Thermal Conductivity of Nearly Stoichiometric Single-Crystal and Polycrystalline UO2

The thermal conductivities, λ, of single-crystal and polycrystalline UO₂ were measured from 80° to 420°K. The results indicate no observable difference in λ between single-crystal and polycrystalline UO₂, and both materials have broad peaks in λ at ∼220°K. The results were used with literature values to determine the effect of closed porosity on λ. The thermal conductivity of theoretically dense UO₂ is described phenomenologically from 80° to 1400°K, where conduction is dominated by the phonon component. The phonon conduction is analyzed by comparison with ThO₂. This analysis indicates that the high-temperature λ is limited by 3-phonon Umklapp scattering processes. Scattering by the disordered spins associated with the paramagnetic U ions contributes a large temperature-independent phonon scattering term. This mechanism has a mean free path of about 51 Å, which implies that grain boundaries and impurities have a relatively insignificant effect on the phonon conduction far above the antiferromagnetic-para-magnetic transition at ∼ 30°K. This implication agrees with the experimental results.     

Effects of Grain Size and Microcracking on the Thermal Diffusivity of MgTi2O5

The laser flash technique was used to study the effect of grain size on the thermal diffusivity of polycrystalline MgTi₂O₅ from 25° to 800°C. Microcracking decreased the thermal diffusivity by as much as a factor of two with the decrease increasing with increasing grain size. When specimens were heated then cooled, the thermal diffusivity exhibited a horizontal flat figure-eight hysteresis. This hysteresis, which appeared to be a function of the thermal history, was attributed to a balance between crack healing, or closure, at high temperatures and the growth of existing cracks or the formation of new cracks during cooling.     

Annealing of Irradiation-Induced Thermal Conductivity Changes in ThO2-1.3 wt% UO2

The thermal conductivities of sintered pellets of ThO₂-1.3 wt% U0₂ were measured at 60°C before and after irradiation. The irradiation temperature was below 156°C, and the exposures varied from 3.1 × 10¹⁴ to 4.7 × lo^L7 fissions/cm³. Each fission fragment damaged a region of 2.2 × 10^-16 cm³ with the reduction in conductivity saturating by about 10¹⁷ fissions/cm³. Samples having exposures from 10¹⁵ to 10¹⁶ fissions/cm³ were annealed isothermally at 651 °C or isochronally from 300° to 1200° C to study the annealing of damage. Most of the annealing occurred between 500° and 900°C. The width of this interval plus the slow isothermal annealing suggest that the damage is annealed by a number of single order processes with a spectrum of activation energies from 1.8 to 3.9 eV or, less probably, by a high order process with an activation energy of 3.55 ± 0.4 eV.     

Thermal Expansion of SrY2O4

Crystals of SrY₂O₄ (space group Pnam ) were examined by high-temperature powder X-ray diffractometry to determine the changes in unit-cell dimensions with temperature. The individual cell dimensions linearly increased with increasing temperature up to 1473 K. The expansion coefficients (K⁻¹) were 1.263(8) × 10⁻⁵ along the a- axis, 7.46(6) × 10⁻⁶ along the b- axis, and 9.93(10) × 10⁻⁶ along the c- axis. The coefficient of mean linear expansion was 1.001(8) × 10⁻⁵ K⁻¹.     

Effect of Microcracking on the Thermal Diffusivity of Fe2TiO5

The effect of microcracking on the thermal diffusivity of polycrystalline Fe₂TiO₅ subjected to a range of annealing treatments was investigated. At fine grain size (∼1 μm), the thermal diffusivity exhibited the decrease with increasing temperature common for dielectrics. Extensive microcracking in the larger-grain-sized materials significantly decreased their thermal diffusivity. On heating, the microcracked materials exhibited increased thermal diffusivity at elevated temperatures which can be attributed primarily to microcrack closure and healing; on cooling, they exhibited a pronounced hysteresis, attributable to irreversible crack opening and closing. Thermal cycling closed the hysteresis curves, which suggests permanent changes in microcrack morphology. It appears that microcracking is a promising technique for tailoring ceramic materials to a combination of high thermal shock resistance and good insulating capability.     

