特种功能材料中的固态相变及应用

固态相变已经从传统结构材料的增强增韧延伸到新型功能材料研究领域,引发多种奇特的物理效应。目前已经形成一批基于固态相变的新型功能材料。这些新型功能材料蕴含着丰富的固态相变理论。固态相变现已成为新型功能材料设计与功能特性实现的重要手段之一。文章结合作者在固态相变及特种功能材料方面的研究工作,重点介绍高温形状记忆合金、高阻尼形状记忆合金、磁致伸缩材料和热障涂层材料中的固态相变特征及其在这些特种功能材料设计与功能实现和调控中应用的研究进展。     

Phenomenological analysis on subloops and cyclic behavior in shape memory alloys under mechanical and/or thermal loads

A theoretical framework is presented, from the phenomenological point of view, for the cyclic uniaxial deformation in shape memory alloys subjected to the thermal and/or mechanical loads by introducing three internal variables; the local residual stress and strain and the volume fraction of the martensic phase accumulated during cyclic forward and reverse martensitic transformations. The cyclic effect on the stress-strain and strain-temperature hysteresis loops is discussed. The subloops due to incomplete transformations are also analyzed by assuming the transformation starting stress or temperature which depends on the preloading. Numerical results explain qualitatively well the observations on the thermomechanical behaviors of shape memory alloys.     

Characterization of phase transformation behavior in electrolytically produced indium-thallium shape memory alloy films

Indium-thallium alloys in the range 15–38 at. % Tl were electrodeposited from a sulfate electrolyte by using pulsed current. The relationship between composition and phase structure of the alloys deposited was investigated with regard to the shape memory effect. To date there have been no reported experimental studies describing the electrodeposition of In---Tl alloys capable of undergoing such transformations. Not only did the deposited alloys exhibit the shape memory effect, but the composition-phase relationship exhibited was shown to deviate from that reported for alloys in an equilibrium condition. The results show that the temperature and the temperature interval for the transformation of the electrodeposited alloys are substantially different from those of the thermally prepared alloys. The shape recovery for the electrodeposited alloys was also confirmed.     

Physical metallurgy of Ti-Ni-based shape memory alloys

Ti-Ni-based alloys are quite attractive functional materials not only as practical shape memory alloys with high strength and ductility but also as those exhibiting unique physical properties such as pre-transformation behaviors, which are enriched by various martensitic transformations. The paper starts from phase diagram, structures of martensites, mechanisms of martensitic transformations, premartensitic behavior, mechanism of shape memory and superelastic effects etc., and covers most of the fundamental issues related with the alloys, which include not only martensitic transformations but also diffusional transformations, since the latter greatly affect the former, and are useful to improve shape memory characteristics. Thus the alloy system will serve as an excellent case study of physical metallurgy, as is the case for steels where all kinds of phase transformations are utilized to improve the physical properties. In short this review is intended to give a self-consistent and logical account of key issues on Ti-Ni based alloys from physical metallurgy viewpoint on an up-to-date basis.     

Study of incomplete transformations of near equiatomic TiNi shape memory alloys by DSC methods

The incomplete transformations of near equiatomic TiNi shape memory alloys were investigated by differential scanning calorimeter (DSC). The results showed that the incomplete transformation can induce multistage phase transformation in a sample showing R-phase transformation, when the turn back temperature located in a value between R_f and M_s, the heat flow detected upon following heating only shows one endothermic peak. With decreasing the turn back temperature to a temperature between M_s and M_f, two endothermic peaks (multistage phase transformation) can be observed upon the following heating. There were no incomplete transformation induced multistage phase transformations in a sample without R-phase transformation.     

变形量对NiTi形状记忆合金相变行为及恢复性能的影响

通过低温DSC测试仪、金相显微镜和拉伸试验机,研究NiTi形状记忆合金冷轧变形量对马氏体相变行和形状恢复率的影响。结果表明：冷轧变形生成的应力诱发马氏体和取向不同的丝织构及高密度位错,使得马氏体相变时界面迁移的阻碍作用增加,抑制了相变的发生;随冷轧变形量的增大合金的形状恢复率降低。     

Deformation and martensitic transformation

The influence of applied stresses and imposed plastic deformation on the martensitic transformation of a parent phase is described. Changes in mechanical properties such as flow stress, work hardening rate, fracture toughness, etc brought about by strain-induced martensitic transformation are briefly examined. In the absence of appreciable dislocation glide, atomic displacements associated with glissile boundaries are highly ordered and reversible modes of (plastic or nonlinear pseudoelastic) deformation. Such processes lead to large strains and are encountered in deformation twinning, martensitic transformations and in the reorientation of martensite units. The reversibility leads to phenomena such as elastic twinning, thermoelastic martensites, superelasticity, shape memory and two-way shape memory effects, and rubber-like behaviour. These are discussed using a unified approach based on thermoelastic equilibrium. The shape memory effect suggests several potential applications of the martensitic transformations in non-ferrous alloys in which the effect is most commonly observed. Recent developments in this area are reviewed with special reference to the prerequisites for the effect and the influence of metallurgical processing on the extent of shape recovery.     

