The High-Silica Liquidus Surface of the System Na2O-B2O3-SiO2

The liquidus surface for the high silica (>60 wt%) portion of the ternary system Na₂O-B₂O₃-SiO₂ is presented. Determinations were made by quench runs and solubility studies. The compound, reedmergnerite, NaBSi₃O₈ was not observed. Tridymite is the major primary phase .     

Effects of MoO3, on Phase Separation of Na2O-B2O3-SiO2 Glasses

Immiscibility temperatures of Na₂O-B₂O₃-SiO glasses, with andwithout 1 mol% MoO₃, additions, were determined and the effect of MoO₃ additions on the 65O°C immiscibility isotherms was established. In addition, immiscibility temperature and phase-separation morphology of an Na₂O-B₂O₃-SiO₂ glass with progressive additions of MoO₃, were investigated. It was found that the addition of small amounts of MoO₃ extends the immiscibility boundary of the system and raises the immiscibility temperature by ∼l8°C for each mol % MoO₃, addition. Analysis of phase-separation morphology suggests that the MoO₃, additions do not significantly alter the tie lines of phase separation in the system, although such additions cause a lowering of the viscosities and the glass-transition temperatures of these glasses.     

Glass Formation and Properties of Glasses in the System Na2O-B2O3-SiO2-TiO2

An investigation was made of the effect of TiO₂ on the glassforming region and on the physical properties of glasses in the system Na₂O-B₂O₃-SiO₂TiO₂. Glasses containing up to 45 mole % TiO₂ may be formed with an alkali content of 30 mole %. At lower alkali contents (10 mole % Na₂O) glasses may be formed containing up to 22 mole % TiO₂. The way in which the coefficient of linear thermal expansion and the transformation and softening temperatures are affected by TiO₂ additions has been determined.     

Precipitation and Magnetic Behavior of Beta NaFeO2 in Glasses Along the Na2SiO3-Fe2O3 Join

The magnetic behavior of β-NaFeO₂ precipitated in compositions along the Na₂SiO₃-Fe₂O₃ join of the Na₂O-Fe₂O₃-SiO₂ system is reported from magnetic susceptibility data and Moessbauer studies. The anomalous magnetic properties observed are discussed in terms of the possibility of the presence of super-paramagnetism.     

Crystallization of Beta NaFeO2 from a Glass Along the Na2SiO3-Fe2O3 Join

Fine-particle beta sodium ferrite (β-NaFeO₂), rather than α-Fe₂O₃, may be responsible for superparamagnetic behavior in a glass of composition (in mole fractions) 0.37Na₂O-0.26Fe₂O₃-0.37SiO₂. The 700°C isothermal section of the phase diagram of the Na₂O-Fe₂O₃-SiO₂ system is given, showing a three-phase field bounded by Na₂SiO₃-NaFeO₂-Fe₂O₃; there is no evidence for the existence (at 700°C) of compounds of molar composition 6Na₂O-4Fe₂O₃-5SiO₂ or 2Na₂O-Fe₂O₃-SiO₂. The Moessbauer spectrum of β-NaFeO₂ has an internal magnetic field of 487 kOe at room temperature.     

Phase Relations in the System CaO-Ta2O5-SiO2

The system CaO-Ta₂O₃-SiO₂ was studied using a combination of hot-stage microscopy and the quenching technique. Primary crystallization fields were defined for the various calcium silicates, and for the calcium tantalates: CaO·2Ta₂O₅, CaO·Ta₂O₅, 2CaO·Ta₂O₅, and 4CaO·Ta₂O₅. A congruently melting ternary compound 10CaO·Ta₂O₅·6SiO₂, isostructural with the mineral niocalite, is the only ternary phase in the system. A large twoliquid region extends across the system from the CaO-SiO₂ binary to within 1 wt% of the Ta₂O₃-SiO₂ binary but does not cut it, in marked contrast to the analogous CaO-Nb₂O₅-SiO₂ system. Other somewhat unexpected differences were noted between these systems.     

