Facile Design and Fabrication of Two-Way Shape Memory TiNi Springs with Narrow Hysteresis

In this article, two-way shape memory TiNi springs with narrow hysteresis are fabricated using two-step successive constrained annealing treatments. The as-fabricated springs inherently exhibit two-way shape memory effect (TW-SME) after constrained annealing treatments. The introduction of stable, preferential internal stresses generated by coherent Ti₃Ni₄ phases into the TiNi matrix is indispensable to the TW-SME behavior, which is found to be closely associated with applied strains and the sequence of phase transformations. A simple structural criterion is proposed to ensure the narrow hysteresis. A chart concerning operating temperature points is also plotted as a reference for tracing annealing treatments. The advantages of the springs fabricated by the proposed design consist in its dimensional controllability and long-term cyclability, which are of great importance in the practical application of actuators.     

Microstructures evolution and phase transformation behaviors of Ni-rich TiNi shape memory alloys after equal channel angular extrusion

Ni-rich TiNi shape memory alloys were subjected to the effect of equal channel angular extrusion (ECAE) processes at 773 K by Bc path. The effects of ECAE processes on microstructures evolution and phase transformation behaviors were investigated. The initial 60-80 μm equiaxed coarse grains of samples were elongated along the shearing force direction of ECAE and refined to 300-400 nm after eight passes ECAE. The R phase transformation of Ni-rich TiNi shape memory alloys was stimulated by ECAE processes within a larger temperature range. The martensite transformation peak temperature (Mp) dropped in previous 1-3 ECAE treatments, but the dropped Mp increased gradually with the increase of ECAE processes. Ti₃Ni₄ phase was observed in the regions with high density of dislocations after ECAE treatment. Reasons for microstructures evolution and phase transformation changes were also discussed.     

A Two-Way Shape Memory Study on Ni-Rich NiTi Shape Memory Alloy by Combination of the All-Round Treatment and the R-Phase Transformation

Ni₄Ti₃ precipitates are formed in Ni-rich NiTi shape memory alloys (SMAs) after a certain heat treatment. Such a treatment then results in the changed phase transformation behavior of the alloy switching from the one-step reversible phase change B2 ? B19′ to the two-step, B2 ? R ? B19′, phase change. The present study reports a two-way shape memory (TWSM) due to an all-round treatment followed by an R-phase constraint aging at room temperature. The enhanced TWSM behavior was observed upon temperature cycling between 273 K (R-phase) and 77 K (B19′ phase). The effect of various constraint strains in R-phase aging by employing different diameters of the constraint ring was studied. However, the TWSM effect due to constraining the R-phase will be eliminated after a temperature rise of specimen to the fully parent phase (373 K).     

Microstructural,mechanical and shape memory characterizations of Ti–Mo–Sn alloys

As a β stabilizing element in Ti-based alloys, the effect of Mo on phase constitution, microstructure, mechanical and shape memory properties was investigated. Different compositions of Ti–xMo–3Sn alloys (where x=2, 4, 6, at.%) were prepared by arc melting. A binary composition of Ti–6Mo alloy was also prepared for comparison. Ti–xMo–3Sn alloys show low hardness and high ductility with 90% reduction in thickness while Ti–6Mo alloy shows high hardness, brittle behavior, and poor ductility. Field emission scanning electron microscopy (FESEM) reveals round morphology of athermal ω (ω_ath) precipitates. The presence of ω_ath phase is also confirmed by X-ray diffraction (XRD) in both as-cast and solution-treated and quenched conditions. The optical microscopy (OM) and FESEM show that the amount of martensite forming during quenching decreases with an increase in Mo content, which is also due to β→ω transformation. The hardness trends reinforce the presence of ω_ath too. The shape memory effect (SME) of 9% is the highest for Ti–6Mo–3Sn alloy. The SME is trivial due to ω_ath phase formation; however, the increase in SME is observed with an increase in Mo content, which is due to the reverse transformation from ω_ath and the stress-induced martensitic transformation. In addition, a new and very simple method was designed and used for shape memory effect measurement.     

Age-induced multi-stage transformation in a Ni-rich NiTiHf alloy

Abnormal multi-stage transformations have already been studied in binary Ni-rich NiTi alloys. In this research, this kind of transformation was investigated in a low supersaturated Ni-rich ternary NiTiHf high-temperature shape memory alloy by aging at intermediate temperatures for various durations. Meticulous examinations of the results of differential scanning calorimetry tests demonstrated the heterogeneous precipitation of (Ti,Hf)₃Ni₄ particles and the three-stage transformation (one-stage R and two-stage B19′) in the aged alloy. Aging provided a significant rise in transformation temperatures (TTs) until they reached their equilibrium states, corresponding to the equilibrium Ni content at each aging temperature. Equilibrium TTs were higher when aging was performed at a lower temperature. The remarkable increase in TTs was compared with those in aged Ni-rich NiTi alloys, and discussed based on the variation in valence electron concentration. A model was also proposed for the microstructural evolution during aging. Furthermore, aging provided enhanced hardness and strain recovery for the alloy. In particular, aging at a lower temperature resulted in a considerable improvement in hardness and shape recovery, which was discussed based on the microstructural changes in the aged alloy. Equilibrium Ni content at each aging temperature proved to be a crucial parameter in controlling the alloy properties, even in heterogeneous precipitations.     

