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.     

Mechanical Relaxations in Mixed Alkali Silicate Glasses: II,Discussion*

The internal friction of mixed Li-Na, Li-K, Li-Rb, Li-Cs, Na-K, Na-Rb, Na-Cs, and K-Rb silicate glasses is interpreted on the basis of the various explanations proposed for the mixed alkali effect. A direct correlation was found between the mechanical loss peak due to the stress-induced movement of the alkali ions, i.e. the alkali peak, and the electrical loss properties. The large mechanical loss peak appearing when the alkalis are mixed was attributed to an interaction between dissimilar alkali ions such that an elastic dipole is formed. The absence of a comparable electrical loss peak was interpreted as indicating that the elastic dipole is electrically inactive. In glasses containing equimolar quantities of two alkalis, the activation energy and height of the new loss peak, i.e. the mixed peak, were more closely related to the size difference than to the mass difference of the alkali ions.     

Elastic and Anelastic Response of Polycrystalline UO2-PuO2

A sonic resonance technique was used to investigate the room-temperature elastic and anelastic properties of physically mixed U_0.8PU_0.2O₂ as a function of density, stoichiometry, and cation homogeneity. The effect of porosity on the elastic moduli was linear and is described by E =2102.7 (1–2.03 P )± 13.5 Kbars for the Young's modulus, G =823.5(1–2.05 P )± 9.1 kbars for the shear modulus, and B = 1584.8(1–1.89 P )± 59.1 kbars for the bulk modulus, where P is the volume fraction porosity. Poisson's ratio was 0.28 and was not a function of porosity. The Debye temperature of U_0.8Pu_0.2O₂ computed from the Young's and shear moduli for theoretically dense specimens was 379°K. Variation of the O/M ratio from 1.968 to 2.006 produced no significant change in either the damping capacity or the elastic moduli of single-phase 80%UO₂-20% PuO₂ solid solutions. An approximate 24% decrease of the room-temperature Young's and shear moduli and an approximate increase by a factor of 14 in the internal friction were observed with gross modifications of plutonium cation homogeneity. Preliminary results suggest that internal friction measurements might be used to assay the homogeneity of UO₂-PuO₂ solid solutions.     

Deformation and Fracture Processes in Calcium Fluoride Single Crystals

The plastic properties of calcium fluoride single crystals tested in compression were investigated in the temperature range 25° to 1000°C. Above 400° C., the crystals showed appreciable ductility. The critical resolved shear stress, t, decreased with absolute temperature, T , according to the equation t = t₀e^+K/T. The rate of work-hardening decreased rapidly as the temperature increased but retained a relatively high value even as the melting point was approached. Air-annealed crystals were harder than as-cleaved crystals. Crystals with a (111) plane normal to the applied stress hardened less rapidly than crystals with a (110) plane normal to the applied stress. The dislocation density increased linearly with strain. (100), (110), and (111) fractures were observed.     

Dissolution in Ceramic Systems: III, Boundary Layer Concentration Gradients

By use of electron microbeam probe analysis on quenched samples, the concentration distribution of CaO, A1₂O₃, and SiO₂ was determined across the boundary layer between molten calcium aluminum silicates and dissolving or growing sapphire and fused silica. A definite shift in the concentration ratios of the solvent components was found near the interface. Analysis of diffusion flux equations for a ternary system successfully related the shift in concentration ratio to the intrinsic diffusion coefficient for each component. For alumina dissolution in a melt rich in CaO, evidence of incongruent dissolution was observed with the formation of new phases, CaO· 6Al₂O₃ and CaO· 2A1₂O₃.     

