Dielectric Bodies in the Quaternary System BaTiO3–BaSnO3–SrSnO3–CaSnO3

Dense bodies were prepared of compositions in the quaternary system BaTiO₃–BaSnO₃–SrSnO₃–CaSnO₃ containing from 3 to 60 mole % stannate. The general effect of the stannate addition to barium titanate was to decrease the Curie temperature and broaden the peak. On a molar basis the three stannates were approximately equivalent in their effect on the dielectric properties of barium titanate, although the rate of shift of the Curie temperature was slightly greater when SrSnO₃ was used. Bodies containing calcium or strontium stannate had lower power factors than those containing barium stannate. Bodies compounded with calcium stannate matured most readily and at lower temperatures. Bodies having dielectric constants ( K ) of 2300 to 2800 at 1 kc. with low positive temperature coefficients up to about 55°C. were obtained with a 3 mole % addition of stannate. Bodies with minimum K 's of 3000 to 4000 at 1 kc. over the range 25° to 85°C. were obtained from BaTiO₃ with an addition of about 6 mole % BaSnO₃, SrSnO₃, or CaSnO₃. Bodies with negative temperature coefficients of K ranging from about 13,000 to about 1000 p.p.m. per °C. were obtained with stannate additions of from 10 to 60 mole %.     

Ti-Rich Nonstoichiometric BaTiO3: I, High-Temperature Electrical Conductivity Measurements

Equilibrium electrical conductivity of nonstoichiometric poly-crystalline BaTiO₃ with varying Ba:Ti ratios was investigated at temperatures between 800° and 1200°C and P o₂ from 10⁻²² to I atm. A transition from p -type to n -type conductivity was observed. Although the electrical conductivity of different specimens varied slightly, these differences did not appear to be a function of the Ba:Ti ratio in the region investigated. An intrinsic band-gap energy of ∼3.1 eV was calculated from the temperature dependence of the minimum conductivity. The O₂ partial pressure dependence of the isothermal n -type conductivity cannot be described by simple defect models incorporating only singly or doubly ionized O vacancies. Likewise, simple defect models incorporating cation vacancies are not consistent with the observed pressure dependence of the p -type conductivity. More complex defect models which correspond to the observed behavior over the entire range of temperature and P o₂ will be discussed in a subsequent paper.     

High-Temperature Deformation of Polycrystalline Fe2O3

The effects of stress, temperature, grain size, porosity, and O₂ partial pressure on the creep of polycrystalline Fe₂O₃ were studied in the range 770° to 1105°C by tests in 4-point bending and compression. Deformation rates are controlled by the stress-directed diffusion of either oxygen or iron. Diffusion coefficients computed from the Nabarro-Herring formula modified by including an empirical porosity-correction term are also consistent with the values reported for oxygen and iron.     

High-Temperature Creep of Y2O3-Stabilized ZrO2

The compression creep behavior of Y₂O₃-stabilized ZrO₂ (YSZ) was studied at temperatures to 2000 ° C. The function of Y₂O₃ content and grain size was tested in specimens with various impurity concentrations and porosity distributions. For relatively fine-grained specimens, creep rates increased with the 1.5 power of the applied stress at low stresses and with the third power at high stresses. The results for coarse-grained specimens can, in general, be fit by the cube dependence. The 1.5 power can be reduced to a linear dependence by correcting for an apparent threshold stress, which decreases with increasing temperature. Creep activation energies for YSZ are 128 ± 10 kcal/mol, independent of Y₂O₃ content, impurity level, grain size, and porosity distribution. In addition, over a broad range of temperatures and stresses the absolute values of the steady-state creep rates are influenced only by grain size and O₂ partial pressure.     

High-Temperature Cation Distributions in Fe3-FeAl2O4

Cation distribution at 1600 K in the system Fe₃O₄-FeA1₂O₄ was derived from Seebeck coefficient measurements assuming that the aluminum distribution behaved according to the thermodynamic model proposed by O'Neill and Navrotsky. Approximately 10% of the aluminum resides tetrahedrally. This system provides a good test of thermodynamic models.     

