The internal oxidation of Nb-Hf alloys

Abstract

The internal oxidation of some binary Nb-Hf and several commercial Nb alloys containing Hf was studied at 1568 and 1755°C in oxygen pressures ranging from 5×10 ⁻⁵ to 1×10⁻³ torr.The reaction kinetics were linear, suggesting that diffusion of oxygen in the substrate was not rate-controlling. The dependence of the reaction rate on oxygen pressure was linear also. Well-defined reaction fronts were observed at higher pressures and the lower temperature, whereas ill-defined fronts occurred at lower pressures and at the higher temperature. The solubility product was much higher than normally encountered in Wagnerian-type behavior and gave rise to varying solute content across the internal-reaction zone. The solute-concentration profiles (EPMA/WDS) of the matrix between particles exhibited a sigmoidal shape for well-defined reaction fronts, whereas the profiles showed a gradual decrease in solute with distance near the front for ill-defined fronts, dropping fairly abruptly at the metal/gas interface. The solute concentration never reached zero at the surface for any condition studied. In contrast to classical, Wagnerian behavior, solute continued to precipitate out after the reaction zone had passed, leading to a variation in the mole fraction of oxide in the zone. SEM/EDXA and XRD showed that precipitation occurred by the formation of “precursors” (Hf-rich regions surrounded by Hf-depleted regions), followed by precipitation of tetragonalHfO₂,which in some cases transformed to monoclinicHfO₂ and subsequently coarsened. The precipitate morphology varied with solute concentration, temperature, oxygen pressure, and location within the reaction zone. High temperature and high oxygen pressure favored a Widmanstätten structure, whereas low temperature and low oxygen pressure favored a spheroidal precipitate structure. Widmanstätten plates were observed to “spheroidize” at longer times, suggesting that the interfacial energy between particles and matrix was very high. The presence of a small amount of Y (0.11 w/o in C129) always resulted in spheroidal particles. It appears that Y markedly increased the particle/matrix interfacial energy. Microhardness profiles showed decreasing values with distance into the sample for some conditions and alloys but increasing values in other cases. Hardness increases in the substrate in advance of the interface showed that oxygen activity did not reach zero at the reaction front, once again contrary to classical behavior but consistent with high solubility products of the oxide. Results are analyzed in terms of oxygen-trapping by reactive solutes as noted in the literature for both lattice-parameter measurements and oxygen diffusivity studies.