Thermodynamic analysis of ageing-induced multiple-stage transformation behaviour of NiTi

Near-equiatomic NiTi shape memory alloys normally exhibit three martensitic transformations among three phases: the B2 phase, the monoclinic (M) phase and the rhombohedral (R) phase. Some recent work, however, has revealed complex transformation behaviour involving multiple-stage martensitic transformations and multiple-stage R-phase transformations. This paper presents an analysis of these complex transformation behaviours based on thermodynamic concepts of reversible and irreversible energies associated with the transformations. The analysis is successful in identifying all observed transformations and in defining relative positions of various stages of transformations on a temperature scale. It also defines positions of thermodynamically prohibited transformations as well as permitted transformations that have not been experimentally measured. Such identifications enable the determination of actual transformation hystereses that are not directly measured experimentally. Based on the thermodynamic principles adopted, the analysis also renders it possible to identify the possible causes that contribute to the complex multiple-stage transformation behaviour.