Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.     

The System HfO2-Y2O3-Er2O3

A mathematical model of the liquidus surface based on a reduced polynomial method was proposed for the system HfO₂-Y₂O₃-Er₂O₃. The results of calculations according to this model agree fairly well with the experimental data. Phase equilibria in the system HfO₂-Y₂O₃-Er₂O₃ were studied on melted (as-cast) and annealed samples using X-ray diffraction (at room and high temperatures) and micro-structural and petrographic analyses. The crystallization paths in the system HfO₂-Y₂O₃-Er₂O₃ were established. The system HfO₂-Y₂O₃-Er₂O₃ is characterized by the formation of extended solid solutions based on the fluorite-type (F) form of HfO₂ and cubic (C) and hexagonal (H) forms of Y₂O₃ and Er₂O₃. The boundary curves of these solid solutions have the minima at 2370°C (15. 5 mol% HfO₂, 49. 5 mol% Y₂O₃) and 2360°C (10. 5 mol% HfO₂, 45. 5 mol% Y₂O₃). No compounds were found to exist in the system investigated.     

11B and 27Al Nuclear Quadrupole Interactions in SiO2-B2O3-Al2O3-R2O Glass Systems

Quadrupole interactions of ¹¹B and ²⁷Al in SiO₂-B₂O₃-Al₂O₃-R₂O glass systems were investigated to determine the structure of these glasses, which should be amenable to chemical strengthening. The ratio of BO₄ units to BO₃ units approached unity as the R₂O/Al₂O₃ ratio for compounds having fixed B₂O₃ contents approached unity. Nuclear quadrupole coupling constants ( e²Qq/h =2.73 to 2.93 MHz) were measured for the NMR spectra of ¹¹B triangles. The line shapes of ²⁷Al spectra varied with chemical composition, but a few glasses exhibited ²⁷Al line shapes similar to those of the AlO₄ triclusters in SiO₂-Al₂O₃-Na₂O glasses. Compositional trends in the formation of BO₄ and AlO₄ were deduced from the NMR spectra.     

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.     

The System Si3N4-SiO2-Y2O3

Subsolidus phase relations were established in the system Si₃N₄-SiO₂-Y₂O₃. Four ternary compounds were confirmed, with compositions of Y₄Si₂O₇N₂, Y₂Si₃O₃N₄, YSiO₂N, and Y₁₀(SiO₄)₆N₂. The eutectic in the triangle Si₃N₄-Y₂Si₂O₇-Y₁₀(SiO₄)₆N₂ melts at 1500°C and that in the triangle Si₂N₂O-SiO₂-Y₂Si₂O₇ at 1550°C. The eutectic temperature of the Si₃N₄-Y₂Si₂O₇ join was ∼ 1520°C.     

Phase Relations in the Pseudobinary System Na2TiSi4O11-Na2Ti2Si2O9

The quenching technique was used to study subliquidus and subsolidus phase relations in the pseudobinary system Na₂ Ti₂Si₂ O₁₁-Na₂ Ti₂ Si₂ O₉. Both narsarukite (Na₂TiSi₄O₁₁) and lorenzenite (Na₂Ti₂Si₂O₉) melt incongruently. Narsarsukite melts at 911°±°C to SiO₂+liquid, with the liquidus at 1016°C. Lorenzenite melts at 910°±5°C to Na₂ Ti₆ O₁₃+liquid; Na₂ Ti₆ O₁₃ reacts with liquid to form TiO₂ and is thus consumed by 985°±5°C. The liquidus occurs at 1252°C.     

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.     

Phase Equilibria in the System CaF2-AlF3-Na3AlF6 and Part of the System CaF2-AlF3-Na3AlF6-Al2O3

The complete phase-equilibrium diagram of the system CaF₂-AlF₃-Na₃AlF₆ and the subsolidus portion of the system CaF₂-AlF₃-Na₃AlF₆-Al₂O₃ were established from microscopic, powder X-ray diffraction, quench, and DTA data obtained from samples encapsulated in sealed tubes and either reacted in the solid state or melted and recrystallized. The system Na₃AlF₆-CaF₂ contains a simple eutectic with no compound formation or solid solution. The system CaF₂-AlF₃-Na₃AlF₆ contains two ternary compounds, NaCaAlF₆ and NaCaAl₂F₉, which melt incongruently at 735° and 712°C, respectively; NaCaAlF₆ exists in three polymorphic forms with transitions at 610° and 722°C and NaCaAl₂F₉ is body-centered cubic with a₀= 10.765 Å. The three binary and two ternary compounds divide the system into eight compatibility triangles. Along the NaCaAlF₆-Na₃AlF₆ join, 7 mol% NaCaAlF₆ is soluble in α-cryolite at 525° and 42% in β-cryolite at 731°C. The quaternary system Na₃AlF₆-AlF₃-CaF₂-Al₂O₃ contains eight compatibility tetrahedra.     

Thermodynamic Properties of Fe3O4-FeV2O4 and Fe3O4-FeCr2O4 Spinel Solid Solutions

Solid solutions of Fe304-FeV204 and Fe304-FeCr204 were prepared and equilibrated with Pt under controlled streams of CO/CO, gas mixtures at 1673 K. The concentration of Fe in Pt was used to determine the activity of Fe304 in the solid solutions. The activity of the second component was calculated by Gibbshhem integration. From these data, the Gibbs energy of mixing was derived for both systems. The experimental results and theoretical values which are determined from calculated cation distribution compare favorably in the case of vanadite solid solutions but not in the case of chromite solid solutions. The difference is attributed to a heat term arising from lattice distortion due to cation size difference. The positive heat of mixing will give rise to a miscibility gap in the system Fe304-FeCr204 at lower temperatures.     

