generations. The formation of the nonlinear optical BiB₃O₆ phase was not confirmed. The formation (writing) region of crystal lines consisting of Sm _x Bi_{1− x} BO₃ by YAG laser irradiation was determined, in which Sm₂O₃ contents were∼10 mol%. The present study demonstrates that Sm₂O₃–Bi₂O₃–B₂O₃ glasses are promising materials for optical functional applications.     

Modification of αAI2O3 Platelet/ZrO2 Matrix Interface by Epitaxial Growth of β-AI2O3 on the α-AI2O3

An epitaxial β-alumina crystal growth method was used to modify α-AI₂O₃ platelet surfaces before inclusion as a reinforcing phase in partially stabilized zirconia (3Y-TZP). The as-grown surface phase was Na-β"-AI₂O₃. This was converted to Ca-β"-AI₂O₃ by ion exchange, as the latter is more temperature-stable at composite sintering temperatures. The conditions of formation, thermal stability, and chemical compatibility of these interfacial phases were examined. α-AI₂O₃ platelets with Ca-β"-AI₂O₃ film were incorporated into 3Y-TZP. The β"-AI₂O₃/ZrO₂ interface was found to promote platelet debonding and pullout, thus enhancing the α-AI₂O₃ platelet/crack interactions during the fracture process.     

CrO2-Cr2O3 Phase Boundary Under High O2 Pressures

The phase boundary between CrO₂ and Cr₂O₃ was reinvestigated under high O₂ pressures by using a new type of gas compressor. The boundary curve can be represented as log Po₂= 7.16-(3579/ T ). Using the observed data, Δ G °, Δ H °, and Δ S ° for the reaction 2CrO₂⇋Cr₂O₃+½O₂ were calculated to be: Δ G °= -(1.55/100) T +7.60 kcal/mol, Δ H °= -8.19 kcal/mol, and Δ S °= (-15.8/ T )+0.0155 kcal/mol.     

Microstructural Development on Crystallizing Hot-Pressed Pellets of Cordierite Melt-derived Glass Containing B2O3 and P2O5

Comparing the crystallization mechanism of stoichiometric and B₂O₃ and P₂O₅ containing glass reveals that the additives extend the gap between the glass transition and crystallization temperatures and suppress formation of μ, cordierite while promoting direct crystallization of α cordierite. Detailed TEM analysis of nucleation and growth of crystals in hot-pressed pellets of B₂O₃/P₂O₅-containing glass particles shows that nucleation occurs on unidentified heterogeneous nuclei at the sites of the previous particle surfaces. Growth of α cordierite with a cellular morphology or μ cordierite with a dendritic morphology is most likely controlled by the glass composition directly ahead of the growth front.     

Crystallization Behavior of CaO–P2O5 Glass with TiO2, SiO2, and Al2O3 Additions

TiO₂ above 4 mol% is an effective nucleating agent for CaO–P₂O₅ glass which also contains substantial SiO₂ and Al₂O₃ additions. Glass ceramics can be made from this glass using a single slow heating ramp with no need for a nucleating heat treatment step. Powder of this composition crystallizes rapidly to β-Ca₂P₂O₇, whereas bulk glass crystallizes from diphasic nuclei consisting of a central cubic Ca-P-Ti-Si-Al oxide phase surrounded by impure AlPO₄ dendrites. Metastable calcium phosphate grows on the AlPO₄ dendrites and later transforms to β-Ca₂P₂O₇.     

Stable and Metastable Equilibria in the Systems Y2O2-Al2O3, and Gd2O3-Fe2O3

The phase equilibrium relations in the systems Y₂O₃-Al₂O₃ and Gd₂O₃-Fe₂O₃ were examined. Each system has two stable binary compounds. A 3:s molar ratio garnet-type compound exists in both systems. The 1:1 distorted perovskite structure is stable in the system Gd₂O₃-Fe₂O₃ but only metastable in the system Y₂O₃-AI₂O₃. This interesting example of metastable formation and persistence of a compound with ions of high Z/r values explains the discrepancies in the literature on the structure of the composition YA1O₃. A new 2:1 molar ratio cubic phase has been found in the system Y₂O₃-A1₂O₃. Since silicon can be completely substituted for aluminum in this compound, the aluminum ions are presumably in fourfold coordination.     

Glass Formation Range, Acid Resistivity, and Surface Charge Density of ZnO-B2O3-SiO2 Passivation Glass Containing Al2O3

The glass formation range in the system ZnO-B₂O₃-SiO₂ increases when 5% Al₂O₃ is added and then decreases with further Al₂O₃ additions. The acid resistivity of the glass also increases when Al₂O₃ is added. An observed increase in negative charge with Al content until the system contains equal amounts of Al and Si (in forms of mole %) is explained by the formation of AlO₄⁻ tetrahedra which substitute in the SiO₄ network. Alkaline-earth oxides cause a positive charge which compensates for the negative charge formed by Al₂O₃. Antimony oxide and lanthanum oxide result in a negative charge in the glass. The formation of a negative or positive charge in the glass is thought to reflect the acidity or basicity of the glass, respectively.     

Prominent Nanocrystallization of 25K2O·25Nb2O5·50GeO2 Glass

Some K₂O-Nb₂O₅-GeO₂ glasses are prepared, and their crystallization behaviors are examined. 25K₂O·25Nb₂O₅·50GeO₂ glass with the glass transition temperature T _g= 622°3C and crystallization onset temperature T _x= 668°3C shows a prominent nanocrystallization. The crystalline phase is K_3,8Nb₅Ge₃O_20,4 with an orthorhombic structure. The sizes of crystals in the crystallized glasses heat-treated at 630° and 720°3C for 1 h are °10 and 20–30 nm, respectively, and the crystallized glasses obtained by heat treatments at 620°-850°3C for 1 h maintain good transparency. The density of crystallized glasses increases gradually with increasing heat-treatment temperature, and the volume fraction of crystals in the sample heat-treated at 630°3C for 1 h is estimated to be ∼35%. The usual Vickers hardness and Martens hardness (estimated by nanoindentation) of 25K₂O·25Nb₂O₅·50GeO₂ glass change steeply by heat treatment at T _g, i.e., at around 35% volume fraction of nanocrystals. The present study demonstrates that the composite of nanocrystals and the glassy phase has a strong resistance against deformation during Vickers indenter loading in crystallized glasses.