Differential Thermal Analysis Investigation of the High-Low Cristobalite Inversion Under Hydrostatic Pressure to 7 Kbar

The high-low inversion in polycrystalline cristobalite, synthesized from quartz at 1500°C, was investigated by differential thermal analysis to 7 kbar in hydrostatic apparatus. A region of anomalous curvature ( d²T/dp² >0) exists to ∼1 kbar; at higher pressure, the low→high and high→low transition temperatures vary linearly with pressure, with slopes of ∼51.₁ and 53. ₆ deg kbar⁻¹, respectively. Extrapolated 1-bar intercepts are ∼232° and ∼209°C, respectively. It is concluded that high cristobalite is less compressible than low cristobalite near the inversion. The hysteresis between the high→low and low→high transition temperatures decreases with increasing pressure.     

EXPERIMENTAL STUDIES OF NUCLEATION PHENOMENA WITHIN THERMAL BOUNDARY LAYERS—INFLUENCE ON CHEMICAL VAPOR DEPOSITION RATE PROCESSES

In carrying out partial vapor condensations using actively cooled surfaces it is known that 'mist' formation can occur within thermal boundary layers (Rosner and Epstein, 1968), dramatically modifying total deposition fluxes. Using a combination of flash-evaporation (Rosner and Liang, 1986) and laser probing techniques, we report new experimental results on binary alkali salt (K₂SO₄ + Na₂SO₄) deposition from combustion gases showing that the deposition rate of potassium sulfate first increases with the addition of sodium sulfate until the concentration of Na₂SO₄ reaches a (target surface temperature dependent) 'threshold' value. Further increases in the concentration of Na₂SO₄ dramatically decrease the total deposition rate of K₂SO₄, implying that potassium sulfate-containing microdroplets are formed within the thermal boundary layer, which, despite their thermophoretic drift toward the target, are not collected as effectively as the 'parent' K₂SO₄-vapor species. Laser light scattering measurements clearly reveal that suspended particles exist near the deposition surface under these conditions. Our experimental results on mass transfer rate and light scattering are consistent with those predicted using laminar boundary layer theory (Castillo and Rosner, 1989b) coupling both binary salt vapor deposition with particle vapor scavenging and deposition. Comparisons of our observed mist onset conditions (implying critical supersaturations near unity) with those expected using homogeneous nucleation theory suggest that the binary alkali sulfate mist nucleation mechanism is, instead, heterogeneous, even in our relatively 'clean' combustion products. Because of the; well-known vapor pressure reduction phenomenon associated here with the formation of non-ideal solutions, binary systems are shown to provide convenient 'vehicles' to investigate BL mist formation onset conditions and CVD-rate consequences without requiring the more extreme surface coolings characteristic of unary condensible vapor systems. An understanding of this dramatic phenomenon, obtained via such laboratory experiments and calculations, will allow its inclusion in future deposition rate calculations of engineering importance.     

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.     

Phase Equilibria in the System CaF2-AlF3-Na3AlF6 and Part of the System CaF2-AlF3-Na3AlF6-Al2O3

The complete phase-equilibrium diagram of the system CaF₂-AlF₃-Na₃AlF₆ and the subsolidus portion of the system CaF₂-AlF₃-Na₃AlF₆-Al₂O₃ were established from microscopic, powder X-ray diffraction, quench, and DTA data obtained from samples encapsulated in sealed tubes and either reacted in the solid state or melted and recrystallized. The system Na₃AlF₆-CaF₂ contains a simple eutectic with no compound formation or solid solution. The system CaF₂-AlF₃-Na₃AlF₆ contains two ternary compounds, NaCaAlF₆ and NaCaAl₂F₉, which melt incongruently at 735° and 712°C, respectively; NaCaAlF₆ exists in three polymorphic forms with transitions at 610° and 722°C and NaCaAl₂F₉ is body-centered cubic with a₀= 10.765 Å. The three binary and two ternary compounds divide the system into eight compatibility triangles. Along the NaCaAlF₆-Na₃AlF₆ join, 7 mol% NaCaAlF₆ is soluble in α-cryolite at 525° and 42% in β-cryolite at 731°C. The quaternary system Na₃AlF₆-AlF₃-CaF₂-Al₂O₃ contains eight compatibility tetrahedra.     

Effect of Grinding on Flaw Geometry and Fracture of Glass

Fracture mechanics is combined with fracture surface analysis to analyze brittle failure of glass bars which were tested relative to the direction of grinding. Grinding essentially produces two sets of flaws from which failure occurs. In the most severe set, formed basically parallel to the grinding direction, the ratio of the average depth ( a ) to the half-width ( b ) is 0.5. In the less severe set, formed perpendicular to the grinding direction, the average a / b ratio is 1.6. In both sets the most severe flaws are generally associated with a particularly deep grinding groove or gouge. The strength reduction resulting from testing perpendicular to the grinding direction results from the larger flaw size and slightly higher stress-intensity factor resulting from the greater ellipticity of the flaws formed parallel to the grinding grooves and perpendicular to the tensile axis. Detailed analysis of these 2 sets of flaws causing failure of appropriately oriented specimens shows that (1) the fracture mirror radius, r , occurs at a constant stress-intensity level independent of flaw geometry; (2) unsymmetric fracture mirrors result from unsymmetric, irregular flaws leading to unsymmetric stress-intensity distributions; (3) is constant for semielliptical flaws; and (4) fracture energy calculated from an expression including mirror constants, the flaw-to-mirror size ratio, and the flaw geometry agrees with measured values over a wide range of a / b values.     

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.     

Defect Structure of NiO-CoO Solid Solutions

Measurements at high temperature of integrated intensities of Bragg peaks were used to examine the defect structure in two NiO-CoO solid solutions. The results indicate that the concentrations of vacant cation sites at 1100° to 1500°C are 4 to 10% and the tetrahedral occupations 2 to 5%. The concentration of these defects increases with temperature and partial pressure of O₂. The mean-square displacements of oxygen ions and cations increase with temperature and CoO concentration.     

Systems of Na-Fe-SiO2 Glasses and Steel: I, Wetting and Adherence

Wetting behavior of molten Na₂O-Fe₂O₃-SiO₂ and Na₂O-FeO-SiO₂ glasses on very-low-carbon steel at 900°C in purified Ar was studied. The steel surface was dry-polished and cleaned by ion bombardment. Glass frit was then placed on the metal, and the system was introduced into the furnace without exposure to air. Dynamic advancing and receding contact angles were measured. Shear (push-off) tests were performed on the glass-steel composite at room temperature to determine adherence. The equilibrium contact angles were obtained from the arithmetic mean of the final advancing and receding angles. As the Fe oxide content of the glasses increased, the degree of wetting improved; Fe³⁺ was more effective than a combination of Fe³⁺ and Fe²⁺ in improving the wettability. Glasses very nearly saturated with Fe oxide exhibited high adherence values and chemically adhered to steel.     

Swelling Control in Uranium Carbide

Fine particles were dispersed in a fuel structure to trap fission gases as very small bubbles and thereby reduce fuel swelling. The dispersions were made by adding 1.5 to 3.0 wt% W to the UC; the specimens were irradiated to a maximum of ∼2 at.% burnup. Density changes were used as the measure of swelling; there was much scatter in the results. Tungsten reduced the swelling when it was uniformly dispersed. For some samples having excess U and W or a segregated structure, W increased the swelling. The results tentatively confirm that fine particles are of value in reducing fission-gas swelling of carbide fuels.