Solid Solubility and Polymorphism in the System Sr2SiO4-Sr2GeO4-Ba2GeO4-Ba2SiO4

The reciprocal salt pair Sr₂SiO₄-Sr₂GeO₄-Ba₂GeO₄-Ba₂SiO₄ was investigated using X-ray powder diffraction and DTA. Unlimited solubility in the low-K₂SO₄ structure type (α') occurs throughout the system above 85°C. The nonlinear changes of some lattice constants of the solid solutions are discussed. A stable monoclinic low-temperature (β) form of Sr₂SiO₄ was found which converts reversibly to the high-temperature α'-modification at 85°C. The enthalpy of the β-α' transition is 51 cal/mol. In the reciprocal salt pair the β-form solid solutions occur in a very narrow region below 85°C.     

Solid Solutions in the System LaMgAl11O19- LaMgGa11O19-LaMgFe11O19

Solid Solutions with the magnetoplumbite structure in the System LaMgAl₁₁O₁₉-LaMgGa₁₁O₁₉-LaMgFe₁₁O₁₉ were studied by X-ray diffractometry of sintered samples. Complete miscibility exists in the subsystem LaMgAl₁₁O₁₉-LaMgGa₁₁O₁₉ and in a narrow adjacent ternary area with low iron content. In the other subsystems and in the major part of the ternary field, a magnetoplumbite phase occurs together with other compounds.     

Electrical Conduction in Nano-Structured La0.9Sr0.1Al0.85Co0.05Mg0.1O3 Perovskite Oxide

Nanocrystalline La_0.9Sr_0.1Al_0.85Co_0.05Mg_0.1O₃ oxide powder was synthesized by a citrate–nitrate auto-ignition process and characterized by thermal analysis, X-ray diffraction, and impedance spectroscopy measurements. Nanocrystalline (50–100 nm) powder with perovskite structure could be produced at 900°C by this process. The powder could be sintered to a density more than 96% of the theoretical density at 1550°C. Impedance measurements on the sintered samples unequivocally established the potential of this process in developing nanostructured lanthanum aluminate-based oxides. The sintered La_0.9Sr_0.1Al_0.85Co_0.05Mg_0.1O₃ sample exhibited a conductivity of 2.40 × 10⁻² S/cm in air at 1000°C compared with 4.9 × 10⁻³ S/cm exhibited by La_0.9Sr_0.1Al_0.85Mg_0.15O₃.     

Fast Li+ Ion Conduction in Li2O-Al2O3-TiO2-SiO2-P2O5 Glass-Ceramics

Fast lithium ion conducting glass-ceramics have been successfully prepared from the pseudobinary system 2[Li_{1+ x} Ti₂Si _x P_{3− x} O₁₂]-AlPO₄. The major phase present in the glass-ceramics was LiTi₂P₃O₁₂ in which Ti⁴⁺ ions and P⁵⁺ ions were partially replaced by Al³⁺ ions and Si⁴⁺ ions, respectively. Increasing x resulted in a considerable enhancement in conductivity, and in a wide composition range extremely high conductivity over 10⁻³ S/cm was obtained at room temperature.     

The Series MgCr2O4-MgFe2O4

The characteristics of spinels in the series MgCr₂O₄-MgFe₂O₄ were determined. The plot of cell size vs. molar composition is unusual in series showing complete solid solution because an unusually large deviation from Vegard's law was observed. This deviation is caused by changes in spinel structure with composition and temperature, and an equation was derived which applies a correction in terms of the degree of inversion. The effects of temperature on compositions high in MgFe₂O₄ include changes in density and refractive index. Solid solution of forsterite in MgCr₂O₄ decreases the cell size to 8.329 A but apparently is less than 1%. Changes in composition caused by vapor loss or by dissociation are small enough that this series is essentially binary below 1400° C.     

The System K2SO4-Cs2SO4

The phase diagram for the system K₂SO₄-Cs₂SO₄ was determined by using DTA for melting relations and DTA and high-temperature X-ray diffractometry for subsolidus relations. At the solidus the system shows complete solid solubility, with a minimum at 940°C and 50 mol% Cs₂SO₄. Orthorhombic K₂SO₄ and Cs₂SO₄, the stable low-temperature forms, show mutual solid solubility and form a eutectoid at 50 mol% Cs₂SO₄ and 430°C, the lowest temperature of stability of the high-temperature hexagonal solid-solution phase. Isothermal plots of the a and c dimensions of this hexagonal phase vs composition show large positive deviations from linearity for c. These deviations are interpreted on the basis of the crystal structure of KNaSO₄ with a similar unit cell.     

Polymorphism of LiGa5O8 and of LiGa5O8-MgGa2O4Solid Solutions

High-temperature X-ray diffraction and differential thermal analyses showed that LiGa₅O₈ exists in two polymorphs related by the first-order transition at 1138°±3°C of the low-temperature simple-cubic form, space group (probably) O⁷, to the high-temperature spinel (fcc) form, space group O _h ⁷. The transition is rapid, and the high-temperature form in pure LiGa₅O₈ could not be quenched to room temperature under the conditions used. However, the high-temperature polymorph can be quenched under equilibrium conditions when 40 mol% or more MgGa₂O₄ is present. The subsolidus equilibrium relations in the system MgGa₂O₄-LiGa₅O₈ are discussed.