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.     

Activated Sintering of ThO2 and ThO2-Y2O3 with NiO

The effect of additives on the sintering of ThO₂ and ThO₂-Y₂O₃ compacts and loose powders was studied by isothermal shrinkage measurements and by scanning electron micrography. Small amounts of the oxides of Ni, Zn, Co, and Cu reduced the sintering temperature. The behavior of NiO at a concentration of 0.8 wt% (2.5 mol%) was studied in detail and found to yield high-density bodies at temperatures below 1500°C. The presence of Y₂O₃ as a separate phase increases the rate of sintering of ThO₂, but smaller amounts of NiO are much more potent. The major portion of the densification occurs very rapidly and is followed by a much slower sintering process typical of volume diffusion. The fast early shrinkage may be caused by the capillary forces of a liquid, but since no evidence of melting was found, a solid-state mechanism may be responsible.     

Diversion Resistance of a Chloride Volatility Reprocessing System for UO2/ThO2 Fuel

A chloride volatility process is considered for reprocessing ²³³U-Th fuel. Isotopes of high gamma activity or neutron capture cross section are designated. The behavior of these isotopes in the process is related to their chemical states in the spent fuel, the free energies of reaction with C1₂ and/or CC1₄, and the volatilities of the chlorides.     

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.     

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.     

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.     

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.     

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)°.     

Alpha Particle Irradiation Damage in ThO2

The effect of α-particle irradiation (5.5 MeV, total dose ∼10¹⁵ particles/cm²) on the microstructure of ThO₂ was studied by transmission electron microscopy. The only as-irradiated damage seen consisted of point defect agglomerations visible as small black spots. Subsequent heating to ∼1500°C in the electron microscope caused the spots to grow into loops 50 to 200 Å in diameter, but no voids, bubbles, or pores were observed. The preferred loop planes were {311}, {110}, and {012}, in that order of frequency.     

Electrical Properties and Defect Structure of ThO2

The electrical conductivity and thermoelectric power of highpurity polycrystalline ThO₂ in thermodynamic equilibrium with the gas phase were measured as a function of temperature from 1000° to 1600°C and as a function of oxygen partial pressure from 1 to 10⁻²² atm. An n -type electronic contribution to the conductivity is observed above 1400°C at low oxygen pressures. An analytic solution is presented for the oxygen pressure dependence of the total conductivity in the mixed ionicelectron hole conduction region observed at higher oxygen pressures. The activation energies for p -type and ionic conduction are 1.0 and 0.9 eV, respectively. The combined conductivity and thermal emf data give a lower limit of ∼6 cm²/V-s for the electron hole mobility.     

Strain Effects and Spalling in Alpha-Bombarded ThO2

Samples of bulk polycrystalline ThO₂ were bombarded with 5-MeV α-particles to doses between 9.4×10¹⁶ and 6.0×10¹⁷ ions/cm². The sample which received the highest dose spalled during bombardment; those receiving lower doses either did not spall or did so only after postirradiation annealing. The spalling was investigated by X-ray analysis and replica and transmission electron microscopy. It is concluded that spalling resulted from severe lattice strains at the interface between damaged and undamaged material and that sintering pores played a part in the fracture process. The role of lattice defects in initiating fracture is discussed.     

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.     

Ionic Domain for Y2O3-Doped ThO2 at Low Oxygen Activities

The emf method was used to determine the lower limit of oxygen activity for essentially pure anionic conduction in Th_0.85Y_0.15O_1.925 from 775° to 1000C. The results show that the oxygen transference number is ≥0.99 when log PO ₂≥−6.5(10⁴/ T °K)+29.     

Interaction Between UO2 Pellets and Cladding in Water Reactor Fuel Pins

The contribution of mechanical interaction between fuel and cladding to the change in length of a fuel pin has been identified from an analysis of data from the Steam-Generating Heavy-Water Reactor. A model which accounts for this effect uses the creep properties of fuel and cladding.     

Phase Relations in the System UO2-UO3– Y2O3

The phase relations in the system U02-U03-Yz03, particularly in the Y203-rich region, were examined by X-ray and chemical analyses of reacted powders heated at temperatures up to 1700°C in H₂, CO₂-CO₂ and air. Four phases were identified in the system at temperatures between 1000° and 1700°C: U308, face-centered cubic solid solution, body-centered cubic solid solution, and a rhombohedral phase of composition (U,Y)₇O₂ ranging from 52.5 to 75 mole % Y₂O₃. The rhombohedral phase oxidized to a second rhombohedral phase with a nominal composition (U,Y), at temperatures below 1000°C. This phase transformed to a face-centered cubic phase after heating in air above 1000° C. The solubility of UO, in the body-centered cubic phase is about 14 mole % between 1000° and 1700°C but decreases to zero as the uranium approaches the hexavalent oxidation state. The solubility of Yz03 in the face-centered cubic solid solution ranges from 0 to 50 mole % Y2O3 under reducing conditions and from 33 to 60 mole % Y2O3 under oxidizing conditions at 1000°C. At temperatures above 1000° C, the face-centered cubic solid solution is limited by a filled fluorite lattice of composition (U,Y)O₂. For low-yttria content, oxidation at low temperatures (<300°C) permits additional oxygen to be retained in the structure to a composition approaching (U,Y)O_2.25 A tentative ternary phase diagram for the system UO₂-UO₃-Y₂O₃ is presented and the change in lattice parameter and in cell volume for the solid-solution phases is correlated with the composition.