Interaction of BaCl2 and BaSO4 at Elevated Temperatures

The effect of adding BaCl₂ to BaSO₄ at elevated temperatures was studied. Differential thermal analysis and hot-stage microscopy revealed that a eutectic occurs at 865°C between BaCl₂ and 13.5 mol% BaSO₄. The microstructure in the reaction zone indicated that BaS04 recrystallizes from the eutectic melt. Thus, BaCl₂ additions can activate BaSO₄ at a temperature as low as 865°C.     

Deformation of UO2 at High Temperatures

The effects of temperature, strain rate, and grain size on the mechanical properties of UO₂ were investigated using the four-point bending technique. Strain rates were varied by two orders of magnitude, and test temperatures up to 1800°C were used. Data are presented on the ultimate tensile stress, yield stress, and plastic strain-to-fracture. Below the brittle-to-ductile transition temperature, T_c , the material fractured in a brittle manner, with no macroscopic plastic deformation. Between T_c and a second transition at a higher temperature, T_t , a small amount of plastic deformation was measured before fracture. Beyond T_t , the strength of UO₂ decreased continuously, and extensive plasticity was observed. This high-temperature plasticity was characterized by a thermally activated rate-controlling process; this behavior is consistent with observations of creep behavior under high stresses. The following phenomenological equations for the strain rate fit the data for the material with 8-μm grain size above T_t :
and
where σ_p and σ_88f are the proportional limit and steady-state flow stress, respectively, and temperature T is in °K.     

Interaction of BaCl2 and BaCO3 at Elevated Temperatures

The effect of adding BaCl₂ to BaCO₃ at elevated temperatures was studied. DTA and hot-stage microscopy revealed that a eutectic occurs at 840°C and 14.0 mol% BaCO₃. The microstructure in the reaction zone indicated that BaCO₃ recrystallizes from the eutectic melt. Thus, BaCl₂ additions can activate BaCO₃ at a temperature as low as 840°C .     

Sublimation of Cr2O3 at High Temperatures

The sublimation of chromic oxide, Cr₂O₃, has been observed in vacuum by the Langmuir technique using induction and solar heating. Extensive sublimation did not yield any new phases on the basis of X-ray powder studies, and condensates of Cr₂O₃ were always obtained. Flash vaporization and flow experiments in CO or O₂ atmospheres and in vacuum indicated no appreciable differences in rates of sublimation. Weight-loss experiments showed that the rate of sublimation was slightly higher than predicted for decomposition to the elements and suggested that small amounts of complex molecules, e.g. CrO and CrO₂, were also present in the equilibrium vapor.     

Spheroidization of Tubular Voids in Al2 O3 Crystals at High Temperatures

Cracks introduced into single-crystal sapphire broke up after annealing, first into channels of cylindrical voids and ultimately into rows of spherical pores, with the thicker gap spacings in the original crack remaining open. Breakup of the cylindrical voids on subsequent annealing conformed to the models for surface-diffusion-controlled material transport. At the temperatures of measurement, the magnitudes of the calculated surface diffusivities agree well with values reported previously.     

The Role of Grain-Boundary Sliding in Fracture of Hot-Pressed Si3N4 at High Temperatures

A new type of internal friction experiment was used to investigate the kinetics of grain-boundary sliding in hot-pressed Si₃N₄. The measured sliding resistance in NC-132 was greater than in HS-110 and HS-130 materials.     

Thermal Conductivity of Sintered UO, and Al2O3 at High Temperatures

The thermal conductivities of sintered Al₂O₃ and UO₂ were measured in the ranges 400° to 1700°C and 300° to 2100°C respectively. The conductivity values for Al₂O₃ agreed with those reported previously at all temperatures investigated. The conductivity of UO, decreased with increasing temperature to a minimum of 0.0050 cal per cm sec °C at about 1400°C, and then increased with increasing temperature to 0.0105 cal per cm sec °C at 2100°C.     

