The System ThO2-P2O5

The existence of compounds with 1:1, 3:2, and 3:1 ThO₂:P₂O₅ ratios in the system ThO₂-P₂O₅ was confirmed. A 1:2 compound found by previous workers was not investigated, and their 2:1 compound was not detected; however, extensive solid solution on either side of the 3:2 compound was established. The linear thermal expansion behavior of the compounds and solid solutions was determined.     

Revised ThO2-Nb2O5 Phase Diagram

The phase equilibrium diagram of the system ThO₂-Nb₂O was redetermined near the composition Th₂Nb₂O₉. This phase was found to melt incongruenlly at 1362°C, with a eutectic temperature at ∼1350°C. The peritectic and eutectic compositions must occur between 60 and ∼64 mol % ThO₂. From single crystal and powder X-ray diffraction data, Th₂ Nb₂O₉ was found to have a primitive monoclinic unit cell with a = 6.711(1), b = 25.254(5), c=7.757(1)×10⁻¹nm, β=90.46 (1)°.     

Grain-Boundary Segregation and Final-Stage Sintering of Y2O3

The addition of ThO₂ to Y₂O₃ inhibits grain growth during sintering and allows the sintering process to proceed to theoretical density by maintaining a high diffusion flux of vacancies from the pores to the grain boundaries. The inhibition of grain growth is accomplished by the segregation of ThO₂ solute at the grain boundaries, causing a decrease in the grain-boundary mobility. The segregation of ThO₂ at the grain boundaries can be inferred from the results of the microhardness and grain-growth studies presented. Further evidence for segregation is provided by quenching experiments and surface activity experiments.     

Phase Stability, Phase Transformation Kinetics, and Conductivity of Y2O3—Bi2O3 Solid Electrolytes Containing Aliovalent Dopants

Single-phase, cubic solid solutions of baseline composition 25% Y₂O₃—75% Bi₂O₃ with and without aliovalent dopants were fabricated by pressureless sintering of powder compacts. CaO, SrO, ZrO₂, or ThO₂ was added as an aliovalent dopant. Sintered samples were annealed between 600° and 650°C for up to 4000 h. Samples doped with ZrO₂ or ThO₂ remained cubic, depending upon the dopant concentration, even after long-term annealing. By contrast, undoped, CaO-doped, and SrO-doped samples transformed to the low-temperature, rhombohedral phase within ∼ 200 h. Conductivity measurements showed no degradation of conductivity in samples that did not undergo the transformation. In samples that underwent the transformation, a substantial decrease in conductivity occurred. The enhanced stability of the ZrO₂- and ThO₂-doped samples is rationalized on the basis of suppressed interdiffusion on the cation sublattice.     

Defect Structure and Electrical Conductivity of ThO2-Y2O3 Solid Solutions

Compositions in the system ThO₂-YO_1.5 were coprecipitated as oxalates and converted to oxides. Disks were pressed and sintered in oxygen at 1400° to 2200°C. Densities of the sintered disks were 96 to 98% of theoretical. Solid solutions with the fluorite-type structure were formed up to 20 to 25 mole % YO_1.5 at 1400°C and up to 45 to 50 mole % YO_1.5 at 2200°C. Density data showed that these solid solutions correspond to Th_{1— x} Y _x O_{2—0.5 x} , having a complete cation sub-lattice filled by Th⁴⁺ and Y³⁺ ions, and vacancies in the anion sublattice. The observed increase in electrical conductivity with increase in YO_1.5content is consistent with charge transport by oxygen ions through a vacancy mechanism. Approximately 7 mole % ThO₂ is soluble in YO_1.5 at 2200°C. Density results indicate an anion interstitial structure for the Y₂O₃ phase. Transference number measurements indicate that the electrical conductivities are only partly due to ions.     

