Recent development of TiNi-based shape memory alloys

Recent developments in China on TiNi-based shape memory alloys (SMAs), including TiNi binary SMAs, TiNiNb wide hysteresis SMAs, TiNiCu narrow hysteresis SMAs, TiNiHf high temperature SMAs and TiNiRE SMAs were concisely reviewed. The damping characteristics and corresponding mechanisms of TiNi and TiNiNb alloys were described and discussed. Some surface modifications of TiNi binary alloys were employed to improve the corrosion resistance and the biocompatibility, which are very useful for the medical applications. Shape memory effect and mechanical properties of TiNiHf alloys were enhanced by aging Ni-rich TiNiHf alloys, while the Ms still remain enough high. The authors found that the addition of RE to TiNi alloys increases the phase transformation temperatures and even changes the transformation sequence. Fundamental research on the TiNi-based alloys is still in the ascendant, leading to increasingly extending of the applications.     

Internal friction of Ti–Ni–Cu ternary shape memory alloys

Low frequency internal friction was measured on three specimens of Ti–Ni–Cu ternary alloys, the Cu content varying from 10 to 20 at.%, while Ti content was fixed at 50 at.%. The internal friction spectrum consists mainly of two peaks, a sharper one associated with the B2–B19 transformation and the other one at around 250 K, which is much broader and higher than the former. The peak height of the latter is 0.2 for the specimen containing 20% Cu, which shows that this alloy can be an excellent high damping material. Transformation behavior was studied by electrical resistivity, thermopower and DSC measurements, and was compared with the result of internal friction measurements. Solution treatment at higher temperatures lowers the internal friction peak markedly. Scanning electron microscopy observation reveals that the behaviors of precipitates are different for different solution treatment temperature, suggesting that the precipitation behavior is crucial in the damping properties.     

Martensitic transformation and shape memory properties of Ti-Ta-Sn high temperature shape memory alloys

The effects of Ta and Sn contents on the martensitic transformation temperature, crystal structure and thermal stability of Ti-Ta-Sn alloys are investigated in order to develop novel high temperature shape memory alloys. The martensitic transformation temperature significantly decreases by aging or thermal cycling due to the formation of ω phase in the Ti-Ta binary alloys. The addition of Sn is effective for suppressing the formation of ω phase and improves stability of shape memory effect during thermal cycling. The amount of Sn content necessary for suppressing aging effect increases with decreasing Ta content. High martensitic transformation temperature with good thermal stability can be achieved by adjustment of the Ta and Sn contents. Furthermore, the addition of Sn as a substitute of Ta with keeping the transformation temperature same increases the transformation strain in the Ti-Ta-Sn alloys. A Ti-20Ta-3.5Sn alloy reveals stable shape memory effect with a martensitic transformation start temperature about 440 K and a larger recovery strain when compared with a Ti-Ta binary alloy showing similar martensitic transformation temperature.     

Repeatable temperature memory effect of TiNi shape memory alloys

An incomplete transformation cycle induces a kinetic stop in the following complete transformation cycle in TiNi shape memory alloys. The kinetic stop can be regarded as a memory of the previous interruption temperature. This memory was generally believed to be a one-time phenomenon. Herein, we show that the temperature memory effect is actually a long-lasting phenomenon. Experimental results show that a repeatable temperature memory effect can be introduced into a TiNi alloy by a deformation lager than 12%. Deformation induced dislocations are considered a main factor to the persistence of the memory. The memory becomes more distinct with increasing numbers of the incomplete thermal cycle, but the memory becomes less distinct with increasing numbers of subsequent complete transformation cycling.     

A constitutive model for cyclic actuation of high-temperature shape memory alloys

In this work, a three dimensional constitutive model for High Temperature Shape Memory Alloys (HTSMAs) is presented. To describe the evolution of the cyclic actuation behavior of such alloys, viscoplastic mechanisms and transformation induced plasticity are introduced in addition to the classical transformation behavior of shape memory alloys. Based on continuum thermodynamics, the evolution of phase transformation, plasticity induced transformation, retained martensite and viscoplasticity are described. Deformation mechanisms that occur over the operational range of such HTSMAs have been identified from the thermomechanical behavior of a NiTiPd alloy. The proposed model has therefore been calibrated and validated based on the thermomechanical response of the studied NiTiPd HTSMA alloy during thermal cycles under compression. Careful attention is devoted to the calibration procedure to identify the contribution of the different mechanisms independently. Finite Element Analysis (FEA) is performed to demonstrate the capabilities of the model to describe the cyclic behavior of HTSMA devices.     