Steam Oxidation Kinetics and Oxygen Diffusion in UOz at High Temperatures

Results of steam oxidation measurements of UO₂ cylinders from 885° to 1835°C may be expressed by the equations:

for the parabolic rate of oxidation and

for the chemical oxygen diffusion coefficient. K_p and D_c, obtained from thermobalance measurements to 1500° C and from pre- and post-test weights for the higher temperatures, were independent of sample weight from 10 to 149 g and of surfaceto-volume ratios from 2.34 to 18.74 cm^-1. D_c varied as the 0.65 power of the final average excess oxygen (x in UO_2+x). The oxidation was accompanied by considerable grain growth. A bulk diffusion mechanism was verified by analyses of partially oxidized samples using both X-ray diffraction and analytical chemistry; an oxygen gradient was demonstrated by each technique.     

The System AI2SiO5 at High Temperatures and Pressures

Experiments on the system Al₂SiO₅ at high temperatures and pressures with the belt apparatus indicate that kyanite melts incongruently above about 1500°C at 25,000 bars to Al₂O₃ (corundum) plus liquid. The pressure-temperature curves obtained by starting with either a 1/1 Al₂O₃/SiO₂ gel or with kyanite are essentially identical but differ considerably from the results with andalu-site and sillimanite. The structure of the starting material has considerable influence on the kinetics of the reaction and the metastable formation of corundum in this system. An "equilibrium" curve based on the andalusite-sillimanite data is described by P = 33.8 × 10-³T - 26.4 (Pin kbars, Tin°C).     

Solid-Solution Ranges of the n= 2 and n= 3 Superconducting Phases in Bi2(SrxCa1 −x)n+1CunOy and the Effect on Tc

The cation solubility limits of the n = 2 and n = 3 superconducting phases in the Bi₂(Sr _x Ca_{1 − x} ) _{n +1}Cu _n O _y system were established along tie lines with compatible phases via electron probe microanalysis on bi- (or poly-) phasic samples prepared at 860°C. Pb additions (15 mol% of the Bi content) were used to facilitate formation of the n = 3 phase. In each case football-shaped volumes in composition space were established as the solubility limits which bordered on the nominal compositions 2212 or 2223 (Bi:Sr:Ca:Cu) with the long axis parallel to the Sr-Ca side of the quaternary (i.e., Sr-to-Ca intersolubility) but also extending toward Bi and Cu. This means that, for the most part, the superconducting phases are alkaline-earth deficient relative to the ideal 2212 and 2223 compositions. The Pb content in the 2223 phase is typically 10% of the Bi content. T _c variations could be correlated with variations in Sr or (Sr + Bi) content and the length of the c -axis parameter.     

Microwave Dielectric Properties of Ti-Substituted Bi2 (Zn2/3Nb4/3)O7 Pyrochlores at Cryogenic Temperatures

Monoclinic pyrochlore ceramic Bi₂Zn_{2/3− x /3}Nb_{4/3−2 x /3}Ti _x O₇ (M–BZN) with x =0–0.4 is synthesized and the structure and microwave cryogenic properties are scrutinized. The dielectric constant (ɛ') and loss tangent (tanδ) of these ceramics are measured at a frequency of 3 GHz and temperature range of 15–300 K. With an increase in x value from 0 to 0.4, the dielectric constant and dielectric loss tangent of the investigated materials increase from 70 to 114 and 0.009 to 0.061, respectively. The Ti-substituted ceramics show an increase in dielectric constant with temperature, and the loss tangent shows a peak around 200 K. The peak in the dielectric loss tangent becomes more prominent with an increase of Ti content. The temperature where the dielectric loss tangent peak appears is found to be decreasing slightly with an increase of titanium doping. The observed dielectric characteristics of the titanium-doped M–BZN ceramics are attributed to the presence of the relaxation in these materials, originating from the disorder caused by the Ti⁴⁺ substitution.     