Sintering and Crystallization of CaO–Al2O3–ZrO2–SiO2 Glasses Containing Different Amount of Al2O3

In this work several complementary techniques have been employed to carefully characterize the sintering and crystallization behavior of CaO–Al₂O₃–ZrO₂–SiO₂ glass powder compacts after different heat treatments. The research started from a new base glass 33.69 CaO–1.00 Al₂O₃–7.68 ZrO₂–55.43SiO₂ (mol%) to which 5 and 10 mol% Al₂O₃ were added. The glasses with higher amounts of alumina sintered at higher temperatures (953°C [lower amount] vs. 987°C [higher amount]). A combination of the linear shrinkage and viscosity data allowed to easily find the viscosity values corresponding to the beginning and the end of the sintering process. Anorthite and wollastonite crystals formed in the sintered samples, especially at lower temperatures. At higher temperatures, a new crystalline phase containing ZrO₂ (2CaO·4SiO₂·ZrO₂) appeared in all studied specimens.     

Preparation of NiAl2O4/SiO2 and Co2+-Doped NiAl2O4/SiO2 Nanocomposites by the Sol–Gel Route

NiAl₂O₄/SiO₂ and Co²⁺-doped NiAl₂O₄/SiO₂ nanocomposite materials of compositions 5% NiO – 6% Al₂O₃– 89% SiO₂ and 0.2% CoO – 4.8% NiO – 6% Al₂O₃– 89% SiO₂, respectively, were prepared by a sol–gel process. NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals were grown in a SiO₂ amorphous matrix at around 1073 K by heating the dried gels from 333 to 1173 K at the rate of 1 K/min. The formations of NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals in SiO₂ amorphous matrix were confirmed through X-ray powder diffraction, Fourier transform infrared spectroscopy, differential scanning calorimeter, transmission electron microscopy (TEM), and optical absorption spectroscopy techniques. The TEM images revealed the uniform distribution of NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals in the amorphous SiO₂ matrix and the size was found to be ∼5–8 nm.     

Piezoelectric Properties of Pb(Mg1/3Nb2/3)O3 PbTiO3 -PbZrO3 Ceramics Modified with Certain Additives

Effects of additives on the piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-PbZrO₃ ceramics in a perovskite-type structure are described. The tetragonality of Pb(Mg_1/3Nb_2/3)_0.375-Ti_0.375Zr_0.25O₃ ceramics increased with the addition of NiO, Cr₂O₃, or Fe₂O₃ but decreased with the addition of MnO₂ or CoO. The dielectric and piezoelectric properties of the base composition were improved markedly through selection of additives in proper amounts. Addition of NiO yielded a high dielectric constant and planar coupling coefficient for compositions at the morphotropic transition boundary. High mechanical Q -factors and low electrical dissipation factors were obtained by addition of MnO₂. Addition of both NiO and MnO₂ produced a mechanical Q -factor of 2051 and a planar coupling coefficient of 0.553. The resonant frequency of Pb(Mg_1/2Nb_2/3)_0.4375Ti_0.4375 zr_0.125O₃ containing MnO₂ had very low temperature and time dependence. The microstructure indicated that ceramics with a high mechanical Q -factor had a fine, uniform grain structure. Addition of Cr₂O₃ retarded grain growth and addition of MnO₂, NiO, CoO, or Fe₂O₃ promoted grain growth in the ternary system.     

High-Temperature Electrical Properties in the ThO2-Rich Region of ThO2-RE2O3 Systems

In the present study the n -type electronic conduction in terms of the parameter p e, and the phase relations in several ThO₂-RE2O₃ systems were examined. Large fluorite solid solution regions exist at elevated temperatures. It was demonstrated that RE₂O₃-doped thoria compositions feature lower parameters p e, and higher chemical stability than the conventional stabilized ZrO2 electrolytes. The results are given in terms of the characteristic parameter p e, in the temperature range from 1000° to 1600°C. The experimental investigations were made using a new thermodynamic measuring system.     

