Ni50.6Ti49.4 single and Ni52Ti48 polycrystalline shape memory alloy samples were subjected to aging under a uniaxial stress, to form a single Ni4Ti3 precipitate variant and to investigate the effects of single versus multi-variant coherent precipitates on the shape memory characteristics including two-way shape memory effect (TWSME). Shape memory and superelasticity properties along with the effects of stress and temperature on the transformation temperatures, strain, hysteresis, dimensional stability, and R-phase formation were investigated. This was accomplished through the use of isobaric thermal cycling and superelasticity experiments and various microscopy techniques that included transmission electron microscopy (TEM), scanning electron microscopy, and optical microcopy. The results showed that it is feasible to use constrained aging to bias R-phase martensite variants upon cooling from austenite without any external stress, however, accomplishing this with B19’martensite was much harder as complete TWSME was only found in the Ni50.6Ti49.4 single crystalline sample oriented along the [112] direction. The onset of irrecoverable strain corresponded to the R-phase temperature hysteresis increase in the single crystalline samples regardless of the aging conditions. Through TEM analysis it was discovered that [112] and [114] twins were found in austenite due to plastic deformation of martensite during the superelasticity experiments. Since [112] twins are theoretically impossible to form in austenite, and since martensite was plastically deformed, [112] austenite twins were attributed to the transformation of compound twins in martensite, in particular [113] martensite twins formed during the plastic deformation of martensite, into austenite twins. In the Ni52Ti48 polycrystalline samples, a compressive R-phase variant was biased through constrained aging under 100 and 200 MPa uniaxial tensile stresses at 400°C and 450°C. Aging, in all conditions, produced a high density of Ni4Ti3 precipitates that was most likely responsible for the small transformation strain observed, less that 2%, upon transformation to martensite. In the future, samples with compositions between 50.8 and 51.5 Ni atomic percent, in addition to altered solution and aging heat treatments as compared to those used in this study should be investigated as it is believed that samples with these compositions will yield better and consistent TWSME responses through constrained aging.

TiNiPd high-temperature shape memory alloys (HTSMAs) have attracted considerable attention as potential solid-state actuators capable of operating at temperatures up to 500 °C, exhibiting excellent corrosion resistance, adequate ductility levels and significant strain recovery under both constrained and unconstrained thermomechanical conditions. During operation, these actuators may be subjected to multiple cycles and from an application point of view, the functional stability, i.e. conservation of original actuator dimensions and transformation temperatures during repeated employment, is of considerable importance. This study addresses the issue of functional stability in a model HTSMA, Ti50.5Ni24.5Pd25, for its use as a compact solid-state actuator. Since the primary reason for functional instability is the creation of lattice defects (dislocations, vacancies, etc.) during repeated transformation cycles, several methods were successfully undertaken to improve the functional stability through inhibiting the generation of these defects. Solid-solution strengthening through Sc microalloying and thermomechanical treatments via severe plastic deformation were the two approaches used to strengthen the HTSMA against defect generation. Thermal cycling the HTSMA under stress was the third method to voluntarily introduce defects into the microstructure such that further defect generation during application would be impeded. Overall, severe plastic deformation was found to be more efficient than other strengthening methods in improving the functional stability of TiNiPd HTSMA, yet it brought about disadvantages such as reduction in transformation strain and transformation temperatures. While functional instability is due to the creation of lattice defects, the generation of these defects is mainly controlled by the crystallographic incompatibility between martensitically transforming phases and the strength levels for plastic deformation. It was shown that TiNiPd HTSMAs, which exhibited martensitic transformation from a cubic (B2) to orthorhombic (B19) symmetry, illustrated better compatibility and thus better functional stability levels compared to TiNi SMAs, which had a B2 to monoclinic (B19’) transition. Although crystallographic incompatibility seems to be the governing factor for the functional stability of the TiNiPd HTSMA, the strength differential between the onset of plastic deformation and local constraint due to the martensitic transformation was also found to be an influential factor determining the overall stable behavior. Functional stability was also investigated for the two-way shape memory effect (TWSME) in TiNiPd HTSMAs. Better strength and compatibility levels compared to TiNi SMAs were also reflected in the TWSME characteristics in the form of enhanced stability under stress-free thermal cycling. The stability during constrained thermal cycling was not as good and TWSME degraded rapidly while doing work against an opposing stress. Nevertheless, work output levels were much higher as compared to those obtained from conventional TiNi and Cu-based SMAs.

NiTi is the most commonly used shape memory alloy (SMA) and has been widely used for bio-medical, electrical and mechanical applications. Nickel rich NiTi shape memory alloys are coming into prominence due to their distinct superelasticity and shape memory properties as compared to near equi-atomic NiTi shape memory alloys. Besides, their lower density and higher work output than steels makes these alloys an excellent candidate for aerospace and automotive industry. Shape memory properties and phase transformation behavior of high Ni-rich Ni54Ti46 (at.%) polycrystals and Ni-rich Ni51Ti49 (at.%) single-crystals are determined. Their properties are sensitive to heat treatments that affect the phase transformation behavior of these alloys. Phase transformation properties and microstructure were investigated in aged Ni54Ti46 alloys with differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) to reveal the precipitation characteristics and R-phase formation. It was found that Ni54Ti46 has the ability to exhibit perfect superelasticity under high stress levels (~2 GPa) with 4% total strain after 550°C-3h aging. Stress independent R-phase transformation was found to be responsible for the change in shape memory behavior with stress. The shape memory responses of [001], [011] and [111] oriented Ni51Ti49 single-crystals alloy were reported under compression to reveal the orientation dependence of their shape memory behavior. It has been found that transformation strain, temperatures and hysteresis, Classius-Clapeyron slopes, critical stress for plastic deformation are highly orientation dependent. The effects of precipitation formation and compressive loading at selected temperatures on the two-way shape memory effect (TWSME) properties of a [111]-oriented Ni51Ti49 shape memory alloy were revealed. Additionally, aligned Ni4Ti3 precipitates were formed in a single crystal of Ni51Ti49 alloy by aging under applied compression stress along the [111] direction. Formation of a single family of Ni4Ti3 precipitates were exhibited significant TWSME without any training or deformation. When the homogenized and aged specimens were loaded in martensite, positive TWSME was observed. After loading at high temperature in austenite, the homogenized specimen did not show TWSME while the aged specimen revealed negative TWSME.