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 .     

The System Na2O-CaO-SiO2-H2O

A portion of the quaternary phase diagram for Na₂O-CaO-SiO₂-H₂O has been constructed. Plotting concentrations as their 10th roots allows compounds having solubilities which differ by several orders of magnitude to be represented on a single diagram. The compositional relationships among sodium-substituted calcium silicate hydrate, calcium-substituted sodium silicate hydrate, calcium bydroxide, a quaternary compound of approximate composition 0.25Na₂O · CaO · SiO₂· 3H₂O, sodium hydroxide monohydrate, and miscellaneous sodium silicate hydrates are presented. The quaternary diagram constructed shows the quaternary compound to exist in equilibrium with sodium-substituted calcium silicate hydrate and calcium hydroxide. Conditions in concrete pore solutions which favor the formation of this quaternary compound may also favor the occurrence of the alkali-silica reaction.     

Phase Diagram of the System Na2O·Ga2O3-Ga2O3 and its Relation to the System Na2O·Al2O3-Al2O3

A new phase diagram for the system Na₂O-Ga₂O₃ (>50 mol% Ga₂O₃) is presented. It is based on information from differential thermal analysis, X-ray examination of quenched samples, and a radiochemical technique for determining the compositions of a primary phase and a liquid in equilibrium with it. The diagram provides a guide for the growth of primary crystals of the two ionically conducting sodium gallates that are analogs of the technologically important β- and β"-aluminas.     

Phase Equilibria and Liquid Immiscibility in the System PbO-B2O3-SiO2

A detailed study of the system Pb0–B₂0₃–Si0₂ was undertaken because of the interest in lead borosilicate fluxes and the possibility of producing opaque low-melting enamels by controlled liquid-phase separations. Studies in the portion of the system containing greater than 60% PbO produced little change from previous work. The shape of the liquidus surface beneath the two-liquid region and the shape of the immiscibility dome were determined. Much of the observed immiscibility is metastable, particularly for compositions containing greater than 40% SiO₂. Using the electron microscope provided information on the way the rate of formation, stability, and texture of the immiscible liquids are affected by composition, time, and temperature. Finally, a high-temperature centrifuge was constructed to separate the immiscible liquids and thus define tie lines within the immiscibility dome.     

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.     

Some Properties of the System Na2O-NaF-B2O2-H2O

It was first shown that the enamel slips which have the best suspnding characteristics contain equal amounts of Na₂O and B₂O₃ and at least a moderate amount of NaF. The solubilities of mixtures of Na₂O, NaF, and B₂O₃ were then investigated. The pH of these solutions and the primary crystalline phases separating on evaporation also were determined. The solubility data obtained at room temperature were summarized. When the solutions were evaporated, NaF was the first crystalline phase to separate from a large proportion of the mixtures investigated. It was concluded that the desirable handling characteristics of enamels whose mill liquors contain the proper proportion of Na₂O, NaF, and B₂O₃ are not due to the formation of complex salts but to the following combination of properties: (1) the presence of salts with a moderate solubility which changes very slightly with temperature, (2) a moderate pH of about 10 in a probably well-buffered solution, (3) a relatively stable crystalline material, NaF, as a primary phase, and (4) a secondary phase which crystallizes slowly with relatively little shrinkage.     

Phase Equilibria in the System Na2O – Nb2O5

Phase equilibria data, obtained both by differential thermal analysis and by quenching, are presented for the system Na₂O-Nb₂O₅. Five compounds corresponding to the formulas 3Na₂O.1Nb₂0₆, lNa₂O. 1Nb₂O₅, lNa₂O 4Nb₂O₆, lNa_zO.7Nb₂O₅, and lNa₂O. 10Nb₂O₆ have been found. The compound 3Na_z0.lNb₂O₅ melts congruently at 992°C. The compounds 1Na₂O. 4Nb₂O₆, lNa₂O.7Nb₂O, and 1Na₂O. 1Onb₂O₅ melt incongruently at 1265°, 1275°, and 1290°C., respectively. The well-known perovskite structure phase NaNbO₃ was found to melt congruently at 1412°C. The transition temperatures in NaNbO₅ were checked by thermal analysis and only the major structural changes at 368° and 640°C. could be detected. A new disordered form of NaNbO₃ could be preserved to room temperature by very rapid quenching.     

Solid Solubility of Na2O in Mullite

Incorporation of up to 0.4 wt% Na₂O was found in the mullites of fused-cast mullite brick. Sodium oxide incorporation probably requires very high temperatures and persists only when the material is quenched rapidly to room temperature; it may be stabilized by simultaneous entry ofZr⁴⁺ into the mullite structure.     