Effect of Iron Oxide on the Sintering Kinetics of Al2O3

Alumina powders with varying iron oxide contents were prepared by coprecipitation. The powders were spheroidized by passing them through an oxygen-acetylene flame. The spheres were sized, annealed, and sintered in air and in N₂ with 132 ppm O₂. Isothermal studies were combined with constant-rate-of-heating studies to identify the mechanism of sintering and to calculate the diffusion coefficients. The contribution of surface diffusion during initial-stage sintering of Fe-doped Al₂O₃ was estimated by combining shrinkage and neck-growth data. The effect of Ti on the sintering rate of Fe-doped Al₂O₃ was also studied. Both Fe²⁺ and Ti⁴⁺ ions enhanced the sintering rate of Al₂O₃. A defect model for corundum is proposed to explain the sintering data for transition-metal-ion-doped Al₂O₃.     

Effect of Alkali Metal Oxide Addition on the Sinterability of MgO–B2O3–Al2O3 Glass–Al2O3 Filler Composites

The sintering of a composite of MgO–B₂O₃–Al₂O₃ glass and Al₂O₃ filler is terminated due to the crystallization of Al₄B₂O₉ in the glass. The densification of a composite of MgO–B₂O₃–Al₂O₃ glass and Al₂O₃ filler using pressureless sintering was accomplished by lowering the sintering temperature of the composite. The sintering temperature was lowered by the addition of small amounts of alkali metal oxides to the MgO–B₂O₃–Al₂O₃ glass system. The resultant composite has a four-point bending strength of 280 MPa, a coefficient of thermal expansion (RT—200°C) of 4.4 × 10⁻⁶ K⁻¹, a dielectric constant of 6.0 at 1 MHz, porosity of approximately 1%, and moisture resistance.     

Solubility of NiO in Al2O3

Solubility of NiO in Al₂O₃ was determined by electron probe microanalysisy A diffusion couple method was used by coupling an NiO-doped Al₂O₃ polycrystal to a pure single crystal of Al₂O₃. The solubility of NiO in Al₂O₃ in air was 230 wt ppm (157 at. ppm of cations) and 170 wt ppm (116 at. ppm) at 2073 and 1973 K, respectively. The solubility of NiO in Al₂O₃ obtained in this work was compared with our previous work of the solubility of MgO in Al₂o₃.     

Final Stage Sintering of ThO2

The addition of CaO to ThO₂ inhibits discontinuous grain growth and allows sintering to proceed to theoretical density by maintaining a high diffusion flux of vacancies from the pores to the grain boundaries. The optimum amount of CaO added is 2.0 mol%, which exceeds the solid solubility limit. A model of second-phase inclusions impeding grain boundary motion was used to explain the results.     

Sintering Kinetics at Isothermal Shrinkage: II, Effect of Y2O3 Concentration on the Initial Sintering Stage of Fine Zirconia Powder

The shrinkage behavior of fine zirconia powders containing 2.9 and 7.8 mol% Y₂O₃ was investigated to clarify the effect of Y₂O₃ concentration on the initial sintering stage. The shrinkage of powder compact was measured under both conditions of constant rates of heating (CRH) and constant temperatures. CRH measurements revealed that when the Y₂O₃ concentration of fine zirconia powder increased, the starting temperature of shrinkage shifted to a high temperature. Isothermal shrinkage measurements revealed that the increase in Y₂O₃ concentration causes the shrinkage rate to decrease. The values of activation energy ( Q ) and frequency-factor term (β₀) of diffusion at initial sintering were estimated by applying the sintering-rate equation to the isothermal shrinkage data. When the Y₂O₃ concentration increases, both Q and β₀ of diffusion increase. It is, therefore, concluded that the increase in Y₂O₃ concentration of fine zirconia powder decreases the shrinkage rate because of increasing Q of diffusion at the initial stage of sintering.     