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.     

Equilibrium Cation Distribution in NiAl2O4, CuAl2O4, and ZnAl2O4 Spinels

Stoichiometric NiAl₂O₄, CuAl₂O₄, and ZnAl₂O₄ spinels were prepared and equilibrated at temperatures from 600° to 1400°C. The parameters u and x , denoting the oxygen position and fraction of divalent cations on tetrahedral sites, respectively, were determined from a detailed X-ray diffraction analysis. In NiAl₂O₄, x increased from 0.07 at 595° to 0.26 at 1391°C; in CuAl₂O₄, x decreased from 0.68 at 613° to 0.64 at 1195°C; and in ZnAl₂O₄, x decreased from 0.96 at 905° to 0.94 at 1197°C. The form of the temperature dependence of x could not be described using theoretically based equations advanced in the literature. A more general equation which allows for a non-distributional contribution to the configurational entropy was derived and observed to properly describe the temperature dependence; the results indicate that short-range order is of definite significance in these intermediate aluminate spinels.     

Effect of Al2O3 and Bi2O3 on the Formation Mechanism of Sn-Doped Ba2Ti9O20

High-performance Ba₂Ti₉O₂₀ ceramics are attracting great attention, but their formation mechanism still is somewhat unclear. The present investigation shows that the formation of Ba₂Ti₉O₂₀ can be promoted strikingly by the participation of Bi₂O₃ and Al₂O₃. The effect of Bi₂O₃ on the formation of Ba₂Ti₉O₂₀ is attributed to the fact that migration of the involved reactants is accelerated by liquid which forms from the melting of Bi₂O₃ above 830°C. This migration, however, is not the only rate-limiting factor. A high potential-energy barrier, resulting from stress that arises along the crystal-structured layers, also heavily restricts the formation of Ba₂Ti₉O₂₀. The participation of Al₂O₃, on the other hand, can reduce the height of this potential-energy barrier and effectively improve the kinetics of the formation of Ba₂Ti₉O₂₀ by causing the formation of BaAI₂Ti₆O₁₆ crystals; these crystals intergrow with Ba₂Ti₉O₂₀ crystals and result in decreased stress.     

Sol–Gel Preparation of BaTi4O9 and Ba2Ti9O20

BaTi₄O₉ and Ba₂Ti₉O₂₀ precursors were prepared via a sol–gel method, using ethylenediaminetetraacetic acid as a chelating agent. The sol–gel precursors were heated at 700°–1200°C in air, and X-ray diffractometry (XRD) was used to determine the phase transformations as a function of temperature. Single-phase BaTi₄O₉ could not be obtained, even after heating the precursors at 1200°C for 2 h, whereas single-phase Ba₂Ti₉O₂₀ (as determined via XRD) was obtained at 1200°C for 2 h. Details of the synthesis and characterization of the resultant products have been given.     

The System UO2-ZrO2

A phase diagram is proposed for the system UO₂-ZrO₂ on the basis of earlier work and the results of new studies in which the mixed oxides were melted in a solar furnace to avoid contamination. X-ray diffraction measurements were made on specimens melted in helium and on the same specimens after heating to 1350°C. in helium. The system shows a narrow two-phase region about the eutectic at high temperatures which increases in extent at lower temperatures. The high-temperature form of zirconia cannot be stabilized by the addition of UO₂.     

Comment on "Effect of Al2O3 and Bi2O3 on the Formation Mechanism of Sn-Doped Ba2Ti9O20"

in a recent article of the Journal , Yu et al .¹ reported their experimental results on the effect of Al₂O₃ and Bi₂O₃ on the formation mechanism of Sn-doped Ba₂Ti₉O₂₀. They claimed that both Al₂O₃ and Bi₂O₃ can dramatically assist the formation of Sn-doped Ba₂Ti₉O₂₀ but are based on different mechanisms. They concluded that first, Bi₂O₃ melts above 830°C and accelerates the migration of the involved reactants to form Ba₂Ti₉O₂₀; second, Al₂O₃ can reduce the height of the potential energy barrier of the formation of Ba₂Ti₉O₂₀ due to the intergrowth of BaAl₂Ti₆O₁₆ phase. They explained their results from a point of view that the formation of Ba₂Ti₉O₂₀ is controlled by (1) the migration of reactants to the interfaces and (2) the height of the potential-energy barrier of the reaction at the interfaces. However, based on their results, we feel their conclusions are incautious and may be misleading, as will be discussed later.     

