PHASE TRANSFORMATIONS IN RAPIDLY SOLIDIFIED TiNi SHAPE MEMORY ALLOYS

ＰＨＡＳＥＴＲＡＮＳＦＯＲＭＡＴＩＯＮＳＩＮＲＡＰＩＤＬＹＳＯＬＩＤＩＦＩＥＤＴｉＮｉＳＨＡＰＥＭＥＭＯＲＹＡＬＬＯＹＳＷａｎｇ；ＳｈｉｄｏｎｇＷｕ；Ｘｉａｏｚｈｅｎ（ＡｎａｌｙｔｉｃａｎｄＴｅｓｔｉｎｇＣｅｎｔｅｒ．ＳｏｕｔｈｅａｓｔＵｎｉｖｅｒｓ...     

Actuator Response of Improved Two-Way Memory TiNi Wires Evaluated by Weight Fraction Diagrams

This paper experimentally studies the improvement in the actuator response of TiNi shape memory wires brought about by thermal treatments. Heat-treated TiNi wires were thermally cycled at zero stress before being trained by constant stress to develop the two-way shape memory effect. Subsequently, the work output of these two-way memory TiNi shape memory alloys are measured during repeated thermomechanical cycling under various levels of constant stress. Changes in the phase transformation behavior in two-way memory and thermomechanically cycled TiNi shape memory alloy wires are quantified by x-ray diffraction as a function of temperature. The weight fraction diagrams of TiNi wires thermally cycled at zero stress before they were trained suggests that during constant stress training they develop a lower quantity of R-phase than samples that have not been thermally cycled at zero stress before being trained. This gives thermally cycled TiNi samples higher levels of transformation strain and work output during thermomechanical cycling than samples that have not been thermally cycled before training. These results suggest that for the best material performance—that is, significant transformation strain and, consequently, substantial work output—the TiNi wire should be thermally cycled at zero stress before training.     

Shape-Memory Intermetallics Development in Taiwan

Ｓｈａｐｅ－ＭｅｍｏｒｙＩｎｔｅｒｍｅｔａｌｌｉｃｓＤｅｖｅｌｏｐｍｅｎｔｉｎＴａｉｗａｎＳ．Ｋ．Ｗｕ（ＩｎｓｔｉｔｕｔｅｏｆＭａｔｅｒｉａｌｓＳｃｉｅｎｃｅａｎｄＥｎｇｉｎｅｅｒｉｎｇ，ＮａｔｉｏｎａｌＴａｉｗａｎＵｎｉｖｅｒｓｉｔｙＴａｉｐｅｉ，...     

Origin of 2-stage R-phase transformation in low-temperature aged Ni-rich Ti–Ni alloys

After aging at intermediate temperatures (400–500 °C), Ni-rich Ti–Ni alloys undergo an abnormal 3-stage martensitic transformation behavior (1-stage R and 2-stage B19′), which stems from a preferential Ti₃Ni₄ precipitation around grain boundary. On the other hand, if aged at low-temperatures (250–300 °C), they undergo 2-stage R-phase transformation, but the origin of this strange phenomenon is unclear. In the present study, we made a systematic study of this phenomenon by considering the grain boundary effect and composition effect. We found that all single crystals undergo 1-stage R-phase transformation; in contrast, the transformation behavior of polycrystals is dependent on Ni content: low-Ni (50.6Ni, 51Ni) polycrystals undergo 2-stage R-phase transformation while high-Ni (52Ni) polycrystals undergo 1-stage R-phase transformation. The abnormal 2-stage R-phase transformation is attributed to a large-scale compositional heterogeneity in B2 matrix between grain boundary region and grain interior, due to the heterogeneity in precipitate density between the grain boundary and grain interior. But for high-Ni polycrystals, precipitates are essentially homogeneously distributed across the whole grain and this leads to normal 1-stage R-phase transformation. The different transformation behavior of low-Ni and high-Ni polycrystals stems from a competition between two opposing tendencies: (1) for preferential precipitation in the grain boundary; (2) for homogeneous precipitation across the whole grain with high-Ni content. The difference between the effect of intermediate-temperature and low-temperature aging lies in the difference in the ability for long-range diffusion of Ni (from the grain interior to the grain boundary), which results in whether or not Ti₃Ni₄ precipitates can form in the grain interior. Our results lead to a unified explanation for different transformation behaviors of both low-temperature and intermediate-temperature aged alloys in terms of the kinetics of precipitation in supersaturated polycrystals.     

