First-Principles Investigation of Phase Transitions in RuNb, RuTa, and Ru-Nb-Ta Ultrahigh Temperature Shape Memory Alloys

Ultrahigh temperature shape memory alloys (UHT-SMAs) have transition temperatures above 600 °C, and they have found applications for sensing and actuating devices in aerospace industry. Among very few such UHT-SMAs currently known are Ru-based alloys such as RuNb and RuTa, whose martensite structures and phase transitions are totally different from those of NiTi-based SMAs and were poorly understood. In this work, we carried out a systematical study of RuNb using first-principles total energy calculations and molecular dynamics (MD) simulations. The transition paths and mechanisms in cubic → tetragonal →monoclinic transitions are revealed. and the transition sequence and martensitic transition temperatures are determined (MTTs) by evaluating the Gibbs free energies using thermodynamic integration. The calculated MTTs are in very good agreement with the experimental data. We found that the monoclinic phase at the second transition has the 𝑃2₁/m symmetry instead of experimentally identified 𝑃2/m. Our calculations demonstrate that RuTa has very similar phase transitions to those of RuTa. Furthermore, we studied the Ru_0.5Nb_0.25Ta_0.25 ternary. Our results can explain the measured significant drop of MTT (~ 200 °C) in the second transition for Ru_0.5Nb_0.25Ta_0.25 compared with those of RuNb and RuTa, while in the first transition its MTT is between MTTs of RuNb and RuTa.

The insights gained by this study and the verified ab initio methods for accurate MTT calculations can be applied to fast screen and quantitatively design novel UHT-SMAs having similar properties with desirable MTTs and much reduced cost.