Degeneration and rejuvenation of shape memory effect associated with the precipitation of coherent nano-particles in a Co-Ni-Si shape memory alloy

In a solution treated Co-20Ni-6Si shape memory alloy,coherent nano-particles were precipitated after annealing at 873 K for 1 min,but the shape memory effect almost vanished.It is attributed to that the coherent nano-particles not only suppressed the stress-induced face-centered cubic to close-packed hexagonal martensite transformation but also damaged the crystallographic reversibility of reverse martensite transformation.After further annealing at 1073 K for 1 min,the shape memory effect was reju-venated owing to the dissolution of nano-particles.Besides,the recovery strain significantly increased to 5.1％ from the solution treatment of 3.1％ after annealing at 1073 K for 1 min.     

Internal friction behaviour of Ni–Mn–Ga

The internal friction (IF) behaviour of shape memory alloys (SMA) is characterised by an IF peak and a minimum of the elastic modulus during the martensitic transformation (MT), and a higher IF value in the martensitic state than in parent phase. The IF peak is considered to be built of three contributions, the most important of them being the so-called “transient” one, existing only at non-zero temperature rate. On the other hand, the ferromagnetic Ni–Mn–Ga system alloys undergoes a MT from the L2₁ ordered parent phase to martensite, the characteristics of the transformation depending largely on the e/a ratio of the alloys. Indeed, a variety of transformation sequences, including intermediate phases between parent and martensite and intermartensitic transformations, have been observed for a wide set of studied alloys. Furthermore, the IF and modulus behaviour during cooling and heating these alloys show specific characteristics, such as modulus anomalies, strong temperature dependence of the elastic modulus, temperature dependent internal friction in martensite, and, as a general trend, a low transient contribution to the IF. In the present work, the IF and modulus behaviour of several Ni–Mn–Ga alloys will be reviewed and compared to that observed for “classical” systems like Cu- or NiTi-based shape memory alloys.     

Factors affecting recovery stress in Fe-Mn-Si-Cr-Ni-C shape memory alloys

The effects of the heating temperature, the carbon content, the amount of pre-strain, the annealing temperature, and the conventional training on the recovery stresses at room temperature of cold-drawn Fe-Mn-Si-Cr-Ni-C shape memory alloys were studied. The results showed that the addition of carbon or the refining of grains could more significantly enhance the recovery stress than the conventional training. The recovery stress of a cold-drawn Fe-Mn-Si-Cr-Ni alloy with 0.18%C could reach 565 MPa only after annealed at 1023 K. Its recovery stress was only improved to 452 MPa after it was subjected to annealing at conventional temperature 1373 K and then four cycles of the conventional training. The dominating factors affecting the recovery stress were the amount of the plastic deformation and that of the martensitic transformation induced by the recovery stress in cooling, not the recovery strain under no constraints.     

Low frequency damping properties of a NiMnTi shape memory alloy

The present study investigated the low frequency damping properties of a NiMnTi shape memory alloy (SMA) for the first time. The NiMnTi SMA had a high β?θ′ internal friction peak at approximately 125 °C and a low relaxation peak at approximately − 45 °C in the dynamic mechanical analysis cooling tan δ curve. The relaxation peak possessed an activation energy of 0.64 ± 0.03 eV and its damping capacity gradually decreased with the increase of thermal cycling. The NiMnTi SMA also had a good inherent internal friction with tan δ = 0.009 at approximately 140 °C and is a promising high damping alloy for high temperature applications.     

