| A systems-based approach, integrating quantum mechanical calculations with efficient experimentation, was employed to design niobium-based superalloys. The microstructural concept of gamma-gamma' nickel-based superalloys was adopted, where, the coherent gamma ' aluminides act both as the strengthening phase and a source of aluminum for Al2O3 passivation. Building on previous research, the selected bcc-type ordered aluminide was L2 1 structured Pd2HfAl phase. Comprehensive phase relations were measured on Nb-Pd-Hf-Al prototype alloys, and key tie-tetrahedra were identified. Aluminide precipitation in a bcc matrix was demonstrated in designed Nb+Pd2HfAl alloys. Thermodynamic databases were developed by integrating first-principles calculations with measured phase relations. Atomic volume models were developed for the bcc matrix and the Pd2HfAl phase and matrix elements which would reduce lattice misfit were identified. An experimental 2-phase alloy demonstrated a misfit of 3%.; A modified Wagner's model was used to predict the required transient properties to form external Al2O3. The principal oxidation design goal was to decrease the oxygen permeability ( NSOx DO ) divided by the aluminum diffusivity (DAl) by 5 orders of magnitude. A multicomponent mobility database was developed to predict the diffusivities. Guided by first-principles calculations the effect of alloying elements on the oxygen diffusivity in Nb was measured, and the mobility database was experimentally validated.; Based on the mobility database, it was found that increasing Al solubility in the bcc matrix greatly increased Al diffusivity. Alloying elements were identified that would increase Al solubility in the bcc matrix. Prototype alloys were prepared and the best oxidation performance was exhibited by a bcc+Nb2Al Nb-Hf-Al alloy, which exhibited parabolic oxidation behavior at 1300°C. The alloy was shown to have achieved the required 5 orders of magnitude reduction in the design parameter. The oxidation performance of the Nb-Hf-Al alloy achieved the IHPTET Phase III oxidation goals. However, the alloy failed to form a continuous Al2O3 scale, due to formation of stable HfO2 and observed NbAlO4, which was shown to be metastable by first-principles calculations. This implies that catalytic formation of Al2O3 is still thermodynamically possible in these systems. A new design strategy is also proposed which exploits fast yttrium diffusion in Nb to form a protective YAG scale. |