Phase Equilibria in the System Na2SiO3-Li2SiO3

Phase equilibria were studied for the system Na₂SiO_:rLi₂SiO₃. The 2 end-member metasilicates show limited mutual solid solubility with the (Na_2-χLi_χ)SiO₃ solid solutions being particularly extensive at solidus temperatures (0 x 1.06). Ordering of the latter solid solution occurs at the NaLiSiO_;) composition with a_supercellx= 6a_subcell During cooling of the solid solutions, metastable phase transformations occur; a twinned monoclinic metastable phase, low (Na, Li)₂SiO₃, has been characterized.     

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.     

Oxidation-Reduction Equilibria in Molten Na2O.2SiO2 Glass

The oxidation-reduction equilibria in molten glasses having a soda/silica ratio of 1/2 and containing small amounts of variable-valence ions of the transition elements titanium, vanadium, iron, cobalt, and nickel, the post-transition elements tin and antimony, and the rare-earth element cerium were obtained by equilibrating the melts with various atmospheres. The simple mass expression
was always applicable. In the expression, n is the number of electrons involved in the valence change of the metal M. The value of n is 1 for all systems except for the ions of antimony and tin where n is 2. The ions found are those generally accepted as existing in glass melts which are Ti³⁺, Ti⁴⁺; Fez+, Fe³⁺; Ce³⁺, Ce⁴⁺; Mn²⁺, Mn³; Co²⁺, Co³⁺; Ni²⁺, Ni³; Sb³⁺, Sb⁵⁺; and Sn²⁺, Sn⁴⁺. Two mass action expressions were needed for vanadium-containing glasses to describe the equilibria between 5+, 4+, and 3 f species.     

Electrical Conductivity of HF-H2O- Impregnated Na2O.3SiO2 Glass

Up to 5.75 WHO of concentrated (49 wt%) HF solution was placed in Nazo.3SiO₂ glass under hydrothermal conditions. Electrical conductivity of the resulting glasses was primarily determined by the water content.     

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.     

Phase Equilibria in the System Na2SiO3-Li2SiO3-SiO2

Ternary phase relations have been studied and several modifications made to Kracek's phase equilibrium diagram. These include location of the primary phase fields of Na₆Si₈O₁₉ and Li₂Si₂O₅. Metastable phases and polymorphs were often encountered, notably a primary phase, δ-Na₂Si₂O₅, and a new polymorph of Li₂Si₂O₅.     

Differences in Surface Behavior of Alkali Ions in Li2O ·3SiO2 and Na2O · 3SiO2 Glasses

The molecular dynamics computer simulation technique was used to determine the short-time dynamics behavior and resultant structures of ions at the surface of Li₂0·3SiO₂ and Na₂O-3SiO₂ glasses. Room temperature and elevated temperatures were used. Results are compared with similar studies of the K₂O·3SiO₂ glass surface and with recent experimental ion-scattering-spectroscopy data. The simulations indicate that a localized surface rearrangement occurs within picoseconds after formation of the free surface, creating a surface excess of alkali in the Na (and K) case, but not in the Li case. Elevated temperatures, even for brief times, enhance the observed surface excess of Na and K. The results correspond to those obtained from the ion-scattering-spectroscopy studies.     

Effect of Na2O/K2O Ratio on Chemical Durability of Alkali-Lime-Silica Glasses

The chemical resistance of mixed-alkali glasses to water was measured by determining the sodium, potassium, calcium, and silicon ions extracted instead of evaluating it from the alkalinity of the mixed-alkali extracts. In glasses of the composition K₂O and Na₂O 18, CaO 10, and SiO₂ 72% the minimum extraction of alkali (maximum durability) occurred for a K₂O/-Na₂O ratio of 2.6/1.0 (by weight). Based on an ionic-composition analysis of the results, an empirical index is suggested for determining the relative degree of ion-exchange and network-breakdown modes of reactions that occur when such mixed-alkali glasses are attacked by water.     

Effect of Small Additions of Al2O3 and Ga2O3 on the Immiscibility Temperature of Na2O-SiO2 Glasses

Alumina and gallia were substituted separately for Na₂O in amounts of 0.2, 0.5, 1.0, 1.5, 2.0, and 3.0 wt% in three Na₂O-SiO₂ glass compositions (82, 84, and 86 wt% SiO₂) within the immiscibility region. The immiscibility regions for each system extend to ∼1.5 mol% of the added oxide. In general, the addition reduced the immiscibility temperature ( T _m), but at the edge of the immiscibility region (82% SiO₂) the Na₂O loss effect initially increased T _m. A structural model of the miscibility of Al₂O₃ added to silicate glasses is presented.     

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.