Effect of phase on debond strength in shape memory alloy reinforced composites

Systematic single fiber pullout tests were performed on epoxy composites embedded with nickel titanium shape memory alloy (SMA) wires. The SMA wires were tested in the austenitic or martensitic states to study and decouple the elastic moduli from martensite transformation or reorientation stresses in the analysis of debond loads. The results reveal that the SMA wires that were in the austenite phase consistently produced higher debond loads as compared to that of those wires that started in the martensite phase, likely due to differences in the Poisson’s ratio. Additionally, there appears to be a relationship between the elastic modulus and debond load where reinforcements with a higher elastic modulus displayed lower debond loads. Lastly, for SMA reinforcements that underwent a martensitic phase transformation or reorientation, the debond load was equivalent to the martensite transformation or reorientation load. The results of this work illustrate the sensitivity of SMA reinforced composites on the mechanical behavior and phase transformation characteristics of the constituent materials.     

Comparative study of martensitic transformation behavior of NiAlMn and NiAlMnFe high temperature shape memory alloys

A comparative study of microstructure and martensitic transformation (MT) behavior of Ni₅₉Al₁₁Mn₃₀ and Ni₆₀Al₁₉Mn₁₆Fe₅ high temperature shape memory alloys (SMAs) has been performed by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDXS), optical microscopy, and micro-hardness testing. The MT temperature (MTT) of Ni₅₉Al₁₁Mn₃₀ alloy is higher than that of Ni₆₀Al₁₉Mn₁₆Fe₅ alloy, and both alloys’ MTT increases with increasing annealing temperature. The temperature hysteresis and hardness of Ni₅₉Al₁₁Mn₃₀ alloy are smaller than that of Ni₆₀Al₁₉Mn₁₆Fe₅ alloy. The MT behavior of Ni₆₀Al₁₉Mn₁₆Fe₅ is sensitive to aging temperature and its MTT and hysteresis decrease with increasing aging temperature. However, the MT behavior of Ni₅₉Al₁₁Mn₃₀ alloy is not sensitive to aging temperature. The MT stabilization effects appear in both alloys during thermal cycles. This stabilization effect vanishes from the second thermal cycle. The quenched microstructure of Ni₅₉Al₁₁Mn₃₀ and Ni₆₀Al₁₉Mn₁₆Fe₅ alloys is M plus gamma phase, in which the volume fraction of gamma phase is about 40 and 20%, respectively, and the microhardness of M is higher than that of gamma phase. No aging effects were found in both alloys after aging at 400 °C.     

Deformation physics of shape memory alloys – Fundamentals at atomistic frontier

Application spectrum of shape memory alloys (SMA) is expanding rapidly and proportionately so is the engineering demand for superior materials. An essential prerequisite to developing novel SMAs is a clear perception of the deformation physics underlying their extraordinary shape recoverability. To that end, modern atomistic simulation tools have proffered state-of-the-art models, which usher in new clarifications for SMA deformation properties. It was found, for example, that ab initio energy pathways are at the core of dictating the extent of shear and shuffle for both phase transformation and variant formation at atomic lengthscale. These important revelations are accomplished by addressing inherent solid-state effects, which underpin the natural tendency to seek the energetic ground state. Moreover, empirical potential based models, benefitting from ab initio calculations, have allowed an atomic-resolution view into the phase evolution and the concurrent twinning phenomena relating directly to constitutive properties. Here, we revisit salient examples of these cutting-edge theoretical discoveries regarding SMA deformation along with discussions on pertinent experimental evidences.     

Magnetic structure of the modulated martensite phase in Ni-Mn-Ga ferromagnetic shape memory alloys

The magnetic structure of the seven layered (7 M) modulated martensite phases in Mn-rich Ni-Mn-Ga alloys was studied using Mössbauer spectroscopy. The Mössbauer results clearly demonstrate that in contrast to the non-modulated tetragonal structure two new magnetic sublattices exists for the 7 M orthorhombic martensite phase. Based on the unit cell symmetry and atomic coordination, the additional magnetic sublattices have been assigned to the Ni site. The variation in the magnetic properties of the martensite phases has been related to the underlying magnetic structure.     

