Eutectic Composition in the Pseudobinary of Y4Al2O9 and Y2O3

The eutectic composition between Y₄Al₂O₉ and Y₂O₃ was determined using electron probe microanalysis (EPMA) on directionally solidified specimens with hypo- and hypereutectic compositions. The microstructures of the specimens as a function of composition differ considerably with small deviation from the eutectic composition (70.5 mol% Y₂O₃ and 29.5 mol% Al₂O₃). Based on the current results and other published data, the pseudobinary system between Al₂O₃ and Y₂O₃ is revised.     

The Effect of Microstructure and Microcracking on the Thermal Conductivity of UO2-U4O9

Several microstructures were produced in dense polycrystalline UO₂-U₄O₉ specimens by cooling UO_2+x, solid solutions at different rates. Void formation (intragranular pores, grain-boundary microcracks) was observed in specimens which had a nonuniform distribution of the U₄O₉ precipitate; such formation was probably caused by the relief of stresses generated by differential thermal contraction. The microstructures were assessed quantitatively and used to calculate thermal conductivities from theoretical models. The effect of microcracking was calculated. Thermal conductivities were also determined from thermal diffusivity values measured by the laser-flash method. The thermal conductivity was primarily influenced by the amount of U₄O₉, present and the occurrence of voids, whereas the effect of U₄O₉, distribution was minor. Good agreement was obtained between theoretical predictions of thermal conductivity based on microstructure and experimental values.     

Thermal Simulation of In-Reactor Microstructures in ThO2-UO2

A device was built to provide the capability for out-reactor simulation of the microstructures seen in irradiated fuel. Out-reactor simulation of nuclear heating makes possible the precise measurement of temperature gradients in the fuel and provides data for correlating microstructural alterations with temperature. The simulation apparatus was designed to produce controlled thermal gradients sufficient to produce both equiaxed and columnar grain growth in the specimens. Provision was made for calorimetric measurements from which thermal conductance could be determined. Micro-structural alterations in UO₂ and ThO₂-UO₂ materials were achieved, and thermal conductivity data were recorded. Microstructural alterations in the ThO₂-10 wt% UO₂ specimens were similar to those that other investigators have observed in UO₂ at lower temperatures.     

Elevated-Temperature Toughening Mechanisms in a SiCw/Al2O3 Composite

Crack growth resistance studies of a Sic-whisker-reinforced Al₂O₃-matrix composite have been correlated with the composite microstructure to determine the active fracture toughening mechanism, at each of three test temperatures through 1400°C. Evidence of cumulative toughening at all temperatures, as reported in the literature, was validated by R -curves; however, isolation of the following wake zone effects from that of the frontal process zone elicits a departure from published assumptions. A frontal zone mechanism, presumably microcrack toughening, dominates at room temperature, while a following wake zone mechanism of crack face whisker-bridging controls at temperatures near 1200°C.     

Oxidation and Strength Retention of Monolithic Si3N4 and Nanocomposite Si3N4-SiC with Yb2O3 as a Sintering Aid

The oxidation behaviors of monolithic Si₃N₄ and nanocomposite Si₃N₄-SiC with Yb₂O₃ as a sintering aid were investigated. The specimens were exposed to air at temperatures between 1200° and 1500°C for up to 200 h. Parabolic weight gains with respect to exposure time were observed for both specimens. The oxidation products formed on the surface also were similar, i.e., a mixture of crystalline Yb₂Si₂O₇ and SiO₂ (cristobalite). However, strength retention after oxidation was much higher for the nanocomposite Si₃N₄-SiC compared to the monolithic Si₃N₄. The SiC particles of the nanocomposite at the grain boundary were effective in suppressing the migration of Yb³⁺ ions from the bulk grain-boundary region to the surface during the oxidation process. As a result, depletion of yttribium ions, which led to the formation of a damaged zone beneath the oxide layer, was prevented.     