Liquid Immiscibility in the Systems X2O-MO-B2O3-SiO2 (X=Na, K; M=Mg, Ca, Ba) and Na2O-MgO-BaO-B2O3-SiO2

The limits of miscibility at 650°C were determined for compositions with the mole ratio SiO₂/B₂O₃=1.07 in the systems X₂O-MO-B₂O₃-SiO₂ (X = Na,K; M = Mg,Ca,Ba) and Na₂O-MgO-BaO-B₂O₃-SiO₂. The form of the miscibility gaps in the quaternary systems is similar to that previously described for the system Na₂O-ZnO-B₂O₃-SiO₂. The topography of miscibility gaps in systems of this type is discussed in detail. The extent of the miscibility gap is correlated with the polarizing power of each cation, X and M (Na > K and Zn ≅ Mg > Ca > Ba) both among the seven quaternary systems and within the single five-component system examined. The possibility of using empirical correlations observed among the quaternary systems to predict the behavior of other compositions, or of more complex systems, is explored.     

Liquid Immiscibility in the System K2O-B2O3-SiO2

The subliquidus miscibility gap in the system K₂O-B₂O₃-SiO₂ has been determined for compositions with molar ratios SiO₂/B₂O₃<2 and T≥550°C. The shape of the miscibility gap is an elongated dome similar in form to, but less extensive than those in the lithium and sodium borosilicate systems. The consolute composition (molar) and temperature are estimated to be 4 ± 1 K₂O -30±8 B₂O₃-66±8 SiO₂ and 629±5°C, respectively .     

Liquid Immiscibility in the System Na2O-ZnO-B2O3-SiO2

The limits of miscibility within a portion of the system Na₂O-ZnO-B₂O₃-SiO₂ were determined at 650°, 800°, and 950°C. The miscibility gap at 800° and 950°C is a low dome, adjoining the zinc borosilicate miscibility gap. Below 755°C the dome intersects the Na2O-B₂O₃-SiO₂ face of the phase diagram. The locus of this intersection is in agreement with literature data on the sodium borosilicate system. Estimated tie-line placement in the ZnO-B₂O₃-SiO₂ miscibility gap at 1300°C resembles those reported for the corresponding CaO and SrO systems. The microscopic morphology of glasses with the weight composition xNa₂O-18ZnO-18B₂O₃-64SiO₂ with 0≤×≤12 is described in detail.     

Phase Relations in the System Na2O-Li2O-Al2O3

A subsolidus phase diagram for the system Li₂O-Na₂O-Al₂O₃ at 1500°C is presented. Unlike the analogous system MgO-Na₂O-Al₂O₃, β" was the only ternary compound observed in the section of the lithia-based system examined in this study. A fairly extensive region of β solid solution was found. In contrast, the range of compositions where β" exists is small and does not extend into the Na₂O-Al₂O₃ binary.     

Studies in Lithium Oxide Systems: XII, Li2O-B2O3-Al2O3

Tentative phase relations in the binary system BnOa-A1₂O₃ are presented as a prerequisite to the understanding of the system Li₂O-B₂O₃-Al₂O₃. Two binary compounds, 2A1₂O₃.B₂O₃ and 9A1₂O₃.-2B₂O₃, melted incongruently at 1030° f 7°C and about 144°C, respectively. Two ternary compounds were isolated, 2Li₂O.A1₂O₃.B₂O₃ and 2Li₂O. 2AI₂O₃. 3B₂0₃. The 2:1:1 compound gave a melting reaction by differential thermal analysis at 870°± 20° C, but the exact nature of the melting behavior was not determined. The 2:2:-3 compound melted at 790°± 20° C to Li_zO.-5Al₂O₃ and liquid. X-ray diffraction data for the compounds are presented and compatibility triangles are shown.     