Effect of ageing on the reverse martensitic phase transformation behaviors of a CuAlMn shape memory alloy

The effect of ageing on the reverse martensitic phase transformation (MT) behaviors of the Cu-11.9Al-2.5Mn (wt.%) alloy was studied and correlated to the microstructures changes in the present study. It is found that both the temperatures and the heights of the internal friction peaks arising from the reverse MT vary non-monotonously with the ageing temperatures due to the annihilation of quenched-in vacancies during the ageing at relatively low temperatures and the decomposition of β phase during the ageing at relatively high temperatures.     

Microstructure and mechanical behaviors of electron beam welded NiTi shape memory alloys

The vacuum electron beam welding (EBW) technique was employed to weld Ni_50.8Ti_49.2 shape memory alloy sheets, and the microstructure, transformation behaviors and mechanical behaviors of the welding joints were investigated systematically. The microstructure observation showed that the weld seam was composed of coarse columnar crystals at the center and relatively fine columnar crystals near the fusion line. The abnormal high intensity of B2_2 0 0 peak in XRD patterns and preferred orientation in EBSD indicated that the grains in the weld seam have grown preferentially along the 〈1 0 0〉 crystal orientation. Differential scanning calorimetry (DSC) curves exhibited an increase of the martensite start temperature (M_s) of the weld seam, which led to the mixed microstructure of martensite and austenite at room temperature. As a result, the ultimate tensile strength of the welding joint was 85% as high as that of the base metal at room temperature, while it could reach 93% at 223 K when both the weld seam and the base metal were in pure martensitic state.     

Advanced resonant ultrasound spectroscopy for measuring anisotropic elastic constants of thin films

This paper presents an advanced resonant ultrasound spectroscopy (RUS) method to determine the elastic constants C_ij of thin films. Polycrystalline thin films often exhibit elastic anisotropy between the film growth direction and the in‐plane direction, and they macroscopically show five independent elastic constants. Because all of the C_ij of a deposited thin film affect the mechanical resonance frequencies of the film/substrate layer specimen, measuring resonance frequencies enables one to determine the C_ij of the film with known density, dimensions and the C_ij of the substrate. Resonance frequencies have to be measured accurately because of low sensitivity of the C_ij of films to them. We achieved this by a piezoelectric tripod. Mode identification has to be made unambiguously. We made this measuring displacement–amplitude distributions on the resonated specimen surface by laser Doppler interferometry. We applied our technique to copper thin film and diamond thin film. They show elastic anisotropy and the C_ij smaller than bulk values of C_ij. Micromechanics calculations indicate the presence of incohesive bonded regions.     

Shape memory effect in Fe-Mn-Ni-Si-C alloys with low Mn contents

An attempt was made to develop a new Fe-Mn-Si-based shape memory alloy from a Fe-17Mn-6Si-0.3C (mass%) shape memory alloy, which was previously reported to show a superior shape memory effect without any costly training treatment, by lowering its Mn content. The shape memory effect and the phase transformation behavior were investigated for the as-solution treated Fe-(17-2x)Mn-6Si-0.3C-xNi (x = 0, 1, 2, 3, 4) polycrystalline alloys. The shape recovery strain exceeded 2% in the alloys with x = 0-2, which is sufficient for an industrially applicable shape memory effect; however, it suddenly decreased in the alloys between x = 2 and 3 although the significant shape recovery strain still exceeded 1%. In the alloys with x = 3 and 4, X-ray diffraction analysis and transmission electron microscope observation revealed the existence of α′ martensite, which forms at the intersection of the ? martensite plates and suppresses the crystallographic reversibility of the γ austenite to ? martensitic transformation.     

Phase transformation in NiTiHf shape memory alloy thin films

In the present study, amorphous NiTiHf thin films with different compositions were deposited on silicon wafers by using D.C. magnetron sputtering. Crystallization and martensitic transformation characteristics were studied. Crystallization temperatures and activation energy increased with increasing Hf content. The addition of Hf caused larger atomic size mismatch and stronger interactions among constituent elements, thus, increasing the thermal stability of amorphous thin films. With increasing annealing temperature or Hf content, martensitic transformation temperature increased. The results imply that NiTiHf thin films may be used as the potential candidates for high temperature applications in microactuators.