H. Tobe

NiTiHf-based shape memory alloys

Abstract NiTiHf-based shape memory alloys have been receiving considerable attention for high temperature, high strength and two-way shape memory applications since they could have transformation temperatures above 100°C, shape memory effect under high stress (above 500 MPa) and superelasticity above 100°C. Moreover, their shape memory properties can be tailored by microstructural engineering. However, NiTiHf-based alloys have some drawbacks such as low ductility and high slope in stress induced martensite transformation region. In order to overcome these limitations, studies have been focused on microstructural engineering by aging, alloying and processing. It has been revealed that microstructural control is crucial to govern the shape memory properties (e.g. transformation temperatures, matrix strength, shape recovery strain, twinning type, etc.) of NiTiHf-based alloys. A summary of the most recent improvements on selected NiTiHf-based systems is presented to point out their significant shape memory properties, effects of alloying, aging and microstructure of transforming phases and precipitates.

Effects of Ni content on the shape memory properties and microstructure of Ni-rich NiTi-20Hf alloys

Shape memory properties and microstructure of four Ni-rich NiTiHf alloys (Ni50.3Ti29.7Hf20, Ni50.7Ti29.3Hf20, Ni51.2Ti28.8Hf20, and Ni52Ti28Hf20 (at.%)) were systematically characterized in the furnace cooled condition. H-phase precipitates were formed during furnace cooling in compositions with greater than 50.3Ni and the driving force for nucleation increased with Ni content. Alloy strength increased while recoverable strain decreased with increasing Ni content due to changes in precipitate characteristics. When the precipitates were small (~5–15 nm), they were readily absorbed by martensite plates, which resulted in maximum recoverable strain of 2% in Ni50.7Ti29.3Hf20. With increasing Ni content, the size (>100 nm) and volume fraction of precipitates increased and the growth of martensite plates was constrained between the precipitates when the Ni concentration was greater than 50.7 at.%. Near perfect dimensional stability with negligible irrecoverable strain was observed at stress levels as high as 2 GPa in the Ni52Ti28Hf20 alloy, though the recoverable strain was rather small. In general, strong local stress fields were created at precipitate/matrix interphases, which lead to high stored elastic energy during the martensitic transformation.

Microstructure and shape memory behavior of [111]-oriented NiTiHfPd alloys

The relationship between the microstructure and shape memory properties of [111]-oriented Ni45.3Ti29.7Hf20Pd5 (at%) single crystals was explored. In this precipitation-strengthened alloy, the size and volume fraction of precipitates and interparticle distances govern the martensite morphology and the ensuing shape memory responses. Aging of the solution-treated material, leading to a microstructure of fine, closely spaced precipitates, resulted in a material capable of a shape memory strain of 2.15% at 1000 MPa in compression. Larger precipitates formed after aging the as-grown single crystals (without a prior solution treatment) resulting in a shape memory strain of 2.5% at this same stress level in constant-stress thermal cycling experiments. Superelastic strains of 4% in compression without any residual strain were possible under various microstructural conditions and the stress hysteresis could be varied between nearly 500 and 1000 MPa depending on the microstructure.