Effects of B2O3 on the Phase Stability of Ba2Ti9O20 Microwave Ceramic

Preparation of dense and phase-pure Ba₂Ti₉O₂₀ is generally difficult using solid-state reaction, since there are several thermodynamically stable compounds in the vicinity of the desired composition and a curvature of Ba₂Ti₉O₂₀ equilibrium phase boundary in the BaO–TiO₂ system at high temperatures. In this study, the effects of B₂O₃ on the densification, microstructural evolution, and phase stability of Ba₂Ti₉O₂₀ were investigated. It was found that the densification of Ba₂Ti₉O₂₀ sintered with B₂O₃ was promoted by the transient liquid phase formed at 840°C. At sintering temperatures higher than 1100°C, the solid-state sintering became dominant because of the evaporation of B₂O₃. With the addition of 5 wt% B₂O₃, the ceramic yielded a pure Ba₂Ti₉O₂₀ phase at sintering temperatures as low as 900°C, without any solid solution additive such as SnO₂ or ZrO₂. The facilities of B₂O₃ addition to the stability of Ba₂Ti₉O₂₀ are apparently due to the eutectic liquid phase which accelerates the migration of reactant species.     

Optical Absorption Spectroscopy of ThO2

The optical absorption spectra from 200 to 2700 nm were determined for arc-fused ThO₂ crystals of much higher purity than any available hitherto. The fundamental absorption edge for these crystals lies at a much higher energy (∼5.9 eV) than the apparent edge reported previously for less pure specimens. This apparent edge is shown to result from one or more prominent high-energy absorption bands superimposed on the true edge for such specimens. By comparing the spectra for different specimens subjected to thermal and γ-irradiation treatments, 31 distinct absorption bands were revealed in the ThO₂ spectrum. A full analysis of certain crystals by spark-source mass spectrometry gave no strong correlation between specific band areas and individual impurity-element concentrations. Most of the bands, however, are believed to be associated with the impurity content.     

In Situ Synthesis of ZrO2/ZrW2O8 Composites With Near-Zero Thermal Expansion

In this paper, ZrO₂ and WO₃ were used as the raw materials to prepare ZrO₂/ZrW₂O₈ composites by in situ reaction method and the thermal expansion property of the composites was studied. This novel method included a heating step up to 1473 K for 24 h, which combines the synthesizing and sintering of ZrW₂O₈. The result indicates that ZrO₂/ZrW₂O₈ composite shows near-zero thermal expansion when the weight ratio of ZrO₂ and WO₃ is 2.5:1. Compared with composites prepared previously by non-reactive sintering of ZrO₂ and ZrW₂O₈, the composites show higher relative density and lower porosity.     

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.     

Thermal Grooving of MgO and Al2O3

High-purity polycrystalline MgO and Al₂O₃ were thermally grooved at 1500° and 1600°C. Accurate techniques were developed for following the growth of a single groove. For high-purity samples growth kinetics were essentially similar to those reported in the literature but were determined to be controlled by volume diffusion. Specimens for thermal grooving were prepared from Al₂O₃ to which transition metal oxides (Fe₂O₃₉, MnO, and TiO₂), which are known to accelerate shrinkage and sintering of Al₂O₃ powder compacts, had been added; the rate of groove growth was increased remarkably by minor amounts of these additives. Control of partial pressure indicated that Fe²⁺ and Ti⁴⁺ are the species active in promoting groove growth. Substantial evidence was found for volume diffusion as the mechanism controlling groove formation.     

Microwave Dielectric Properties of 5Li2O–0.583Nb2O5–3.248TiO2 Ceramics with V2O5

The effects of V₂O₅ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O–0.583Nb₂O₅–3.248TiO₂ (LNT) ceramics have been investigated. With addition of low-level doping of V₂O₅ (≤2 wt%), the sintering temperature of the LNT ceramics could be lowered down to around 920°C due to the liquid phase effect. A secondary phase was observed at the level of 2 wt% V₂O₅ addition. The addition of V₂O₅ does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the excellent microwave dielectric properties of ɛ_r=21.5, Q × f =32 938 GHz, and τ_f=6.1 ppm/°C could be obtained for the 1 wt% V₂O₅-doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as an internal electrode.