Electrical Conductivity of MgAl2O4 and Y3A15O12

The electrical conductivities of single crystal and polycrystalline MgAl₂O₄ and Y₃Al₅O₁₂ were measured to 1260 K using a three-contact, guard-ring technique. The electrical conduction mechanisms change with temperature, with anomalous oxygen pressure and time-dependent inflections in log σ versus T⁻¹ curves between 900 to 1000 K. The conduction processes of Y₃Al₅O₁₂ and MgAl₂O₄ appear to be similar and possibly related to A1³⁺ ion diffusion.     

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.     

Electrical Conductivity of Glasses in the Systems P4O10-V2O5 and P4O10-WO3

The electrical conductivities of P₄O₁₀-V₂O₅ and P₄O₁₀-WO₃ glasses were compared. The P₄O₁₀ content of a glass from each system was replaced by increasing amounts of several oxides. The conductivity of the vanadium phosphate glass was insensitive to oxide replacement, in contrast to the conductivity of the tungsten phosphate glass, which decreased by almost five decades when a small amount of V₂O₅ was introduced. The change was attributed to the effect of oxidation-reduction on the tungsten ions.     

Thermal Expansion and Athermal Phase Transition of Y4AI2O9 Ceramics

Thermal expansion of Y₄A1₄O₉ ceramics prepared at 1600° and 1800°C was measured from room temperature to 1500°C in air. Volume changes at the phase transition of Y₄A1₂O₉, along with thermal hysteresis, were observed around 1400°C. The volume of the high-temperature phase was about 0.5% lower than that of the low-temperature phase. The hysteresis width for the sample prepared at 1600°C was 56°C, wider than that (14°C) for the sample prepared at 1800°C. The averages of phase transition start temperatures on heating and on cooling for these samples were, however, almost the same at 1377°C. The phase transitions did not occur at fixed temperatures, and the proportions of the high-temperature phase and the low-temperature phase did not change with time as long as the temperature remained constant ( athermal character). The sample prepared at 1800°C also showed another thermal hysteresis behavior from room temperature to about 1000°C.     

Thermal Expansion of Uranium Pyrophosphate and of Ceramic Bodies in the System UO2–UP2O7

During an investigation of methods of predicting the thermal expansion of pure, single-phase ceramics, uranium pyrophosphate (UP₂O₇) was synthesized and the thermal-expansion properties were measured by the X-ray diffraction and dilatometer methods. The basis for the selection of UP₂O₇ is discussed. Cubic UP₂O₇ expands with increasing temperature up to 400°C. Above this temperature the material contracts so that the specimen returns to the room-temperature length at about 1000°C. Intermediate phases in the system UO₂–UP₂O₇ were prepared and the thermal-expansion properties were measured. Ceramic bodies in the system UO₂–UP₂O₇ were prepared. The thermal-expansion properties of these bodies are discussed in relation to the properties of the individual phases.     

Microcracking of Eu2O3=Ta2O5 Bodies

Europium sesquioxide is of interest as a control material for reactors because it has several large-cross-section isotopes which form successively on neutron capture. Pure monoclinic Eu₂O₃ tends to grow large grains during sintering, causing microcracks to develop and leading to anomalous mechanical properties. The effect of doping the Eu₂O₃ with the grain growth suppressant Ta₂O₃ was determined using studies of the elastic properties and internal friction by the sonic resonance technique. Compositions with <3 at.% Ta cation substitution had anomalously low room temperature elastic moduli values and showed a hysteresis on thermal cycling. These specimens also had high internal frictions. The finer-grained specimens which resulted when the dopant level exceeded 3 at.% Ta did not show these anomalous characteristics.