Effect of variable material properties and environmental conditions on thermomechanical phase transformations in shape memory alloy wires

This paper reports a computational study of the impact of variable material properties and environmental conditions (thermal boundary conditions and convection coefficients) on shape memory alloy wires undergoing (i) zero-stress, thermally-induced phase transformations, and (ii) stress-induced phase transformations at constant stress rates. A finite difference numerical approach has been employed, and has been validated by comparing with two analytical solutions. The results have been all given in non-dimensional form, and within the context of the range of parameters that have been studied, the following recommendations can be made for shape memory alloys (SMA) actuator design: (i) an uncertainty in the thermal boundary condition is not as important as long as the design process allows for a full transformation back to martensite at the end of a cycle of martensite–austenite–martensite thermal transformation, (ii) uncertainties in the thermal boundary condition, convection coefficient and thermal material properties are not as important when the phase transformation in a SMA is induced by stress.     

高温形状记忆合金的研究进展

本文综述了近年来有关高温形状记忆合金的最新研究进展。重点介绍了ＣｕＡｌＮｉ基，ＮｉＴｉ基及ＮｉＡｌ基三大系列高温形状记忆合金。概括了有关合金的设计，马氏体相变及形状记忆效应，显微结构特征，合金相稳定性及热处理效应，材料制备及生产加工工艺及性能等。     

磁性形状记忆合金研究进展

磁性形状记忆合金是上世纪90年代开始出现的一类新型金属功能材料。这类合金兼具热弹性马氏体相变和磁性转变,其形状记忆效应可以由磁场控制。此外这类合金还具有磁阻、磁热等丰富的物理效应,因而一直是近期研究热点。首先介绍了磁性形状记忆合金的3个基本特征,即马氏体相变与磁性转变、磁场驱动孪晶再取向和磁场诱发相变。然后分别对Ni基、Co基和Fe基磁性形状记忆合金的研究现状进行了评述。最后展望了磁性形状记忆合金的发展趋势。     

机械合金化和粉末冶金法制备Fe-Mn-Si基形状记忆合金的研究进展

铁基形状记忆合金由于价格低廉、强度高、加工性能好、可焊接等优点引起广泛重视。机械合金化(MA)和粉末冶金(PM)作为制备材料的新工艺,可以用来制备性能优越的形状记忆合金。本文详述了机械合金化和粉末冶金工艺在制备Fe-Mn-Si基形状记忆合金过程中对合金相变、组织与性能的影响,以及此类合金在新领域的应用。最后提出了现阶段在研究MA/PM工艺制备Fe-Mn-Si基SMA中有关工艺参数、相变机制以及回复应力和低温应力松弛所存在的问题。     

形状记忆合金的力学及界面参数和体积分数对大块金属玻璃基复合材料增韧的影响

采用考虑塑性的超弹性材料模型和基于损伤塑性的准脆性材料模型,建立了三维单胞有限元模型,模拟了形状记忆合金颗粒增韧大块金属玻璃基复合材料的单调拉伸行为。讨论了形状记忆合金的力学参数、体积分数、界面厚度和界面材料参数对金属玻璃增韧效果的影响。结果表明:提高形状记忆合金的相变应变和马氏体塑性屈服应力将显著提高形状记忆合金颗粒增韧大块金属玻璃基复合材料的拉伸失效应变;形状记忆合金弹性模量超过50.0GPa、马氏体塑性屈服应力超过1.8GPa后,复合材料的拉伸失效应变变化不大。能同时兼顾失效应变和失效应力的形状记忆合金体积分数为15%左右。复合材料界面弹性模量和界面屈服应力的增加将提高复合材料的失效应力,但对失效应变影响不大;复合材料界面厚度的增加在提高失效应变的同时,也降低了复合材料的失效应力。     

Micromechanics of Tension‐Compression Asymmetry of Polycrystalline Shape‐Memory‐Alloys

The asymmetry associated with martensitic transformations observed in tension/compression experiments of shape‐memory‐alloys (SMAs) is investigated on the basis of a recently suggested micromechanical model. The approach is based on crystallographic theory and utilizes a framework of energy minimization in a finite deformation context. Polycrystalline NiTi under tension demonstrates smaller phase‐transformation start‐strain, differe phase‐transformation stress‐levels and flatter phase‐transformation stress‐strain slopes than that under compression in our numerical simulation. The phase‐transformation start‐stress is followed to have a linear relationship with respect to the temperature within a certain range. These results agree well with experimental results reported in the literature.     