High-Temperature Phase Transitions in PbZrO3

A high-temperature X-ray diffraction study of a high-purity PbZrO₃ specimen at 25° to 236°C is reported. The symmetry of the perovskite sub-cell of PbZrO₃ was determined unambiguously by observing the splitting of the line groups N = 12 and N = 16 when the diffraction pattern was indexed on the basis of the perovskite cell being a unit cell for the structure. Diffractometer studies were conducted of the N = 12 line group using Fe K α radiation and of the N = 16 line group using Cu K α radiation. The ferroelectric phase of PbZrO₃ possessed a rhombohedral sub-cell with the angle α being acute. Stable two-phase mixtures and considerable thermal hysteresis were observed at the antiferroelectric α ferroelectric transition temperature. A very weak "extra" diffraction line was observed in the diffraction patterns of the ferroelectric and paraelectric phases, indicating that the unit cells of these structures may be multiples of the perovskite subcell.     

High-Temperature Stability of the Al2O3-LaPO4 System

The compatibility of Al₂O₃ and LaPO₄ at temperatures up to 1600°C is examined. Provided the ratio of La to P was close to 1:1, no reactions were observed after 200 h at 1600°C. Moreover, the Al₂O₃/LaPO₄ interface remained sufficiently weakly bonded to cause deflection of cracks, as reported previously. In the presence of excess P or La, reactions occurred as expected, forming AlPO₄ in the case of excess P, and LaAlO₃ and LaAl₁₁O₁₈ in the case of excess La.     

High-Temperature Behavior of MoSi2 and Mo5Si3

The high-temperature stability and behavior of MoSi₂ was studied by heating dense sintered specimens under a vacuum of 10⁻⁵ mm Hg in the temperature range 1700° to 2000°C. The resulting material was examined using physical measurements, X-ray analysis, and metallographic techniques. The decomposition of MoSi₂ into Mo₅Si₃ is described. The Mo₅Si₃-MoSi₂ eutectic temperature was determined as 1900° C, and the melting points of MoSi₅ and Mo₅Si₃ were determined as 1980° and 2085° C, respectively.     

High-Temperature Failure Mechanisms of Hot-Pressed Si3N4 and Si3N4/Si3N4-Whisker-Reinforced Composites

The high-temperature flexural strength of hot-pressed silicon nitride (Si₃N₄) and Si₃N₄-whisker-reinforced Si₃N₄-matrix composites has been measured at a crosshead speed of 1.27 mm/min and temperatures up to 1400°C in a nitrogen atmosphere. Load–displacement curves for whisker-reinforced composites showed nonelastic fracture behavior at 1400°C. In contrast, such behavior was not observed for monolithic Si₃N₄. Microstructures of both materials have been examined by scanning and transmission electron microscopy. The results indicate that grain-boundary sliding could be responsible for strength degradation in both monolithic Si₃N₄ and its whisker composites. The origin of the nonelastic failure behavior of Si₃N₄-whisker composite at 1400°C was not positively identified but several possibilities are discussed.     

High-Temperature Hall Measurements on Cerium Dioxide Thin Films

Simultaneous Hall and conductivity measurements have been performed on sputtered polycrystalline thin films and on bulk ceramic specimens of nearly stoichiometric CeO₂ in the temperature range between 900° and 1040°C. The measurements have been performed in air using low-frequency alternating current. In the case of the bulk ceramic specimens, an upper limit for the carrier mobility of ≤0.2 cm²/(V·s) has been obtained, which is in accordance with data from the literature for bulk samples. The conductivity of the thin films (l/1Ω·m) at 1000°C) is in accordance with data from the literature for bulk ceramics. The carrier density derived from the Hall measurements (3 × 10¹⁶/cm³ at 1000°C) increases with increasing temperature, whereas the Hall mobility (4 cm²(V·s) at 1000°C) decreases with increasing temperature. These values differ from literature data for bulk ceramic specimens. The difference may be duelo the small grain diameters (∼200 nm) in the 1-μm-thick thin films.     

