Dwight L. Myers

High-temperature vaporization of B2O3(l) under reducing conditions.

The vaporization of B(2)O(3) in a reducing environment leads to the formation of both B(2)O(3)(g) and B(2)O(2)(g). Whereas the formation of B(2)O(3)(g) is well understood, many questions about the formation of B(2)O(2)(g) remain. Previous studies using B(s) + B(2)O(3)(l) have led to inconsistent thermodynamic data. In this study, it was found that, after heating, B(s) and B(2)O(3)(l) appeared to separate and variations in contact area likely led to the inconsistent vapor pressures of B(2)O(2)(g). To circumvent this problem, the activity of boron was fixed with a two-phase mixture of FeB and Fe(2)B. Both second- and third-law enthalpies of formation were measured for B(2)O(2)(g) and B(2)O(3)(g). From these values, the enthalpies of formation at 298.15 K were calculated to be -479.9 ± 25.7 kJ/mol for B(2)O(2)(g) and -833.4 ± 13.1 kJ/mol for B(2)O(3)(g). Ab initio calculations to determine the enthalpies of formation of B(2)O(2)(g) and B(2)O(3)(g) were conducted using the W1BD composite method and showed good agreement with the experimental values.

Rhenium/Oxygen Interactions at Elevated Temperatures

The oxidation of pure rhenium was examined from 600 to 1400°C in oxygen/argon mixtures. Linear weight-loss kinetics were observed. Gas pressures, flow rates, and temperatures were methodically varied to determine the rate-controlling steps. The reaction at 600 and 800°C appeared to be controlled by a chemical-reaction step at the surface; whereas the higher-temperature reactions appeared to be controlled by gas-phase diffusion of oxygen to the rhenium surface. Attack of the rhenium appeared along grain boundaries and crystallographic planes.

Computational and Experimental Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures

Gaseous titanium hydroxide and oxyhydroxide species were studied with quantum chemical methods. The results are used in conjunction with an experimental transpiration study of titanium dioxide (TiO2) in water vapor-containing environments at elevated temperatures to provide a thermodynamic description of the Ti(OH)4(g) and TiO(OH)2(g) species. The geometry and harmonic vibrational frequencies of these species were computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. For the OH bending and rotation, the B3LYP density functional theory was used to compute corrections to the harmonic approximations. These results were combined to determine the enthalpy of formation. Experimentally, the transpiration method was used with water contents from 0 to 76 mol % in oxygen or argon carrier gases for 20-250 h exposure times at 1473-1673 K. Results indicate that oxygen is not a key contributor to volatilization, and the primary reaction for volatilization in this temperature range is TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods using the thermal functions derived from the theoretical calculations. The third law enthalpy of formation at 298.15 K for TiO(OH)2(g) at 298 K was -838.9 ± 6.5 kJ/mol, which compares favorably to the theoretical calculation of -838.7 ± 25 kJ/mol. We recommend the experimentally derived third law enthalpy of formation at 298.15 K for TiO(OH)2, the computed entropy of 320.67 J/mol·K, and the computed heat capacity [149.192 + (-0.02539)T + (8.28697 × 10-6)T2 + (-15614.05)/T + (-5.2182 × 10-11)/T2] J/mol-K, where T is the temperature in K.

Hysteresis in the Active Oxidation of SiC

Si and SiC show both passive oxidation behavior where a protective film of SiO2 forms and active oxidation behavior where a volatile suboxide SiO(g) forms. The active-to-passive and passive-to-active oxidation transitions are explored for both Si and SiC. Si shows a dramatic difference between the P(O2) for the two transitions of ~10-4 bar. The active-to-passive transition is controlled by the condition for SiO2/Si equilibrium and the passive-to-active transition is controlled by the decomposition of SiO2. In the case of SiC, the P(O2) for these transitions are much closer. The active-to-passive transition appears to be controlled by the condition for SiO2/SiC equilibrium. The passive-to-active transition appears to be controlled by the interfacial reaction of SiC and SiO2 and subsequent generation of gases at the interface which leads to scale breakdown.

THERMODYNAMICS OF THE TL-O SYSTEM AND TL-SUPERCONDUCTORS

Experiments have been performed to determine vaporization reactions in the Tl–O system. When the starting sample was pure Tl2O3(c), the vapor was initially rich in oxygen compared to the starting Tl2O3(c) composition. When the extent of vaporization of the sample was between 30% and 80%, the residue composition was Tl4O3(c). The congruently vaporizing composition was concluded to be in the Tl4O3(c) single phase region. This conclusion supports the thermodynamic data for thallium oxides which was published by Holstein. Vapor pressure data for the two phase region with Tl-superconductors Tl-2223(c) and Tl-1223(c), which we measured previously and reported as activities, have been reevaluated.