Super-Elasticity Characteristics of TiNi Alloy Processed by Equal Channel Angular Extrusion

A Ni-rich TiNi alloy was processed by Equal Channel Angular Extrusion (ECAE) at 500℃. After four passes ECAE treatment, microstructure of the alloy was refined but slightly inhomogeneous, to sub-micron scale, approximately 0.5～0.6 μm. Comparing with the solution-treated TiNi specimen, the martensitic transformations start (Ms) and peak temperatures (Mp) of TiNi specimens processed by ECAE were dramatically lowered. After ECAE treatment, the R-phase transformation was stimulated and separated from martensiti...     

孔隙对NiTi形状记忆合金中B2-R相变影响的相场模拟

建立了适用于含孔隙NiTi合金中B2-R相变的相场模型,并用该相场模型研究了多孔NiTi合金中B2-R转变的微观组织演化过程以及孔隙率和孔尺寸对R相变体生长动力学行为的影响.多孔NiTi合金中R相变体以相互协调的方式形成"带状"的三维结构和"鱼骨"状的二维组织,变体之间形成的孪晶面包括{101}B2和{001}B2 2...     

Ti49.4Ni50.6超弹性弹簧的相变和形变特性

用示差扫描量热仪、拉伸实验和应力-应变循环实验系统研究了退火温度、变形温度以及热循环和室温应力-应变循环对Ti49．4Ni50．6超弹性(SE)弹簧的相变和形变特性的影响。冷加工加中温退火态Ti49．4Ni50．6合金冷却→←加热时的相变类型为母相B2→←R相→←马氏体B19′。随退火温度升高，马氏体转变温度升高，R相转变温度降低。623-773K退火态Ti49．4Ni50．6弹簧室温下可获得SE特性，随变形温度升高，SE弹簧剐度增加；当退火温度超过823K后，SE持性变差。热循环时SE弹簧的切变量取值越小，其应变恢复率越高。预循环训练可增强SE的稳定性。     

A Methodology for the Development, Production, and Validation of R-Phase Actuators

The R-phase transformation has interesting features with potential for applications that need a small temperature hysteresis and good dynamic behavior, such as thermostatic valves. The aim of this article is to show the development, production, and validation process of different R-phase shape memory alloy (SMA) actuators, starting with a semi-finished wire and concluding with a finalized R-phase spring actuator. This study focuses mainly on the calculation, the thermomechanical treatment, and experimental validation of the designed actuators. The first section of this article presents a mathematical dimensioning tool for different R-phase actuators, especially for extension SMA springs. The second part shows specific parameters on the R-phase transformation during thermomechanical treatment. The parameters Ni-content and annealing temperature are being varied to achieve different transformation behavior of the R-phase. The third section relates to the production process of calculated SMA spring actuators based on the R-phase transformation. In the fourth and last section of the article, the performance of selected actuators will be characterized in functional tests, and the results will be compared with the calculated results of the mathematical model.     

In situ TEM observation of two-step martensitic transformation in aged NiTi shape memory alloy

Martensitic transformation was investigated in an aged NiTi alloy with DSC and a temperature controllable TEM specimen stage to observe the influence of Ti₁₁Ni₁₄ precipitates and R-phase on martensitic transformation in situ. The R-phase, conventional martensitic twins, and a new morphology of interwoven austenite/martensitic structure were observed.     