Subsolidus Phase Equilibria in the System Na2O-Bi2O3-TiO2 at 1000°C

Subsolidus phase relations in the system Na₂O-Bi₂O₃-TiO₂ at 1000°C were investigated by solid-state reaction techniques and X-ray diffraction methods. Five ternary compounds were observed in the system: Na_0.5Bi_4.5Ti₄O₁₅; Na_0.5Bi_0.5TiO₃; a cubic pyrochlore solid solution composed of xNa₂O.25Bi₂O₃.(75−;x) TiO₂ where x is 2.5 to 3.75; a new compound Na_0.5Bi_8.5Ti₇O₂₇ indexed with the orthorhombic cell of a = 5.45, b = 5.42, and c = 36.8 Å; and an unidentified phase with the probable composition NaBiTi₆O₁₄.     

Phase Equilibria and Crystallization of Melts in the System Na2O-BaO-SiO2

Phase-equilibrium studies of the liquidus surface of the Na₂O-BaO-SiO₂ system are presented. The system contains 5 ternary compounds, Na₂Ba₄Si₁₀O₂₅, Na₂Ba₄Si₂O₆, Na₂Ba₂Si₂O₇, X (probably Na₂Ba₁₈Si₂₈O₇₅), and Y (probably Na₂Ba₄₅Si₇₃O₁₉₂), all of which melt incongruently. Twenty-three liquidus invariant points, including 13 peritectics, 4 eutectics, and 6 thermal maxima, were located. Metastable crystallization reactions are commonly encountered, and some of the metastable equilibria are described.     

Studies in Lithium Oxide Systems: VII, Li2O–B2O2–SiO2

Phase relations in the system Li₂O–B₂O₃–SiO₂ were studied by quenching and solid-state reactions. No ternary compounds were detected in the portion of the system containing less than 53% Li₂O. Compatibility triangles were formed from the binary borate and silicate compounds. Liquidus data obtained by quenching are reported for four joins, Li₂O·2SiO₂–Li₂O·2B₂O₃, Li₂O·SiO₂-Li₂O·2B₂O₃, Li₂O·SiO₂-Li₂O·B₂O₃, and Li₂O·2B₂O₃-SiO₂. The last join cuts across the two-liquid region and is not a true binary system. Some probable ternary invariant points were located in the portion of the system which was quenchable to glass and adjacent to the two-liquid region. Further data on the previously reported immiscible liquid formation are given and the significance is discussed. Data on the thermal expansion behavior of certain glasses are presented.     

Phase Relations in the System Na2O-TiO2-SiO2

Liǵuid us and subsolidus phase relations were studied using the quenching technique. The system contains four ternary compounds stable to liquidus temperatures: Na₂TiSi₄O₁₁, Na₂TiSi₂O₇, Na₂TiSiO₅, and Na₂Ti₂Si₂O₉. Six eutectics, eight peritecties, and eight thermal maxima were located and a region of liquid immiscibility was delineated. X-ray powder data are given for the stable and metastable crystalline phases. Glass-transition temperatures were determined by thermal analysis. The relation between physical properties of melts and glasses and the configuration of the liquidus is discussed.     

Determination of OH Extinction Coefficients in R2O-B2O3-SiO2 Glasses (R = Li, Na, K)

Infrared spectra of glasses of the system R₂O-B₂O₃-SiO₂ were investigated. The extinction coefficients of the hydroxyl absorption band ("free OH") were calculated by a method proposed for alkali borate glasses. The results confirmed the applicability of this method to homogeneous and phase-separated alkali borosilicate glasses. The variation of the hydroxyl absorption band position was interpreted according to the structural characteristics of the studied glasses.     