Low-Temperature Firing and Microwave Dielectric Properties of Ca[(Li1/3Nb2/3)0.84Ti0.16]O3−δ Ceramics for LTCC Applications

The effects of LiF and ZnO–B₂O₃–SiO₂ (ZBS) glass combined additives on phase composition, microstructures, and microwave dielectric properties of Ca[(Li_1/3Nb_2/3)_0.84Ti_0.16]O_3−δ (CLNT) ceramics were investigated. The LiF and ZBS glass combined additives lowered the sintering temperature of CLNT ceramics effectively from 1150° to 880°C. The main diffraction peaks of all the specimens split due to the coexistence of the non-stoichiometric phase (A) and stoichiometric phase (B), which all possess CaTiO₃-type perovskite structures. The transformation from A into B became accelerated with the increase of LiF or ZBS content. ZBS glass restrained the volatilization of lithium salt, which greatly affected the microstructures and microwave dielectric properties. CLNT ceramics with 2 wt% LiF and 3 wt% ZBS sintered at 900°C for 2 h show excellent dielectric properties: ɛ_r=34.3, Q × f =17 400 GHz, and τ_f=−4.6 ppm/°C. It is compatible with Ag electrodes, which makes it a promising ceramic for low-temperature cofired ceramics technology application.     

Fracture Toughness of MgO-Partially-Stabilized ZrO2 Specimens with KR-Curve Behavior from Transformation Toughening

Transformation-toughened MgO-partially-stabilized ZrO₂ exhibits a crack-wake-induced load-point displacement in fracture samples. The equations of linear elastic fracture mechanics were self-consistently reformulated to include the residual displacement from the transformation wake. Application of these equations to double-cantilever-beam specimens of transformation-toughened ZrO₂, with the martensitic start transformation temperature close to the testing temperature, gives a decreasing K_R curve and initial toughness values near 30Mpa·m^l/2.     

Fabrication and Microstructures of MoSi2 Reinforced–Si3N4 Matrix Composites

Details of the fabrication and microstructures of hot-pressed MoSi₂ reinforced–Si₃N₄ matrix composites were investigated as a function of MoSi₂ phase size and volume fraction, and amount of MgO densification aid. No reactions were observed between MoSi₂ and Si₃N₄ at the fabrication temperature of 1750°C. Composite microstructures varied from particle–matrix to cermet morphologies with increasing MoSi₂ phase content. The MgO densification aid was present only in the Si₃N₄ phase. An amorphous glassy phase was observed at the MoSi₂–Si₃N₄ phase boundaries, the extent of which decreased with decreased MgO level. No general microcracking was observed in the MoSi₂–Si₃N₄ composites, despite the presence of a substantial thermal expansion mismatch between the MoSi₂ and Si₃N₄ phases. The critical MoSi₂ particle diameter for microcracking was calculated to be 3 μm. MoSi₂ particles as large as 20 μm resulted in no composite microcracking; this indicated that significant stress relief occurred in these composites, probably because of plastic deformation of the MoSi₂ phase.     

Evolution of Microstructure and V-Shaped Positive Temperature Coefficient of Resistivity of (Pb0.6Sr0.4)TiO3 Materials

The effects of various liquid-phase sintering aids on (Pb_0.6SrO_0.4)TiO₃ ceramics have been investigated. The relationships between electrical properties and microstructures have been scrutinized. It has been found that, among the sintering aids studied, only SiO₂ exhibits a significant effect on the grain growth of (Pb_0.6SrO₄)TiO₃. The optimum firing profiles for sound microstructure and good electrical properties of (Pb_0.6SrO_0.4)TiO₃+ 5.0 mol% SiO₂ have been established. The V-shaped electrical behavior is prominent, and a PTCR jump of about 10^2.9 is observed. The formation of cation vacancies may increase the resistivity of the over-fired specimens. Various milling methods to pulverize the calcined powder and the optimum amount of packing protection powder during sintering are also discussed.     

Densification of Si3N4-Y2O3/Al2O3 by a Dual N2 Pressure Process

Sintering studies of Si₃N4-Y₂O3/Al₂O₃ compositions indicated that increased densification could be produced using a dual N₂ pressure process. RT modulus of rupture values and microstructures were found to be similar to hot-pressed material. The technique should be adaptable to complex shaped Si₃N₄ bodies where high density and strength are required .     