High-Temperature Phase Relations in the System Gd2O3-Ta2O5

The Phase relations of the system Gd₂O₃-Ta₂O₅ in the composition range 50 to100 mol% Gd2O3 was studied by solidstate reactions at 1350°, 1500°, or 1700°C and by thermal analyses up to the melting temperatures. Weberite-type orthorhombic phase (W2 phase, space group C2221) with the composition of Gd3 TaO7 seems to melt incongruently; at about 2040°C, although this Gd₃TaO₇ Phase was previously reported to melt congruently. A new fluorite-type cubic phase (F phase, space group Fm3m ) was found for the first time above 1500°C in the system. It melts congruently with the composition of about 80mol% Gd2O3at 2318° 3°C. A phase diagram was proposed for the system Gd₂O3–Ta2O₅ in the Gd₂O₃–rich portion     

High-Temperature Phase Relations in the Sc2O3-Ta2O5 System

The phase relations for the Sc₂O₃-Ta₂O₅ system in the composition range of 50-100 mol% Sc₂O₃ have been studied by using solid-state reactions at 1350°, 1500°, or 1700°C and by using thermal analyses up to the melting temperatures. The Sc_5.5Ta_1.5O₁₂ phase, defect-fluorite-type cubic phase (F-phase, space group Fm 3 m ), ScTaO₄, and Sc₂O₃ were found in the system. The Sc_5.5Ta_1.5O₁₂ phase formed in 78 mol% Sc₂O₃ at <1700°C and seemed to melt incongruently. The F-phase formed in ∼75 mol% Sc₂O₃ and decomposed to Sc_5.5Ta_1.5O₁₂ and ScTaO₄ at <1700°C. The F-phase melted congruently at 2344°± 2°C in 80 mol% Sc₂O₃. The eutectic point seemed to exist at ∼2300°C in 90 mol% Sc₂O₃. A phase diagram that includes the four above-described phases has been proposed, instead of the previous diagram in which those phases were not identified.     

High-Temperature Phase Relations in the System Y2O3-Ta2O5

The phase relations for the system y₂o₃–Ta₂o₅ in the composition range 50 to 100 mol% Y₂O₃ have been studied by solid-state reactions at 1350°, 1500°, or 17000C and by thermal analyses up to the melting temperatures. Weberite-type orthorhombic phases (W2 phase, space group C222₁), fluorite-type cubic phases (F phase, space group Fm3m )and another orthorhombic phase (O phase, space group Cmmm )are found in the system. The W2 phase forms in 75 mol% Y₂O₃ under 17000C and O phase in 70 mol% Y₂O₃ up to 1700°C These phases seem to melt incongruently. The F phase forms in about 80 mol% Y₂O₃ and melts congruently at 2454° 3°C. Two eutectic points seem to exist at about 2220°C 90 mol% Y²O₃, and at about 1990°C, 62 mol% Y₂O₃. A Phase diagram including the above three phases were not identified with each other.     

High-Temperature Strength and Fracture Toughness of Y2O3-Partially-Stabilized ZrO2/Al2O3 Composites

The temperature dependence of bending strength, fracture toughness, and Young's modulus of composite materials fabricated in the ZrO₂ (Y₂O₃)-Al₂O₃ system were examined. The addition of A1203 enhanced the high-temperature strength. Isostatically hot-pressed, 60 wt% ZrO₂ (2 mol% Y₂O₃)/40 wt% Al₂O₃ exhibited an extremely high strength, 1000 MPa, at 1000°C.     