The System Al2O3-Cr2O3-Sio2

Liquidus phase equilibrium data are presented for the system Al₂O₃-Cr₂O₃-SiO₂. The liquidus diagram is dominated by a large, high-temperature, two-liquid region overlying the primary phase field of corundum solid solution. Other important features are a narrow field for mullite solid solution, a very small cristobalite field, and a ternary eutectic at 1580°C. The eutectic liquid (6Al₂O₃-ICr₂O₃-93SiO₂) coexists with a mullite solid solution (61Al₂O₃-10Cr₂O₃-29SiO₂), a corundum solid solution (19Al₂O₃-81Cr₂O₃), and cristobalite (SO₂). Diagrams are presented to show courses of fractional crystallization, courses of equilibrium crystallization, and phase relations on isothermal planes at 1800°, 1700°, and 1575°C. Tie lines were sketched to indicate the composition of coexisting mullite and corundum solid solution phases.     

Growth of α-Al2O3 Crystals by Na2O Evaporation

A technique for growing α-Al₂O₃ crystals is described in which Na₂O·11Al₂O₃ is dissolved in a liquid of composition Na₂O·4TiO₂·3Al₂O₃. Alpha Al₂O₃ is precipitated as Na₂O evaporates from the system; Na₂O·11Al₂O₃ serves as a source of Al₂O₃, and Na₂O in the liquid. The content of solids in the mixture is always such that it does not melt completely. The size of the α-Al₂O₃ crystals grown is related to the Na₂O content of the composition. Crystals as large as 4000 by 3000 μm in the α-axis direction and 500 μm in the c -axis direction have been grown.     

The System Iron Oxide-TiO2-SiO2 in Air

Phase relations at liquidus temperatures in the system iron oxide-TiO₂-SiO₂ have been determined in air. The equilibrium existence of the crystalline phases magnetite (ss), hematite (ss), pseudobrookite(ss), rutile(ss), and silica (tridy-mite or cristobalite) has been established. Three isobaric eutectic points are formed by the intersections of quaternary liquidus univariant lines of the system Fe-Ti-Si-O and the 0.21 atmosphere isobaric surface. The liquid misci-bility gaps present in the bounding "binary" systems iron oxide-Si0₂ and TiO₂-SiO₂ extend across the composition triangle representing the "ternary" system iron oxide-TiO₂-SiO₂. Liquidus temperatures decrease within the two-liquid region from approximately l <57Q^a C. in the system iron oxide-SiO₂ and 1780°C. in the system Ti(VSiO₂ to 1540°C. at the cristobalite-rutile(ss) boundary curve which bisects the two-liquid region. Paths of equilibrium crystallization of representative mixtures are discussed with reference to a simplified projection into the plane FeOFe₂O₃-TiO₂-SiO₂ as well as in terms of the tetrahedron representing the system FeO-Fe₂O₃-TiO₂-SiO₂.     

Phase Formation in the System Na2O · Al2O3-CaO · A12O3-Al2O3 at 1200°C in Air

Phase relations in the system Na₂O_· Al₂O₃-CaO· Al₂O₃-Al₂O₃ at 1200°C in air were determined using the quenching method and high-temperature X-ray diffraction. The compound 2Na₂O · 3CaO · 5Al₂O₃, known from the literature, was reformulated as Na₂O · CaO · 2Al₂O₃. A new compound with the probable composition Na₂O · 3CaO · 8Al₂O₃ was found. Cell parameters of both compounds were determined. The compound Na₂O · CaO-2Al₂O₃ is tetragonal with a = 1.04348(24) and c = 0.72539(31) nm; it forms solid solutions with Na₂O · Al₂O₃ up to 38 mol% Na₂O at 1200°C. The compound Na₂O · 3CaO · 8Al₂O₃ is hexagonal with) a = 0.98436(4) and c = 0.69415(4) nm. The compound CaO · 6Al₂O₃ is not initially formed from oxide components at 1200°C but behaves as an equilibrium phase when it is formed separately at higher temperatures. The very slow transformation kinetics between β and β "-Al₂O₃ make it very difficult to determine equilibrium phase relations in the high-Al₂O₃ part of the diagram. Conclusions as to lifetime processes in high-pressure sodium discharge lamps can be drawn from the phase diagram.