High-Q Microwave Dielectrics in the (Mg1−xCox)2TiO4 Ceramics

The microwave dielectric properties and the microstructures of (Mg_{1− x} Co _x )₂TiO₄ ceramics prepared by the conventional solid-state route were investigated. Lattice parameters were also measured for specimens with different x . The formation of solid solution (Mg_{1− x} Co _x )₂TiO₄ ( x =0.02–0.1) was confirmed by the X-ray diffraction patterns, energy dispersive X-ray analysis, and the lattice parameters measured. By increasing x from 0 to 0.05, the Q × f of the specimen can be tremendously boosted from 150 000 GHz to a maximum of 286 000 GHz. A fine combination of microwave dielectric properties (ɛ_r∼15.7, Q × f ∼286 000 GHz at 10.4 GHz, τ_f∼−52.5 ppm/°C) was achieved for (Mg_0.95Co_0.05)₂TiO₄ ceramics sintered at 1390°C for 4 h. Ilmenite-structured (Mg_0.95Co_0.05)TiO₃ was detected as a second phase. The presence of the second phase would cause no significant variation in the dielectric properties of the specimen because it possesses compatible properties compared with that of the main phase. In addition, only a small deviation in the dielectric properties was monitored for specimens with x =0.04–0.05 at 1360°–1420°C. It not only provides a wide process window but also ensures an extremely reliable material proposed as a very promising dielectric for low-loss microwave and millimeter wave applications.     

Effects of Excess Bi2O3 on the Ferroelectric Behavior of Nd-Doped Bi4Ti3O12 Thin Films

Effects of excess Bi₂O₃ content on formation of (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) films deposited by RF sputtering were investigated. The microstructures and electrical properties of BNT thin films are strongly dependent on the excess Bi₂O₃ content and post-sputtering annealing temperature, as examined by XRD, SEM, and P – E hysteresis loops. A small amount of excess bismuth improves the crystallinity and therefore polarization of BNT films, while too much excess bismuth leads to a reduction in polarization and an increase in coercive field. P – E loops of well-established squareness were observed for the BNT films derived from a moderate amount of Bi₂O₃ excess (5 mol%), where a remanent polarization 2P _r of 25.2 μC/cm² and 2E _c of 161.5 kV/cm were shown. A similar change in dielectric constant with increasing excess Bi₂O₃ content was also observed, with the highest dielectric constant of 304.1 being measured for the BNT film derived from 5 mol% excess Bi₂O₃.     

Microstructural Evolution of Gas-Pressure-Sintered Si3N4 with Yb2O3 as a Sintering Aid

Microstructural evolution of gas-pressure-sintered Si₃N₄ with Yb₂O₃ as a sintering aid was observed. Microstructures typical for in situ toughened Si₃N₄, i.e., large elongated grains randomly distributed in a fine matrix, were observed. However, the size of the elongated grains near the surface was much larger than that at the center, resulting in two distinct regions: an inner region and an outer region. The smaller the amount of Yb₂O₃ added, the larger the difference in the size of the elongated grains between the outer and inner regions. The difference between microstructures was diminished when 16 wt% Yb₂O₃ was added. The microstructural change with Yb₂O₃ content was attributed to the evaporation of Yb-containing liquid phase from the surface.     

Mechanical Properties of β-Si3N4-Whisker/Si3N4-Matrix Composites

Composites containing 30 vol%β-Si₃N₄ whiskers in a Si₃N₄ matrix were fabricated by hot-pressing. The composites exhibited fracture toughness values between 7.6 and 8.6 MPa · m^1/2, compared to 4.0 MPa · m^1/2 for unreinforced polycrystalline Si₃N₄. The improvements in fracture toughness were attributed to crack wake effects, i.e., whisker bridging and pullout mechanisms.     

Ag2O-Doped Bi2Sr2Ca1Cu2Ox Superconductors Prepared via Melt-Quenching

Ag₂O-doped superconducting Bi₂Sr₂Ca₁Cu₂O _x ceramics were prepared by a melt-quenching–reheating method. It is found that the Ag₂O-doped, as-cast specimens exhibit superconductivity ( T _c= around 80 K) by heat treatment at temperatures around 800°C even in an evacuated and sealed silica glass tube, while the undoped specimens do not and vaporize by the corresponding heat treatment. Conversion of the Ag₂O-doped, as-cast specimens into superconducting ceramics when heated in an evacuated vessel is explained in terms of the oxygen donor of Ag₂O in the specimen. This finding enables us to fabricate a desired shape of superconducting Bi₂Sr₂Ca₁Cu₂O _x ceramics sealed in metals or glasses. The addition of Ag₂O to Bi₂Sr₂Ca₁Cu₂O _x melt, however, had deleterious influences on the superconducting properties ( T _c and J _c) of the resultant ceramics when obtained by heat treatment in air.     