Fracture Mechanisms of a Coarse-Grained, Transparent MgAl2O4 at Elevated Temperatures

The fracture of a transparent, large-grain-sized MgAl₂O₄ spinel has been studied through temperatures of 1400°C. Fracture toughness values, falling between about 1.3 and 2.3 MPa.m^12;1/2, behaved sigmoidally with temperature, with a lower shelf transition appearing near 800°C. Rising R -curves, displaying a run-arrest character, were found at both the lowest and the highest temperatures, while only minimal values of d K _R/dΔ a were produced at intermediate temperatures of 800°C. This fracture character is ascribed largely to finite concentrations of a residual LiF pressing aid identified on the fracture surface, while additional influences associated with the lower shelf region at the highest temperatures may include the increased fraction of intergranular crack path and the onset of plasticity. This cubic monolithic ceramic displayed strong nonlinear fracture behavior in both temperature regimes. In both cases the fracture character is linked directly to an active toughening mechanism in the wake region, which depends upon crack face bridging.     

Synthesis and Thermal Expansion of MZr4P6O24 (M=Mg, Ca, Sr, Ba)

MZr₄P₆O₂₄ (M=Mg, Ca, Sr, Ba), which belongs to a new, low-thermal-expansion family of materials known as [NZP] or [CTP], were synthesized by solid-state reaction (oxide mixing) and sol-gel methods, and their sinterability in two cases was investigated and compared. Thermal-expansion measurements were made on sintered samples by dilatometry, high-temperature X-ray diffractometry, and the laser speckle technique. An anisotropy in axial thermal-expansion coefficients was observed in these materials. CaZr₄P₆O₂₄ and SrZ₄P₆O₂₄ showed reverse anisotropy as well as opposite bulk thermal expansion; i.e., CaZr₄P₆O₂₄ had negative bulk thermal expansion and SrZr₄P₆O₂₄ positive bulk thermal expansion in the temperature range 25° to 500°C. The microstructure of the sintered samples was also examined by scanning electron microscopy.     

Preparation of Porous Ca10(PO4)6(OH)2 and β-Ca3(PO4)2 Bioceramics

Submicrometer-sized, pure calcium hydroxyapatite (HA, (Ca₁₀(PO₄)₆(OH)₂)) and β-tricalcium phosphate (β-TCP, Ca₃(PO₄)₂) bioceramic powders, that have been synthesized via chemical precipitation techniques, were used in the preparation of aqueous slurries that contained methyl cellulose to manufacture porous (70%–95% porosity) HA or β-TCP ceramics. The pore sizes in HA bioceramics of this study were 200–400 μm, whereas those of β-TCP bioceramics were 100–300 μm. The pore morphology and total porosity of the HA and β-TCP samples were investigated via scanning electron microscopy, water absorption, and computerized tomography.     

Microstructures and Microwave Dielectric Characteristics of CaRAlO4 (R = Nd, Sm, Y) Ceramics with Tetragonal K2NiF4 Structure

CaRAlO₄ (R = Nd, Sm, Y) ceramics with a K₂NiF₄ structure were prepared by a solid-state reaction approach, and their microwave dielectric characteristics were evaluated, along with their microstructures. Dense CaNdAlO₄, CaSmAlO₄, and CaYAlO₄ ceramics were obtained by sintering at 1425°–1500°C in air for 3 h, and good microwave dielectric characteristics were achieved: (1) ɛ= 18.2, Qf = 17 980 GHz, τ_f=−52 ppm/°C for CaNdAlO₄; (2) ɛ= 18.2, Qf = 51 060 GHz, τ_f=−3 ppm/°C for CaSmAlO₄; and (3) ɛ= 18.9, Qf = 39 960 GHz, τ_f= 6 ppm/°C for CaYAlO₄.     

