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.

Shape memory alloys (SMAs) are an important class of smart materials that have the ability to remember a shape. Current practical uses of SMAs are limited to below 100 degrees C which is the limit for the transformation temperatures of most commercially successful SMAs such as NiTi and Cu-based alloys. In recent years, the CoNiGa system has emerged as a new ferromagnetic shape memory alloy with some compositions exhibiting high martensitic transformation temperatures which makes CoNiGa a potential high temperature shape memory alloy (HTSMA). In this study, the microstructural evolution and martensitic transformation characteristics of CoNiGa (mainly Co46Ni27Ga27 and Co44Ni26Ga30 in at.percent) HTSMAs were investigated in as-cast and hot-rolled conditions as a function of different heat treatments. Heat treatment conditions were selected to introduce single, two, and three phase structures, where two precipitate phases (ductile Y and hard Y') do not martensitically transform. Calorimetry, X-ray analysis, scanning and transmission electron microscopy, thermo-mechanical process and cycling techniques are applied to understand the structural and chemical factors influencing the thermal stability and transformation characteristics. The main findings include improvement of ductility, most cyclically stable compositions with narrow transformation hysteresis (<40 degrees C) and transformation temperatures in the range of 100 degrees C to 250 degrees C, formation of new phases and their effects, and associated compositional changes in the matrix, on the transformation temperatures and on the microstructural evolution. In addition, Ms temperature depends linearly on the valence electron concentration (e/a) of the matrix, only if the Ga content is constant, and the samples with narrow transformation hysteresis demonstrate reversible martensitic transformation in constant-stress thermal cycling experiments.

Shape memory alloys (SMAs) represent a revolutionary class of active materials that can spontaneously generate strain based on an environmental input, such as temperature or stress. SMAs can provide potential solutions to many of today's engineering problems due to their compact form, high energy densities, and multifunctional capabilities. While many applications in the biomedical, aerospace, automotive, and defense industries have already been investigated and realized for nickel-titanium (NiTi) based SMAs, the effects of controlling and designing the microstructure through processing (i.e. extreme cold working) have not been well understood. Current Ni-Ti based SMAs could be improved upon by increasing their work output, improving dimensional stability, preventing accidental actuation, and reducing strain localization. Additionally, there is a strong need to increase the transformation temperature above 115 °C, the current limit for NiTi and is especially important for aerospace applications. Previous research has shown that the addition on ternary elements such as Au, Hf, Pd, Pt, and Zr to NiTi can greatly increase these transformation temperatures. However, there are several limiting factors with these ternary additions such as increased cost, especially with Au, Pd, and Pt, as well as, difficulty in conventionally processing these alloys. Therefore, the main objectives of this research is to study how processing can alter the mechanical properties of NiTi and characterizing it using in situ synchrotron radiation x-ray diffraction (SR-XRD), understanding how we can process ternary SMAs (NiTiHf) by conventional means, and lastly how this processing alters precipitation characteristics and mechanical properties of these alloy systems.

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.

No description available.

