Coherent Precipitates as a Condition for Ultra-Low Fatigue in Cu-Rich Ti53.7Ni24.7Cu21.6 Shape Memory Alloys

Sputtered Ti–rich TiNiCu alloys are known to show excellent cyclic stability. Reversibility is mostly influenced by grain size, crystallographic compatibility and precipitates. Isolating their impact on cyclic stability is difficult. Ti2Cu precipitates for instance are believed to enhance reversibility by showing a dual epitaxy with the B2 and B19 lattice. Their influence on the functional fatigue, if they partly lose the coherency is still unknown. In this study, sputtered Ti53.7Ni24.7Cu21.6 films have been annealed at different temperatures leading to a similar compatibility (λ2 ~ 0.99), grain size and thermal cyclic stability. Films annealed at 550 °C exhibit a superior superelastic fatigue resistance but with reduced transformation temperatures and enthalpies. TEM investigations suggest the formation of Guinier–Preston (GP) zone-like plate precipitates and point towards a coherency relation of the B2 phase and finely distributed Ti2Cu precipitates (~ 60 nm). Films annealed at 700 °C result in the growth of Ti2Cu precipitates (~ 280 nm) with an irregular distribution and a partial loss of their coherency. Thus, GP zones are assumed to cause the reduction of transformation temperatures and enthalpies due to increased internal stresses, whereas the coherency relation of both, Ti2Cu and GP zones, help to increase the superelastic stability, well beyond 107 cycles.

Continuous Heating Dissolution and Continuous Cooling Precipitation Diagrams of a Nickel-Titanium Shape Memory Alloy

Binary NiTi alloys are the most common shape memory alloys in medical applications, combining good mechanical properties and high biocompatibility. In NiTi alloys, the shape memory effect is caused by the transformation of an austenite phase to a martensite phase and the reverse process. Transformation temperatures are strongly influenced by the exact chemical composition of the NiTi phase and the presence of precipitates in the microstructure induced by thermo-mechanical treatment, especially solution annealing and ageing. Isothermal time–temperature precipitation diagrams can be found in the literature. Cooling is frequently not considered, as water quenching is typically assumed to be sufficient. To the best of our knowledge, continuous heating dissolution (CHD) and continuous cooling precipitation (CCP) diagrams do not exist. Differential scanning calorimetry (DSC) is a common method to analyse the austenite/martensite transformation in shape memory alloys, but it has not yet been used to analyse precipitation processes during continuous temperature changes. We have enabled DSC to analyse dissolution and precipitation processes in situ during heating as well as during cooling from the solution annealing temperature. Results are presented as CHD and CCP diagrams, including information from microstructure analysis and the associated changes in the austenite/martensite transformation temperatures.