Electrical Conduction in Single-Crystal and Polycrystalline Al2O3 at High Temperatures

The electrical conductivity and ion/electron transference numbers in Al₃O₃ were determined in a sample configuration designed to eliminate influences of surface and gas-phase conduction on the bulk behavior. With decreasing O₂ partial pressure over single-crystal Al₂O₃ at 1000° to 1650°C, the conductivity decreased, then remained constant, and finally increased when strongly reducing atmospheres were attained. The intermediate flat region became dominant at the lower temperatures. The emf measurements showed predominantly ionic conduction in the flat region; the electronic conduction state is exhibited in the branches of both ends. In pure O₂ (1 atm) the conductivity above 1400°C was σ≃3×10³ exp (–80 kcal/ RT ) Ω⁻¹ cm⁻¹, which corresponds to electronic conductivity. Below 1400°C, the activation energy was <57 kcal, corresponding to an extrinsic ionic condition. Polycrystalline samples of both undoped hot-pressed Al₂O₃ and MgO-doped Al₂O₃ showed significantly higher conductivity because of additional electronic conduction in the grain boundaries. The gas-phase conduction above 1200°C increased drastically with decreasing O₂ partial pressure (below 10⁻¹⁰ atm).     

Combustion Synthesis of Sialon Powders (Si6-zAlzOzN8-z, Z = 0.3, 0.6)

Fine sialon powders (Si_6-zAl_zO_zN_8-z, Z = 0.3, 0.6) were prepared by nitriding combustion. Silicon powders was reacted with AlN and Si₃N₄ under 10 MPa of nitrogen gas. The reaction temperature reached above 2000°C and single-phase sialon powders were synthesized within minutes. The obtained powders were fully densified without additives by hot isostatic pressing. The sintered body had a flexural strength of 600 MPa by 4-point bending.     

Doped Ca(Ca1/4A2/4Ti1/4)O3 (A=Nb, Ta) Dielectrics for Microwave Telecommunication Applications

Ca(Ca_1/4A_2/4Ti_1/4)O₃ (A=Nb, Ta) dielectric resonator materials have been prepared by the solid-state ceramic route. The effects of various amounts of di-, tri-, tetra-, penta-, and hexavalent impurities on the structure, microstructure, density, and microwave dielectric properties of the complex perovskites have been investigated. The structure of the parent materials remained unchanged while slight increase in density was observed with a small amount of certain dopants. An improvement in dielectric constant, quality factor, and temperature coefficient of resonant frequency was observed with the doping of small amounts of MgO, ZnO, NiO, CuO, Co₃O₄, Cr₂O₃, SnO₂, and Sb₂O₅. A correlation between the microwave dielectric properties of Ca(Ca_1/4A_2/4Ti_1/4)O₃ (A=Nb, Ta) ceramics and ionic radius of the dopant has been observed. The reported ceramics are potential candidates for dielectric resonator applications in wireless communication devices operating in the S and C bands.     

Creep of Polycrystalline MgO and MgO-Fe2O3 Solid Solutions at High Temperatures

Polycrystalline MgO and MgO-Fe₂O₃ solid solutions (0.10 to 8.08 wt% Fe₂O₃) were fabricated to almost theoretical density by vacuum hot-pressing. Specimens were creep-tested in air under four-point dead-load conditions between 1000° and 1400°C at stresses between 50 and 550 kg/cm². Steady-state creep was never achieved in the experiments, which sometimes lasted more than 50 h. The strain rate vs time ( t ) data were described by an equation of the form = c₁/(t+C₂)^p , which is consistent with the assumptions that creep occurs at least in part by a "viscous" mechanism and that grain growth occurs simultaneously. Doping MgO with Fe₂O₃ enhanced the viscous contributions to creep and inhibited the nonviscous ones. Creep rates in these specimens increased with increasing Fe₂O₃ additions. The occurrence of simultaneous grain growth during the high-temperature creep of magnesiowustite (i.e. MgO-Fe₂O₃ solid solutions) was used in establishing the strain rate vs grain size dependence. The results of this study are consistent with a transition between grain boundary and lattice diffusion mechanisms as the grain size increases (4 to 44 μan). The creep of polycrystalline MgO is a mixed process in that viscous and nonviscous (dislocation) contributions are present.