High-Temperature Creep Behavior of Polycrystalline SrZrO3

The high-temperature creep behavior of sintered polycrystalline SrZrO₃ containing 1.35 wt% Fe₂O₃ was investigated as a function of temperature, stress, grain size, and strain level over the ranges 1160° to 1275°C, 780 to 3110 psi, 0.45 to 2.04 μm, and 0.0014 to 0.014, respectively. A constant-load 4-point (pure bending) method was used to load the specimens. The creep rate is time-dependent, decreasing exponentially with strain, i.e.     , where the decay constant (β=118, measured at the 1560 psi stress level over the strain range 0.0014 to 0.014) is independent of temperature and grain size. No significant grain growth occurred during creep. The activation energy of 169±10 kcal/mol obtained for creep is relatively independent of temperature, stress, grain size, and strain level over the ranges investigated. The creep rate is directly proportional to the cube of the stress and the reciprocal of the grain size; this result is consistent with nonviscous creep theories based on dislocation generation and climb as the rate-controlling deformation mechanism.     

High-Temperature Tensile Strength of Er2O3-Doped ZrO2 Single Crystals

The deformation and fracture mechanisms in tension were studied in single-crystal Er₂O₃-doped ZrO₂ monofilaments processed by the laser-heated floating zone method. Tensile tests were carried out between 25° and 1400°C at different loading rates and the dominant deformation and fracture mechanisms were determined from the shape of the stress–strain curves, the morphology of the fracture surfaces, and the evidence provided by monofilaments deformed at high temperature and broken at ambient temperature. The tensile strength presented a minimum at 600°–800°C and it was controlled by the slow growth of a crack from the surface. This mechanism was also dominant in some monofilaments tested at 1000°C and above, while others showed extensive plastic deformation before fracture at these temperatures. The strength of plastically deformed monofilaments was significantly higher than those which failed by slow crack growth due to the marked strain hardening capacity of this material.     

High-Temperature Neutron Diffraction of the AlN–Al2O3–Y2O3 System

The importance of aluminum nitride (AlN) stems from its application in microelectronics as a substrate material due to high thermal conductivity, high electrical resistance, mechanical strength and hardness, thermal durability, and chemical stability. Yttria (Y₂O₃) is the best additive for AlN sintering. AlN densifies by a liquid-phase mechanism, where the surface oxide, Al₂O₃, reacts with Y₂O₃ to form an Y-Al-O-N liquid that promotes particle rearrangement and densification. Construction of the phase relations in this multicomponent system is essential for optimizing the properties of AlN. The ternary phase diagram of the AlN–Al₂O₃–Y₂O₃ was developed by Gibbs energy minimization using interpolation procedures based on modeling the binary subsystems. This paper aims at testing the resultant understanding experimentally at selected compositions using in situ high-temperature neutron diffractometry. These experimental results agree with the thermodynamic calculations of AlN–Al₂O₃–Y₂O₃. The ternary phase diagram has been constructed for the first time in this work. High-temperature neutron diffractometry has permitted real time measurement of the reactions involved in this ternary system, especially to determine the temperature range for each reaction, which would have been difficult to establish by other means.     

Syntheses and Unit-Cell Determination of Ba3V4O13 and Low-and High-Temperature Ba3P4O13

The syntheses and the results of unit-cell determinations ofBa₃V₄O₁₃ and the two forms (low- and high-temperature) of Ba₃P₄O₁₃ are presented. Ba₃V₄O₁₃ crystallizes in the monoclinic system, space group Cc or C2/c with unit-cell dimensions a=16.087, b=8.948, c=10.159 (x10nm), β=114.52° Low-Ba₃P₄O₁₃ crystallizes in the triclinic system, space group P1 or P1 with unit-cell dimensions a=5.757, b=7.243, c=8.104 (x10 nm) α=82.75°, β=73.94°, γ=70.71°. Low-Ba₃P₄O₁₃ transforms at 870°C into high-Ba₃P₄O₁₃ which crystallizes in the orthorhombic system, space group Pbcm (No. 57) (or Pbc2, No. 29) with unit-cell dimensions a =7.107, b=13.883, c=19.219 (x10 nm). No relations have been found between the structures of the tribarium tetravanadate and the tribarium tetraphosphate.