Sr3LaNb3O12: A New Low Loss and Temperature Stable A4B3O12-Type Microwave Dielectric Ceramic

The microwave dielectric properties of dense ceramics of a new A₄B₃O₁₂ type cation-deficient hexagonal perovskite Sr₃LaNb₃O₁₂ are reported. Single-phase powders can be obtained from the mixed-oxide route at 1320°C and dense ceramics (>96% of the theoretical X-ray density) with uniform microstructures (5–12 um) can be obtained by sintering in air at 1430°C. The ceramic exhibits a moderate dielectric constant ɛ_r∼36, a high quality factor Q × f ∼45 327 GHz, and a low temperature coefficient of resonant frequency τ _f of −9 ppm/°C.     

Processing and Properties of in Situ-Reinforced α-SiAlONs Stabilized with Y2O3 and Lu2O3

α-SiAlONs with equiaxed and elongated microstructures stabilized with Y₂O₃ and Lu₂O₃ were produced by hot pressing, and the phase structure and room- and high-temperature mechanical properties were assessed. Additional liquid added to the starting composition in the form of 5 wt% rare-earth monosilicate resulted in the formation of elongated microstructures and improvements in room-temperature strength and fracture toughness. The elongated grain growth was promoted by the additional liquid phase, which crystallized to form a secondary grain-boundary phase thought to be J ' (Re₄Si_{2– x} Al _x O_{7+ x} N_{2– x} ). For the equiaxed and the elongated samples, those sintered with Lu₂O₃ showed higher hardness than the comparable Y₂O₃-sintered materials, and, at elevated temperature, the strength retention of the elongated Lu₂O₃ SiAlON was much higher than that of the Y₂O₃ sample, which was attributed to properties of the residual grain-boundary phase associated with the difference in the cationic radius of the stabilizing cation.     

Mechanical Properties of Interpenetrating Microstructures: The Al2O3/c-ZrO2 System

Composites of Al₂O₃ (A) and cubic ZrO₂ (Z) (8 mol% Y₂O₃) (with c -ZrO₂ volume fractions ranging from O to 1) were fabricated by pressureless sintering of mechanically mixed powders. The microstructures of the AZ composites were duplex, with the grains of both phases exhibiting similar size. Room-temperature mechanical properties including Young's modulus (determined from elastic wave velocity measurements), strength and toughness (by indentation-strength-in-bending), and Vickers microhardness were evaluated for the full range of compositions. All properties exhibited a linear decrease with increasing c -ZrO₂ content, and no R -curve behavior was seen in any of the composite compositions. Fracture morphology, observed from cracks emanating from microhardness indentations, changed from essentially intergranular for the tougher Al₂O₃ to transgranular for c -ZrO₂, with AZ composites exhibiting mixed morphology.     

Phase Relations in the System Ce2O3–Al2O3 in Inert and Reducing Atmospheres

The 1:1 compound, CeA1O₃, in the system Ce₂O₃–Al₂O₃ has been synthesized from the oxides and shown to have a perovskite-like tetragonal unit cell with the lattice parameters a = 3.763 and c = 3.792 Å. A new XRD pattern is suggested for CeA1O₃. This compound is shown to be stable up to 1950°C. The 1:11 compound, CeAl₁₁O₁₈, has also been synthesized and shown to possess a magnetoplumbite-like hexagonal unit cell with the lattice parameters α= 5.558 and c = 22.012 å. An XRD pattern is suggested for CeAl₁₁O₁₈ for the first time. The evolution of eutectic-like microstructures was observed and reported in the Ce₂O₃-rich side of this binary system.     

Synthesis and Processing Characteristics of Ba0.65Sr0.35TiO3 Powders from Catecholate Precursors

Powders of composition Ba_0.65Sr_0.35TiO₃ were prepared from catecholate precursor phases, BaTi(C₆H₄O₂)₃ and SrTi (C₆H₄O₂)₃. The physical and chemical properties of the base powders, and those doped with 0.2 wt% manganese, are reported in detail. The dimensions of the primary particles in the starting powders were of the order of 20–50 nm, but the occurrence of abnormal grain growth during sintering promoted grain sizes in the ceramic of up to ∼100 μm. In some microstructures, coarse grains coexisted with a ∼1-μm fraction to produce a characteristic bimodal grain size distribution. By contrast, under comparable sintering conditions, namely 1350° or 1400°C for 1 h, grain growth in Mn-doped samples was suppressed, leading to uniform microstructures with a grain size of only a few micrometers. The pellet densities were nevertheless similar, 97% of theoretical in both doped and undoped samples. No significant difference was observed in the dielectric permittivity of the two compositions: the peak relative permittivity occurred at ∼20°C, with a maximum value of ∼22 000.