Effect of Annealing Temperature on the Shape Memory Properties of Cold-Rolled Dual-Phase Ni-Mn-Ga-Gd Alloy

The influence of annealing temperature on the shape memory effect (SME) and recovery ratio of cold-rolled dual-phase Ni₅₈Mn₂₅Ga_16.9Gd_0.1 high-temperature shape memory alloy were investigated. The results showed that the SME can be improved by appropriate annealing. SME of 6.0% and recovery ratio of 98% were observed in the rolled alloy at 550 °C annealing, which were larger than that of the samples annealed at other temperatures. The annealing temperature was in between the recrystallization temperatures of the martensite and γ phase, which leads to the work-hardening state of γ phase kept unchanged during annealing process, and therefore, the critical slip stress of γ phase increased. Thus, the plastic deformation of γ phase reduced during the compression process, and the SME increased.     

Effects of equal channel angular extrusion and aging treatment on R phase transformation behaviors and Ti3Ni4 precipitates of Ni-rich TiNi alloys

Ni-rich TiNi alloys were subjected to the effect of multiple equal channel angular extrusion (ECAE) treatments by B_C path at 500 °C. The characteristics of R phase transformation in aging treatment were dissimilar in the appearance and the temperature range to those counterparts induced by ECAE treatments. The fine lens-like shape Ti₃Ni₄ particles precipitated mainly in the regions of near grain boundaries and on the tangled grain boundaries after ECAE treatments. The effects and mechanisms of aging treatments and ECAE treatments on R phase transformation behaviors and Ti₃Ni₄ precipitates were investigated and discussed.     

Thermal and transport properties of as-grown Ni-rich TiNi shape memory alloys

Electrical resistivity, Seebeck coefficient, specific heat and thermal conductivity measurements on the Ti_50−xNi_50+x (x = 0.0–1.6 at.%) shape memory alloys are performed to investigate their thermal and transport properties. In this study, anomalous features are observed in both cooling and heating cycles in all measured physical properties of the slightly Ni-rich TiNi alloys (x ≤ 1.0), corresponds to the transformation between the B19′ martensite and B2 austenite phases. Besides, the transition temperature is found to decrease gradually with increasing Ni content, and the driving force for the transition is also found to diminish slowly with the addition of excess Ni, as revealed by specific heat measurements. While the signature of martensitic transformation vanishes for the Ni-rich TiNi alloys with x ≥ 1.3, the characteristics of strain glass transition start to appear. The Seebeck coefficients of these TiNi alloys were found to be positive, suggesting the hole-type carriers dominate the thermoelectric transport. From the high-temperature Seebeck coefficients, the estimated value of Fermi energy ranges from ∼1.5 eV (Ti_48.4Ni_51.6) to ∼2.1 eV (Ti₅₀Ni₅₀), indicating the metallic nature of these alloys. In addition, the thermal conductivity of the slightly Ni-rich TiNi alloys with x ≤ 1.0 shows a distinct anomalous feature at the B19′ → B2 transition, likely due to the variation in lattice thermal conductivity.     

Effect of precipitation on the shape memory effect of Ti50Ni25Cu25 melt-spun ribbon

The present research aims to provide accurate understanding of the relation between precipitation (volume fraction, morphology, type) and shape memory effect of Ti₅₀Ni₂₅Cu₂₅ melt-spun ribbon. Rapid thermal annealing was used to control the microstructural development while the shape memory effect of the ribbon was determined under constraint thermal cycling. The results show that the precipitation process takes the following sequence: B11 TiCu → B11 TiCu + Ti₂(Ni, Cu) → Ti₂(Ni, Cu) with increasing annealing temperature or duration. The shape memory effect is found to depend on both the volume fraction and the distribution of the precipitates. The former affects the shape recovery strain through reduction of the transformation volume participating the shape recovery. The latter affects the shape recovery strain through strengthening the matrix thus reducing the martensite strain which is more predominant under low constraint stresses. Precipitation strengthening, on the other hand, reduces the tendency of dislocation generation/movement, thus reducing the irreversible strain and improving shape recovery strain. This understanding provides guidelines on the optimization of the shape memory properties of the Ti₅₀Ni₂₅Cu₂₅ melt-spun ribbon via post-processing annealing.     