Low-Temperature Sintering of Uranium Dioxide

Studies of the fabrication of uranium oxide fuel pellets by the low-temperature sintering of nonstoichiometric oxide are described. Completer reversion to stoichiometric UO₂ in the sintered pellets was attained by two methods: (1) Sintering in a nitrogen atmosphere which contained a small amount of hydrogen and (2) sintering in pure nitrogen and then exposing the pellets to hydrogen at the sintering temperature. Large variations in sinterability were found in commercially procured ceramic-grade UO₂ powder. In studying these variations, it was discovered that fluorine was a powerful inhibitor of low-temperature sintering. This impurity could be readily removed by oxidation in air at 500°C. The data strongly indicated that the primary mechanism responsible for the removel of residual fluorine was pyrohydrolysis. It was found that a preliminary oxidation-reduction cycle activated the less-sinterable oxides so that in every case densities of at least 95% of theoretical were obtained by sintering at 1200°C.     

Effect of Aspect Ratio and Viscosity Gradients on Flow Through Open Channels

The effect of aspect (height to half width) ratio on flow through open channels is considered by evaluation of St. Venant's solution. Near the center line, flow through moderately wide channels is unatrected by the side walls. Therefore, analytical solutions for the single-dimension case of flow above a flat plate are determined. They reveal that until viscosity differentials are extreme, the velocity distribution is relatively insensitive to viscosity gradients. With several simplifying assumptions the temperature distribution and the corresponding viscosity field in a cross section of the melting end of a glass tank can be calculated. This permits a numerical solution of open-channel flow for conditions appropriate to a glass tank. Calculated temperature and velocity distributions are presented for three values of the ratio of effective thermal conductivity of glass to thermal conductivity of refractory. Applications of this type of information to glass-tank technology are briefly discussed.     

Kinetics of Opacification of a TiO2-Opacified Cover Coat Enamel

Quantitative X-ray diffraction measurements were used to study the firing behavior of a typical TiO₂-opacified cover coat enamel. A model was developed for predicting the anatase and rutile concentrations as a function of time and temperature of firing. The model consists of three first order reactions: crystallization of anatase, crystallization of rutile, and inversion of anatase to rutile. It predicts successfully over a wide range of time-temperature conditions. Discrepancies are found, however, for short-time, low-temperature firings. The reflectance data do not correlate well with the crystalline concentration data. The correlation with color data is better, but is not perfect.     

Phase Equilibria in the TiO2-Rich Region of the System BaO-TiO2

Phase relations in the system BaO-TiO₂ from 67 to 100 mol% TiO₂ were investigated at 1200° to 1450°C in O₂. Data were obtained by microstructural, X-ray, and thermal analyses. The existence of the stable compounds Ba₆Ti₁₇O₄₀, Ba₄Ti₁₃O₃₀, BaTi₄O₉, and Ba₂Ti₉O₂₀ was confirmed. The compound BaTi₂O₅ is unstable and either forms as a reaction intermediate below the solidus or crystallizes from the melt. The compounds Ba₆Ti₁₇O₄₀ and Ba₄Ti₁₃O₃₀ decompose in peritectic reactions, and BaTiO₃ and Ba₆Ti₁₇O₄₀ react to form a eutectic. Special conditions are required for the formation of Ba₂Ti₉O₂₀, which decomposes in a peritectoid reaction at 1420°C. The new phase diagram is presented.     

Raman Study of Isothermal Devitrificatn Kinetics of NaPO3 Glass

A laser Raman spectroscopic method was developed by which the increase in crystallinity of a devitrifying glass can be monitored continuously and isothermally at the devitrification temperature, without sample quenching, in a molecularly specific manner that yields high-quality kinetic data for the glass-crystal transformation. Applied to the study of vitreous (NaPO₃)_n( gl ), the method yielded continuous data which were fitted, by a nonlinear least-squares method, to an equation of the form α( t ) = 1- exp (- k_Nt^N ) with sufficient precision to permit optimization with respect to both N and k_N. The values of N and k_N vary with glass thermal history, i.e. with variations in time of heating at T_g for otherwise identical samples, although the material does not phase separate. The activation energy from any plot of In ( k_N )^{1/ N} vs (1/ T ) does not vary, but the offset of the curves indicates different preexponential terms in the Arrhenius expression. The results are analyzed in terms of current theories.