MARTENSITE AND REVERSE TRANSFORMATION IN PRESTRAINED TiNi SHAPE MEMORY ALLOY THIN FILM

The effect of pre-strain on phase transformation of TiNi shape memory alloy film was studied by differential scanning calorimeter measurement (DSC). Compared with un-defarmed TiNi film, the reverse transformation of pre-strained specimens was elevated to a higher temperature on the first heating, but martensite and reverse transformation on subsequent thermal cycles occurred at a lower temperature. The evolution of transformation behavior in pre-strained TiNi film was related to the change of elastic strain energy, irreversible energy and internal stress field.     

A direct method for the crystallography of martensitic transformation and its application to TiNi and AuCd

A simple and straightforward method to obtain a complete set of twining planes and habit planes of martensitic crystals by using the crystallographic data is proposed under the bulk strain energy minimization hypothesis. This method can also be used to obtain the diffraction pattern corresponding to martensitic transformation forming the invariant planes. Applications to the cubic→trigonal and cubic→monoclinic martensitic transformation are presented. The results well explain the morphological differences between R-phase in TiNi and ζ′₂ martensite in AuCd.     

Effect of post-deformation annealing on the R-phase transformation temperatures in NiTi shape memory alloys

In NiTi shape memory alloys, both the annihilation of dislocations and the formation of Ni₄Ti₃ precipitates may occur during post-deformation annealing. Different responses of the R-phase transformation temperatures to the annealing conditions have been reported. In order to find out the main factor(s) affecting the R-phase transformation temperatures during post-deformation annealing, a Ti-49.8 at% Ni and a Ti-50.8 at% Ni alloy were subjected to various post-deformation annealing and thermal cycling treatments. The results show that the R-phase transformation temperatures are very stable in the Ti-49.8 at% Ni alloy, while a significant variation is observed in the Ti-50.8 at% Ni alloy with respect to the annealing and thermal cycling conditions. These findings suggest that the R-phase transformation temperatures are not susceptible to the change of dislocation density and depends mainly on the Ni concentration of the matrix, which can be modified by the formation of Ni₄Ti₃ precipitates.     

R-phase formation in Ti39Ni45Cu16 shape memory thin films and bulk alloys discovered by combinatorial methods

The combinatorial fabrication and high-throughput characterization of a Ti–Ni–Cu shape memory thin film composition spread led to the discovery of the shape memory alloy Ti₃₉Ni₄₅Cu₁₆, which exhibits a single B2 → R-phase transformation above 25 °C with a thermal hysteresis width <1 K. Here we show that the thin film results correctly predict the phase transformation behavior of bulk material upon cooling from the high temperature phase. For both thin film and bulk, a two-step B2 → R-phase → B19′ transformation was found. The B2 → R-phase transformation can be exploited independently, due to a significant temperature separation of the two transformation steps. The shape memory effect in both thin film and bulk samples is limited due to the two-phase microstructure. Transmission electron microscopy investigations revealed the existence of Ti(Ni,Cu)₂ precipitates within the TiNi(Cu) matrix, which are concluded to be responsible for the R-phase formation and separation of the transformation steps.     

Martensite fraction-temperature diagram of TiNi wires embedded in an aluminum matrix

The martensite fraction-temperature diagrams of TiNi wires embedded in a pure aluminum matrix were studied by differential scanning calorimetry (DSC) measurement. Results showed that the initial phase constitution at the deformation temperature affects significantly the transformation behaviors of the constrained TiNi wires. However, for all composites with different phase constitution, the DSC curves are similar in the second and following heating cycles, where only one peak appears on each curve that corresponds to the reverse transformation of the self-accommodating martensite. There is always some amount of preferentially oriented martensite left in the TiNi wire, but its reverse transformation cannot be detected by conventional DSC.     

Texture of TiNi shape memory alloy sheets produced by roll-bonding and solid phase reaction from elementary metals

We have developed a new process to produce Ti–Ni shape memory alloys from titanium and nickel sheets. This process is composed of repetitive roll-bonding for producing a Ti/Ni laminated sheet from them, and of subsequent heat treatment for forming a TiNi intermetallic phase by reactive diffusion. The Ti/Ni laminated sheet changed to a nearly single phase TiNi material through the formation of Ti₂Ni and Ni₃Ti intermediate products. TiNi sheets obtained by this process consisted of a near <111>//ND texture such as {223}<110> in the B2 austenite phase. Recoverable strain associated with martensitic transformation of TiNi was fairly isotropic in the sheet plane due to the relatively isotropic character of {111}<uvw> texture. The formation of such texture through phase transformations by reactive diffusion has been discussed in view of texture inheritance.     