铁基形状记忆合金（续完）

简介形状记忆效应(SME)的基本概念和形状记忆合金的发展。评述了Fe-Mn-Si,Fe-Mn-Si-Cr-Ni,Fe-Ni-Co-Ti和Fe-Ni-C等系铁基形状记忆合金的生长背景,特性及其SME的机制。     

Reproducibility Study of NiTi Parts Made by Metal Injection Molding

Powder metallurgy (P/M) is an attractive manufacturing process for net-shaped NiTi parts considering the limited machinability of NiTi alloys. Nevertheless, the industrial implementation of P/M processing for NiTi alloys is not trivial. To become competitive to manufacturing of NiTi alloys based on established ingot metallurgy, combination of fully pronounced shape memory behavior with sufficient mechanical properties is required. Successful use of P/M technology is strongly influenced by high affinity of NiTi alloys for uptake of oxygen and carbon, which leads to the formation of oxygen-containing Ti₂Ni and TiC phases coupled with increase of Ni content in the matrix. In the case of Ni-rich NiTi alloys, this increase leads to a shift of phase transformation temperatures to lower values. Furthermore, precipitation of Ni₄Ti₃ during cooling from sintering temperature is difficult to avoid. Even if these precipitates might be used to decrease the Ni:Ti ratio of the matrix balancing oxygen and carbon uptake, significant loss of ductility arises, especially in the case of finely dispersed Ni₄Ti₃ precipitates. In the present work, each step of P/M manufacturing is discussed regarding its influence on the specific properties of NiTi alloys. The work is based on the application of prealloyed, gas atomized NiTi powders. Metal injection molding was used for net-shaped manufacturing of tensile samples, which enabled detailed study of sintering behavior combined with investigation of shape memory and mechanical properties depending on particle size, oxygen and carbon content as well as precipitation of Ni₄Ti₃ phase.     

Co对Ti-Ni形状记忆合金相变和形变特性的影响

用热重分析仪、X射线衍射仪、示差扫描量热仪及拉伸试验研究了Co对Ti-49.8Ni(at%,下同)形状记忆合金相变和形变特性的影响。结果表明,中温退火态Ti-49.8Ni合金冷却/加热时的相变类型为A→R→M/M→A(A—母相,R—R相,M—马氏体相);随退火温度升高,该合金的马氏体相变温度升高,R相变温度先升高后降低;该合金室温相组成为马氏体,具有形状记忆效应(SME)。用1%Co置换等量Ti后所得Ti-49.8Ni-1Co合金冷却/加热时的相变类型为A→R→M/M→R→A,相变温度低,室温组成相为母相A,具有超弹性(SE)特性。退火温度低于600℃时,Ti-Ni基合金的SME和SE特性良好,退火温度超过600℃后,合金氧化加剧,SME和SE特性变差,塑性显著提高。     

铁基形状记忆合金（待续）

简介形状记忆效应(SME)的基本概念和形状记忆合金的发展。评述了Fe-Mn-Si,Fe-Mn-Si-Cr-Ni,Fe-Ni-Co-Ti和Fe-Ni-C等系铁基形状记忆合金的生长背景,特性及其SME的机制。     

Effects of nanoprecipitation on the shape memory and material properties of an Ni-rich NiTiHf high temperature shape memory alloy

Shape memory properties of a Ni_50.3Ti_29.7Hf₂₀ (at.%) polycrystalline alloy were characterized after selected heat treatments. The effects of heat treatment temperature and time on the transformation temperatures (TTs) and temperature hysteresis were determined by differential scanning calorimetry. Thermal cycling under constant compressive stress was carried out to reveal the changes in transformation strain, temperature hysteresis, and TT as a function of stress. Isothermal stress cycling experiments were conducted to reveal the critical stresses, transformation strain, and stress hysteresis as a function of temperature. The crystal structure and lattice parameters of the transforming phases were determined by X-ray diffraction at selected temperatures. Precipitate characteristics and martensite morphology were revealed by transmission electron microscopy. Precipitation was found to alter the martensite morphology and significantly improve the shape memory properties of the Ni-rich NiTiHf alloy. For the peak aged condition shape memory strains of up to 3.6%, the lowest hysteresis, and a fully reversible superelastic response were observed at temperatures up to 240 °C. In general, the nickel-rich NiTiHf polycrystalline alloy exhibited a higher work output (≈16.5 J cm^?3) than other NiTi-based high temperature alloys.     

