镍钛形状记忆合金的开发应用

综述了镍钛形状记忆合金在国内外的开发应用情况。对今后的发展提出了建议。     

浅析NiTi形状记忆合金的疲劳机理

由于NiTi形状记忆合金具有可逆的热弹性马氏体相变效应等不同与一般金属的特性，使得其疲劳机理也不同于一般的工程材料。为此，本文侧重分析了温度变化对NiTi形状记忆合金疲劳机理的影响和应力诱发马氏体相变等特征相变过程，以及相关的研究方法与主要结果，将为进一步研究其疲劳过程及增韧工艺提供理论参考依据．     

NiTi形状记忆合金超弹性的研究现状

综述了NiTi形状记忆合金在有关超弹性性能方面的基础研究、应用研究、力学行为、磨损性能以及数学建模等问题。     

Mechanical Properties of TiTaHfNbZr High-Entropy Alloy Coatings Deposited on NiTi Shape Memory Alloy Substrates

TiTaHfNbZr high-entropy alloy (HEA) thin films with thicknesses of about 750 and 1500 nm were deposited on NiTi substrates by RF magnetron sputtering using TiTaHfNbZr equimolar targets. The thorough experimental analysis on microstructure and mechanical properties of deposited films revealed that the TiTaHfNbZr films exhibited amorphous and cauliflower-like structure, where grain size and surface roughness increased concomitant with film thickness. More importantly, the current findings demonstrate that the TiTaHfNbZr HEA films with mechanical properties of the same order as those of the NiTi substrate constitute promising biomedical coatings effective in preventing Ni release.     

Nanostructured NiTi Shape Memory Alloy Via Ni/Ti Nanolamination

Ultrafine grained NiTi shape memory alloy was consolidated from Ni/Ti laminates via accumulative roll bonding (ARB) followed by hot isostatic pressing (HIP). Due to the extensive plastic deformation arising from ARB and the attainment of ultra-thin layers of both Ti and Ni laminates, the subsequent HIP processing time was significantly reduced. Differential scanning calorimetry (DSC) analysis confirms that the shape memory effect was obtained in the consolidated NiTi alloy.     

Ti-Ni-Ce合金的相变行为及其形状记忆效应

通过示差扫描量热仪(DSC)等试验手段,系统分析了添加稀土元素Ce后所形成的Ti-Ni-Cex(x＝2 at%、3 at%、4 at%)系合金的相变行为和形状记忆效应,以及相变温度和相变潜热与稀土含量之间的关系.研究结果表明,相变温度(Ms,Mf,As,Af)受稀土含量的影响较大,总的趋势是先升高后下降,然后有稍微升高;而对相变潜热(马氏体相变潜热ΔHB2M、逆马氏体相变潜热ΔHMB2)的影响,则是随着稀土元素Ce含量的升高呈现上升的趋势;稀土的添加使Ti-Ni二元合金的相变滞后明显变窄,但与稀土的含量没有明显关系.研究发现,添加稀土后Ti-Ni形状记忆合金优良的形状记忆效应没有改变,而相变温度却有明显的提高.     

Effect of Thermomechanical Treatment on Functional Properties of Biodegradable Fe-30Mn-5Si Shape Memory Alloy

The structure, martensitic γ ↔ ε transformation temperatures, Young’s modulus, mechanical properties, and electrochemical behavior of Fe-30Mn-5Si (wt pct) biodegradable shape memory alloy subjected to various thermomechanical treatments (TMT) comprising hot rolling or cold rolling with post-deformation annealing were characterized by optical microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, differential scanning calorimetry, tensile testing, open circuit potential, and polarization curves measurements in Hanks’ solution, as compared to reference heat treatment. The optimum combination of mechanical properties (low Young’s modulus, high tensile strength, and appropriate ductility) for biomechanical compatibility was obtained after TMT with hot rolling at 600 and 800 °C due to the formation of favorable dynamically polygonized and recrystallized structures and decrease in the γ↔ε transformation starting temperature down to the human body temperature. The TMT did not show a significant effect on the corrosion rate as compared to the appropriate corrosion rate after the reference heat treatment. It is concluded that the TMT with hot rolling at 600 or 800 °C, which provides an optimum combination of the required corrosion rate in the simulation body fluid with high biomechanical compatibility, can be considered a promising treatment of Fe-30Mn-5Si biodegradable alloy for bone implants.