NiTiHf shape memory alloys have been receiving considerable attention for high temperature and high strength applications since they could have transformation temperatures above 100 °C, shape memory effect under high stress (above 500 MPa) and superelasticity at high temperatures. Moreover, their shape memory properties can be tailored by microstructural engineering. However, NiTiHf alloys have some drawbacks such as low ductility and high work hardening in stress induced martensite transformation region. In order to overcome these limitations, studies have been focused on microstructural engineering by aging, alloying and processing. 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. The effects of the heat treatments on the transformation characteristics and microstructure of the Ni-rich NiTiHf shape memory alloys have been investigated. Transformation temperatures are found to be highly annealing temperature dependent. Generation of nanosize precipitates (~20 nm in size) after three hours aging at 450 °C and 550 °C improved the strength of the material, resulting in a near perfect dimensional stability under high stress levels (> 1500 MPa) with a work output of 20–30 J cm– 3. Superelastic behavior with 4% recoverable strain was demonstrated at low and high temperatures where stress could reach to a maximum value of more than 2 GPa after three hours aging at 450 and 550 °C for alloys with Ni great than 50.3 at. %. Shape memory properties of polycrystalline Ni50.3Ti29.7Hf20 alloys were studied via thermal cycling under stress and isothermal stress cycling experiments in tension. Recoverable strain of ~5% was observed for the as-extruded samples while it was decreased to ~4% after aging due to the formation of precipitates. The aged alloys demonstrated near perfect shape memory effect under high tensile stress level of 700 MPa and perfect superelasticity at high temperatures up to 230 °C. Finally, the tensioncompression asymmetry observed in NiTiHf where recoverable tensile strain was higher than compressive strain. The shape memory properties of solutionized and aged Ni-rich Ni50.3Ti29.7Hf20 single crystals were investigated along the [001], [011], and [111] orientations in compression. [001]-oriented single crystals showed high dimensional stability under stress levels as high as 1500 MPa in both the solutionized and aged conditions, but with transformation strains of less than 2%. Perfect superelasticity with recoverable strain of more than 4% was observed for solutionized and 550 °C-3h aged single crystals along the [011] and [111] orientations, and general superelastic behavior was observed over a wide temperature range. The calculated transformation strains were higher than the experimentally observed strains since the calculated strains could not capture the formation of martensite plates with (001) compound twins.

No description available.

Shape memory alloys (SMAs) exhibit unique combination of structural and functional properties and hence have a variety of current and potential applications. The mechanical behaviour of SMAs, in particular the influence of processing on the microstructure, which in turn influences the performance of the alloy, mechanical properties at the nano-scale, and under cyclic loading conditions, are of great current interest. In this thesis, specific issues within each of these broad areas are examined with a view to suggest further optimize/characterize SMAs. They are the following: (a) For thermo-mechanical secondary processing of SMAs, can we identify the optimum combination of temperature- strain rate window that yields a desirable microstructure? (b) How can indentation be used to obtain information about functional properties of shape memory alloys so as to complement traditional methods? (c) How can the information obtained from indentation be utilized for the identification of the alloy composition that yields a high temperature SMA through the combinatorial diffusion couple approach? Towards achieving the first objective, we study the hot deformation behavior of a cast NiTi alloy with a view of controlling the final microstructure. The “processing maps” approach is used to identify the optimum combination of temperature and strain rate for the thermomechanical processing of a SMA system commonly used in actuators applications (NiTiCu). Uniaxial compressions experiments are conducted in the temperature range of 800- 1050 °C and at strain rate range of 10-3 and 102 s-1. 2-D power dissipation efficiency and instability maps are generated and various deformation mechanisms, which operate in different temperature–strain rate regimes, are identified with the aid of these maps. Complementary microstructural analysis of specimens (post deformation) is performed with the help of electron backscattered diffraction (EBSD) analysis to arrive at a processing route which produces stress free grains. A safe window suitable for industrial processing of this alloy which leads to grain refinement and strain-free grains (as calculated by various methods of misorientation analysis representation) is suggested. Regions of the instability (characterized by the same analysis) result in strained microstructure, which in turn can affect the performance of the SMA in a detrimental manner. Next, to extract useful information from indentation responses, microindentation experiments at a range of temperatures (as the shape memory transformation is in progress) are conducted underneath the Vickers indenter. SME was observed to cause a change in the calculated recovery ratios at temperatures above As. Spherical indentation of austenite and martensite show different characteristics in elastic and elasto- plastic regimes but are similar in the plastic regime. NanoECR experiments are also conducted under a spheroconical indenter at room temperature, where the resistance measured is observed to increase during the unloading of room temperature austenite SMA. This is a signature of the reverse transformation back to austenite during the withdrawal of the indenter. Lastly, recovery ratios are monitored in the case of a NiTiPd diffusion couple before and after heat treatment at different temperature intervals using non- contact optical profilometry. The recovery ratio approach is successfully used to determine the useful temperature and %Pd range for a potential NiTiPd high temperature SMA. The method makes high throughput identification of high temperature shape memory alloys possible due to promising alloy compositions being identified at an early stage.