Preparation of multi-walled carbon nanotube-reinforced TiNi matrix composites from elemental powders by spark plasma sintering

Carbon nanotube (CNT)-reinforced TiNi matrix composites were synthesized by spark plasma sintering (SPS) employing elemental powders.The phase structure,morphology and transformation behaviors were studied.It was found that thermoelastic martensitic transformation behaviors could be observed from the samples sintered above 800 ℃ even with a short sintering time (5 min),and the transformation temperatures gradually increased with increasing sintering temperature because of more Ti-rich TiNi phase formation.Although decreasing the sintering temperature and time to 700 ℃ and 5 min could not protect defective MWCNTs from reacting with Ti,still-perfect MWCNTs remained in the specimens sintered at 900 ℃.This method is expected to supply a basis for preparing CNT-reinforced TiNi composites.     

Phase transformation and microstructure of quaternary TiNiHfCu high temperature shape memory alloys

The effect of Cu addition on the phase transformation and microstructure of TiNiHf high temperature shape memory alloy has been studied. The experimental results show that the TiNiHfCu alloy undergoes a B2↔B19′ transformation with a concentration of 3 at.% Cu. And a two-step phase transformation occurs upon heating when the Cu content is 5 at.%. The constitutional phases of TiNiHfCu quaternary alloys are the matrix and (Ti,Hf,Cu)₂Ni particles. The substructure of martensite is mainly (001) compound twin in TiNiHfCu alloys. The martensite variants are (011) type I twin related. The phase transformation temperatures decrease rapidly during the initial several thermal cycles and then keep constant with further increasing of the thermal cycles. It should be noticed that the R-phase transition is separated from the martensitic transformation during the cooling process in the TiNiHfCu alloys. The underlying reasons have been discussed.     

R-phase transformation of aged Ti-Ni shape memory alloy

Ti-50.6Ni（molar fraction, %） shape memory alloy solution treated at 850 ℃ for lh followed by ageing treatment at 450 ℃ for 3 h was studied with differential scanning calorimetry（DSC）, X-ray diffractometry（XRD） and transmission electron microscopy（TEM）. DSC measurement reveals two separate transformation peaks. XRD and TEM demonstrate that a three-stage transformation occurs. The Ti3 Ni4 precipitates are coherent with the R- phase. The crystal structure of R-phase was analyzed by two diffraction patterns method. The diffraction patterns of R-phase were obtained in detail from the same region.     

Ni含量和时效对TiNi形状记忆合金相变热的影响

用示差扫描热分析仪（ＤＳＣ）、光学显微镜、扫描电镜和ＥＤＸ能谱仪系统研究了Ｎｉ含量和时效对ＴｉＮｉ合金Ｒ、马氏体（Ｍ）相变热（Ｑ）的影响。揭示了ＱＭ、ＱＲ与Ｎｉ含量和时效工艺的关系。     

METASTABLE R-PHASE IN Fe-Cr-Mo AND Fe-Cr-W ALLOYS

The precipitation behaviour of Fe-Cr-Mo and Fe-Cr-W alloys during aging has been ex- perimentally studied.It was found that in the early stage of aging,a metastable R phase pre- cipitated in both alloys,it was transformed into stable μ-phase,Laves-phase,X-phase or σ-phase in the later stages.The crystallographic structure of metastable R-phase is rhombohedral with lattice parameters of a=0.9075 nm and α=74.45°.The chemical compo- sition of R-phase is Fe-(27.5—34.9)Mo-(0—25.5)Cr and Fe-(28.9—33.0)W-(9.36— 21.0)Cr in at.-% in Fe-Cr-Mo and Fe-Cr-W system,respectively.