     

镍钛形状记忆合金薄膜的相变温度和力学性能

利用直流磁控溅射法溅射沉积了NiTi形状记忆合金薄膜，对NiTi形状记忆合金薄膜进行晶化热处理以使其获得形状记忆效应。研究了550℃晶化热处理1h后Ti-48.2%Ni薄膜的相变温度和力学性能，研究结果表明，NiTi薄膜550℃晶化热处理1h后，升温过程中发生M→A的相变，而降温过程中则先发生A→R相变，再发生R→M的相变，薄膜的断裂强度随测试温度的升高而增大，残余应变随温度的升高而减小，当温度大于Af点时，表现为超弹性。     

Cu-Zn合金的形状记忆效应

通过扭转法和电阻测量法对Cu-Zn合金的形状记忆效应进行了实验研究。发现在M_s点以上,不存在热弹性马氏体的情况下,由应力诱发马氏体可以引起形状记忆效应。另外,在M_s点以下有热弹性马氏体的情况下,根据实验结果可以证明,应力诱发马氏体在形状记忆效应中仍然起主要作用。     

High Strain Rate Compression of Martensitic NiTi Shape Memory Alloy at Different Temperatures

The compressive response of martensitic NiTi shape memory alloy (SMA) rods has been investigated using a modified Kolsky compression bar at various strain rates (400, 800, and 1200 s^?1) and temperatures [room temperature and 373 K (100 °C)], i.e., in the martensitic state and in the austenitic state. SEM, DSC, and XRD were performed on NiTi SMA rod samples after high strain rate compression in order to reveal the influence of strain rate and temperature on the microstructural evolution, phase transformation, and crystal structure. It is found that at room temperature, the critical stress increases slightly as strain rate increases, whereas the strain-hardening rate decreases. However, the critical stress under high strain rate compression at 373 K (100 °C) increase first and then decrease due to competing strain hardening and thermal softening effects. After high rate compression, the microstructure of both martensitic and austenitic NiTi SMAs changes as a function of increasing strain rate, while the phase transformation after deformation is independent of the strain rate at room temperature and 373 K (100 °C). The preferred crystal plane of the martensitic NiTi SMA changes from (\( 1\bar{1}1 \))_M before compression to (111)_M after compression, while the preferred plane remains the same for austenitic NiTi SMA before and after compression. Additionally, dynamic recovery and recrystallization are also observed to occur after deformation of the austenitic NiTi SMA at 373 K (100 °C). The findings presented here extend the basic understanding of the deformation behavior of NiTi SMAs and its relation to microstructure, phase transformation, and crystal structure, especially at high strain rates.     

Texture Development in the Ni47Ti44Nb9 Shape Memory Alloy During Successive Thermomechanical Processing and Its Effect on Shape Memory and Mechanical Properties

For improving the shape memory performance and mechanical properties of shape memory alloys (SMAs), crystallographic texture and second phase are generally induced in SMAs by suitable thermomechanical processing. For this purpose, the development of texture in the Ni₄₇Ti₄₄Nb₉ SMA during successive processing (e.g., hot forging, hot rolling, cold rolling, and heat treatment) and the effects of texture, grain size, and β-Nb particle precipitation on recoverable strains and tensile properties were studied. In the hot-forged and hot-rolled Ni₄₇Ti₄₄Nb₉ alloy rods, intense 〈111〉 fibers are formed, and water quenching from 873 K and 1123 K (600 °C and 850 °C) leads to the decrease in intensity of 〈111〉 fiber in the hot-rolled rod. When the hot-forged rod is hot-rolled into sheet, intense {001} and weak {123} fibers appear, but grain growth leads to the disappearance of {001} fiber and {110}〈001〉 becomes the strongest component. Cold-rolling deformation of the hot-rolled sheet promotes the development of γ-fiber and the convergence of {332} and {123} fibers to {233}〈110〉 and {123}〈121〉 components, respectively, and the intense component is turned into {111}〈110〉; in this case, the recoverable strain (ε _SRS) and tensile yield strength (σ _YS ) exhibit an anisotropy. When the quenching temperature is 1123 K (850 °C), some weaker components appear, the anisotropy of ε _SRS disappears, and the difference level in σ _YS along the rolling direction (RD) and transverse direction (TD) becomes smaller. Therefore, an appropriate heat-treatment temperature should be selected to maintain the deformation texture and also to obtain fine grains for different thermomechanical processing.     

Influence of Composition and Thermomechanical Training Process on the Transformation Behavior and Shape Memory Properties of NiTi Based Alloys

The effects of composition, specially the Cu element and thermomechanical training process on the transformation and one way shape memory behavior (OWSM) of NiTi based alloys were investigated using differential scanning calorimetry and microstructural analysis. The hot rolled strips with different compositions were trained under various applied pre-strains by bending test at martensitic state. It was found that the presence of Cu in the NiTi alloy results in an improvement of the OWSM effect by reducing the transformation hysteresis and forming the longer martensitic variants with lower interfacial energy than the NiTi binary alloys. Increasing the applied pre-strain and the number of thermomechanical training cycles caused OWSM effect to decrease. Although the transformation temperature increased at the higher applied pre-strain, it was reduced during the thermomechanical training process.     