The combustion synthesis of Ni-Ti shape memory alloys

Combustion synthesis is a new and promising method of producing Ni-Ti series shape memory alloys. It has the advantage of both time and energy savings compared with the conventional melting or powder metallurgy approaches. The value of the ratio ΔH°_?,298/ C_p,298 plays a key role in this method, especially if a liquid product is required. Solidified products made by the combustion synthesis process were hot rolled into plates exhibiting the shape memory effect. It was discovered that shape memory transition temperatures can be tailored over a wide temperature range (from ?78 to 460°C) by substituting a third element, such as palladium or iron, for nickel. This approach should greatly extend the application of such alloys.     

Transformation behaviors of Ti48.5Ni48Fe2Nb1.5 dependence of annealing and thermomechanical cycling

The effect of annealing treatments and thermomechanical cycling on the transformation behaviors and shape memory effect of Ti48.5Ni48Fe2Nb1.5 shape memory alloys were investigated using electrical resistivity measurement and tensile testing. It is found that the transformation behaviors are influenced considerably by the annealing treatments. Both Ms and As increase with increasing annealing temperature and cooling rate. Martensite stabilization occurs during thermomechanical cycles, thus resulting in lower...     

Factors Influencing the Reversion of Stress-induced Martensite to Austenite in a Fe-Mn-Si-Cr-Ni Shape Memory Alloy

It is well known that one way shape memory effect (SME) in Fe-Mn-Si-based shape memory alloys (SMAs) is related to the thermally induced reversion of ε (hexagonal close packed, hcp) stress-induced martensite (SIM) to γ (face centered cubic, fcc) austenite. In the case of a Fe-Mn-Si-Cr-Ni SMA, this reverse martensitic transformation was analyzed in regard to the critical temperature for the beginning of austenite formation (A _s) in different states characterized by quenching temperature and permanent tensile strain. For this purpose, dynamic mechanical analysis (DMA), dilatometry (DIL), differential thermal analysis (DSC), and optical microscopy (OM) were employed to determine the influence of quenching temperature and permanent tensile straining on SIM reversion to austenite during heating.     

热诱发ε马氏体量对Co-30Ni合金形状记忆效应的影响

为了明确具有ε马氏体转变的Co-Ni基合金形状记忆效应的来源,通过控制不同变形温度,在Co-30Ni合金中获得不同数量的热诱发ε马氏体,在此基础上利用OM和XRD研究了变形时预先存在的热诱发ε马氏体的演化及其对应力诱发ε马氏体转变的影响,并采用弯曲法表征了合金的形状记忆效应。结果表明:合金的形状记忆效应都随热诱发和应力诱发ε马氏体数量的增加而升高,但原位金相未观察到热诱发ε马氏体在应力下的长大合并。Co-Ni基合金的形状记忆效应来源于应力诱发ε马氏体转变,而不是热诱发ε马氏体在应力下的长大合并。低的母相屈服强度是Co-Ni合金形状记忆效应差的原因。预先形成的热诱发ε马氏体能提高母相的屈服强度,因而有利于形状记忆效应的提高。     

Role of thermal martensite in shape memory effect of CoAl and CoNi alloys

To address the role of the HCP martensite in CoAl and CoNi shape memory alloys, the relationship between the shape memory effect (SME) and the content of the thermal and stress-induced HCP martensite was investigated in the solution-treated CoAl and CoNi alloys. In-situ optical observations were employed to investigate the contents of thermal HCP martensite before and after deep cooling and its influence on the stress-induced HCP martensite transformation and SME. The results show that the SME in both the CoAl and the CoNi alloys results from the stress-induced HCP martensite. The role of the thermal HCP martensite in both of them is the strengthening of the matrix. The much higher yield strength in the solution-treated CoAl alloy due to solution strengthening of Al is responsible for its better SME compared with the CoNi alloy.     

Functionally-graded shape memory alloy by diffusion annealing of palladium-coated NiTi plates

Diffusion annealing of palladium-coated Ti-Ni plates was performed at temperatures ranging from 900 °C to 1,000 °C, to accomplish a compositional gradient in Ti-rich, Ti-Ni shape memory alloys. The aim of this study was to increase the transformation temperatures and transformation temperature intervals. Palladium diffusion profiles were measured by energy dispersive spectroscopy, and the corresponding approximate diffusion coefficients of the annealed specimens were calculated. The Gaussian solution of Fick’s second law for the one-dimensional lattice diffusion of a tracer was used. The transformation behavior studies were performed by differential scanning calorimetry. It was depicted that annealed specimens show longer transformation intervals compared to the bare alloy. In addition, annealed specimens showed improved shape memory properties that were attributed to the lower amount of Ti₂Ni precipitates in the diffusion layer. The shape memory behaviour of the samples was detected using micro-indentation at room temperature, followed by heating them above the austenite formation temperature to calculate the shape recovery ratio.