铁基形状记忆合金马氏体相变研究进展

铁基形状记忆合金的形状记忆效应和超弹性取决于合金的马氏体相变特征,掌握铁基合金的马氏体相变规律是开发和优化铁基形状记忆合金的前提。根据马氏体相变类型将目前发现的铁基形状记忆合金分成3类：Fe-Mn-Si系,Fe-Ni-Co系和Fe-Pt／Fe-Pd系,分别阐述了3类铁基形状记忆合金马氏体相变的研究进展,总结了铁基合金形状记忆效应的不同机理和影响马氏体相变特征的各种因素,探讨了开发新型铁基形状记忆合金的需要关注的方向。     

Multiscale bifurcation and stability of multilattices

A lattice-level model is developed for active materials, such as shape memory alloys, that undergo martensitic phase transformations. The model is investigated using equilibrium path following and bifurcation techniques. It is shown that a multiscale stability criterion is essential for correctly interpreting the stability of crystal equilibrium configurations under both thermal- and stress-loading conditions. A two-stage temperature-induced phase transformation is predicted from a cubic B2 phase to an orthorhombic Cmmm phase to a final orthorhombic B19 phase. Under stress-loading conditions, martensitic transformations from the B2 austenite phase to a number of possible martensite phases are identified. These include reconstructive transformations to B11, B33, and C2/m structures and proper transformation to a C2/m monoclinic phase which displays characteristic tension-compression asymmetry. The prediction of both temperature-induced and stress-induced proper martensitic transformations indicates the likelihood that the current model will exhibit shape memory behavior.     

X-ray diffraction study of the phase transformations in NiTi shape memory alloy

The phase transformations occurring in heat-treated NiTi shape memory alloys have been studied through the analysis of variation in integrated peak area (integrated intensity) with temperature, under the XRD peak profiles in the transformation temperature range. For this purpose, integrated peak area under the prominent peak corresponding to (110) plane of the austenitic phase has been chosen. The results so obtained are compared with those got from the DSC method. The XRD method is found to be more sensitive.     

磁驱动相变材料研究进展

磁驱动相变材料利用外磁控制下铁弹马氏体变体重排或磁诱导一级相变产生的形状记忆效应来捕获应变,兼具铁弹形状记忆与磁致伸缩功效特征。Heusler型Ni-Mn-X(X=Ga或In)系磁驱动相变合金材料具有磁感生应变大、能量密度高、反应速度快等优点,是未来重要磁传感器和磁驱动器研制的关键。主要介绍了国内外Ni-Mn-Ga、Ni-Co-Mn-In、反铁磁体等磁驱动相变材料的研究进展,以及本课题组利用高能X射线衍射和中子散射技术对磁驱动相变材料的原位研究。最后,展望了磁驱动相变合金材料的发展趋势。     

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.     

Study of the Thermal Properties of a Ni<Subscript>3</Subscript>Ta Shape Memory Alloy

Dilatation characteristics, thermal diffusivity, and thermal conductivity of a Ni₃Ta shape memory alloy were studied over the temperature range from room temperature up to 950 °C. The Ni₃Ta alloy was investigated in both polycrystalline and single crystal forms. The shape memory effect was positive for the polycrystalline samples and negative for the single crystal. While the transformation temperature of the M (martensite) → A (austenite) phase transformation was the same for both types of alloys and all measurements, the transformation temperature for the reverse phase transformation A → M was dependent on the maximum cycle temperature. Higher maximum temperatures of the thermal cycle yielded lower transformation temperatures for the A → M transformation. The thermal diffusivity and thermal conductivity of the austenite were higher than those of the martensite. No latent heat was found for the phase transformations.     

新型磁驱动形状记忆合金研究进展

磁驱动形状记忆合金是一种新型功能材料,由于兼具大的输出应变和高响应频率等综合特性,成为智能材料领域的研究热点之一.本研究首先总结了Ni-Mn-Ga合金在相变和磁致应变性能方面的特点,然后着重介绍了Co-Ni-Ga和Ni-Fe-Ga两类新型磁驱动记忆合金在结构、相变、形状记忆效应、磁性能等方面的研究进展,并对其中存在的问题进行了讨论.