淬火温度对Fe-Mn-Si-C合金形状记忆性能的影响

研究淬火温度对Fe-Mn—Si—C合金的形状记忆性能的影响，发现在700℃淬火可以获得最佳的形状记忆性能。通过对合金光学显微组织、透射电镜组织的观察并结合奥氏体晶粒尺寸、形状回复率、层错几率等性能的测量，系统地讨论了不同淬火温度下，热诱发马氏体数量、Ms点、空位浓度、层错能等对形状记忆性能的综合影响，进一步探讨淬火温度对形状记忆性能影响的微观机制。     

镍钛形状记忆合金线材无模拉拔成形过程的电磁场和温度场模拟

无模拉拔成形过程的电磁场和温度场数值模拟对于正确制定加工工艺,精确控制线材质量十分重要。利用ANSYS有限元软件,对镍钛形状记忆合金线材无模拉拔成形过程的电磁场和温度场进行了数值模拟,获得了镍钛形状记忆合金线材无模拉拔成形时的电磁场和温度场信息,并进行了讨论。提出了较合理的镍钛形状记忆合金线材无模拉拔成形工艺参数范围:电流频率59~61 kHz、电流密度(2.95~3.05)×107A.m-2、冷却水与感应加热线圈之间的距离19~22 mm、冷却水流量22~26 ml.s-1。     

Seismic Response Control of Building Structures with Superelastic Shape Memory Alloy Wire Dampers

This paper presents a simulation-based benchmark control study in which shape memory alloy (SMA) wire dampers are utilized to control the seismic response of a three-story nonlinear steel frame building. The SMA wire damper uses superelastic Nitinol wires for energy dissipation because of its high fatigue life and large recoverable strain. An analytical model which considers the training effect of SMA wires is used to describe the stress-strain relationship of superelastic SMA wires. The performance of SMA wire dampers is investigated in the framework of the third-generation benchmark problem on structural control. A comparative study of the seismic response control performance of SMA wire dampers with either unprestrained or prestrained SMA wires was also conducted. The results of this simulation-based benchmark control study show that SMA wire dampers, as a passive structure control measure, can effectively reduce the seismic responses of the three-story nonlinear benchmark building structure and has the potential to withstand several design earthquakes without the need for repair.     

Oxide Scales Formed on NiTi and NiPtTi Shape Memory Alloys

Ni-49Ti and Ni-30Pt-50Ti (nominal at. pct) shape memory alloys (SMAs) were isothermally oxidized in air over the temperature range of 773?K to 1173?K (500?°C to 900?°C) for 100?hours. The oxidation kinetics, presented in detail in a companion study, show ~4 times reduction in oxidation rate due to Pt.[1] The microstructure, composition, and phase content of the scales and depletion zones were determined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). A relatively pure TiO₂ rutile structure was identified as the predominant scale surface feature, typified by a distinct highly striated and faceted crystal morphology, with crystal size proportional to oxidation temperature. The complex layered structure beneath these crystals was characterized by semiquantitative XRD of serial/taper polished sections and SEM/EDS of cross sections for samples oxidized at 973?K (700?°C). In general, graded mixtures of TiO₂, NiTiO₃, NiO, Ni(Ti), or Pt(Ni) metallic dispersoids, and continuous Ni₃Ti or Pt-rich metal depletion zones, were observed from the gas surface to the substrate interior. Overall, substantial depletion of Ti occurred due to the formation of predominantly TiO₂ scales. It is proposed that the Ni-30Pt-50Ti alloy oxidized more slowly than the binary Ni-49Ti alloy by decreasing oxygen and titanium diffusion through the thin Pt-rich layer.     

Investigation of the Effect of Magnesium on the Microstructure and Mechanical Properties of NiTi Shape Memory Alloy Prepared by Self-Propagating High-Temperature Synthesis

This work aims to describe the effect of magnesium on the microstructure, phase composition, amount of undesirable Ti₂Ni phase, martensitic transformation, mechanical properties, and corrosion resistance of NiTi alloy. To minimize the quantity of Ti₂Ni phase, we use the magnesium as an element with high affinity to oxygen, because this phase is stabilized by oxygen. Various quantities of magnesium (1, 3, and 5 wt pct) were tested. Self-propagating high-temperature synthesis (SHS) was used as a production method of the alloys. The samples prepared by SHS were pulverized by a vibrating mill, and the obtained powders were used for consolidation by means of spark plasma sintering. Results showed a significant reduction of the content of undesirable Ti₂Ni phase by the addition of magnesium. Further, magnesium increased corrosion resistance and yield strength.

     

重熔镍钛合金的形状记忆效应分析

采用不同的工艺及设备对近等原子比的形状记忆合金进行重熔,获得铸态组织形状记忆合金,对采用不同坩埚所制备出的NiTi合金进行对比分析,采用金属坩埚所得到的形状记忆合金的成分满足医疗器械及外科植入物用NiTi形状记忆合金的成分要求,且具有良好的形状记忆效应。