NiTiHf alloys have emerged as potential materials for applications requiring high transformation temperatures (> 100 °C) with high strength and work output. Although they have high transformation temperatures, their low damping capacity, brittleness and poor superelastic responses (of Ti-rich NiTiHf) impedes their wider usage in many industrial applications. In this study, the quaternary alloying element of Pd has been added to NiTiHf alloys to improve and tailor their shape memory behavior,. NiTiHfPd alloys were systematically examined regarding the composition and heat treatments effects. Effects of substituting Hf with Ti on the shape memory behavior of NiTHfPd alloys were investigated. There compositions were selected as Ni40.3Ti34Hf20Pd5 Ni40.3Ti39.7Hf15Pd5 and Ni40.3Ti44.7Hf10Pd5 (at.%). Their transformation temperatures, microstructure and shape memory properties were revealed and compared with conventional shape memory alloys. It was revealed that their transformation temperatures increases but transformation strain decreases with the increment of Hf content. Additionally, superelastic responses of Ni45.3Ti29.7Hf20Pd5 andNi45.3Ti39.7Hf10Pd5 alloys were investigated. Transformation temperatures of polycrystalline Ni45.3Ti29.7Hf20Pd5are highly dependent on aging temperatures and they can be altered widely from room temperature to 250 oC. Finally, the damping capacity of the Ni45.3Ti39.7Hf10Pd5 polycrystal and [111]-oriented Ni45.3Ti29.7Hf20Pd5 single crystal were investigated. The damping capacities were found to be 16-25 J.cm-3, and 10-23 J.cm-3 for the Ni45.3Ti39.7Hf10Pd5 and [111]-oriented Ni45.3Ti29.7Hf20Pd5 alloys, respectively.

NiTiHf high temperature shape memory alloys are attractive due to their high operating temperatures (>100 oC) and acceptable transformation strain compared to NiTi. However, NiTiHf has limitations due to their lack of ductility and low strength, resulting in poor shape memory properties. In this study, Pd has been added to NiTiHf alloys in an attempt to improve their shape memory behavior. A combined approach of quaternary alloying and precipitation strengthening was used. The characterization of a Ni45.3Ti29.7Hf20Pd5 (at. %) polycrystalline alloy was performed in compression after selected aging treatments. Transmission electron microscopy was used to reveal the precipitation characteristics. Differential scanning calorimetry, load-biased (constant stress) thermal cycling experiments and isothermal stress cycling (superelasticity) tests were utilized to investigate the effects of aging temperature and time. The crystal structure and lattice parameters were determined from X-ray diffraction analysis. Significant improvement in the shape memory properties of Ni45.3Ti29.7Hf20Pd5 was obtained through precipitation strengthening. The effects of chemical composition (effects of Hf content replacing with Ti) on the shape memory properties of NiTiHfPd alloys were also revealed. Orientation dependence of the shape memory properties in aged Ni45.3Ti29.7Hf20Pd5 single crystals were investigated along the [111], [011] and [-117] orientations. The shape memory properties were determined to be strong functions of orientation and aging condition. A perfect superelastic behavior (with no irrecoverable strain) with 4.2 % recoverable compressive strain was obtained in the solutionized condition at stress levels as high as 2.5 GPa while 2 % shape memory strain under a bias stress of 1500 MPa was possible in an aged [111] oriented single crystal. A mechanical hysteresis of 1270 MPa at -30 oC, which is the largest mechanical hysteresis that the authors are aware of in the SMA literature, was observed along the [111] orientation. Finally, thermodynamic analyses were conducted to reveal the relationships between microstructure (e.g. precipitate size and interparticle distances) and martensitic transformations in Ni45.3Ti29.7Hf20Pd5 SMAs. Precipitate characteristics were found to be effective on the elastic energies for nucleation, propagation with dissipation energy and these energies influenced the TTs and the constant stress shape memory properties in Ni45.3Ti29.7Hf20Pd5 alloys.