New aspects of martensite stabilization in Ni–Mn–Ga high-temperature shape memory alloy

We report on new aspects of martensite stabilization in high-temperature shape memory alloys. We show that, due to the difference in activation energies among various structural defects, an incomplete stabilization of martensite can be realized. In material aged at high temperatures, this gives rise to a variety of unusual features which are found to occur in the martensitic transformation. Specifically, it is shown that both forward and reverse martensitic transformations in a Ni–Mn–Ga high-temperature shape memory alloy can occur in two steps. The observed abnormal behaviour is evidence that, in certain circumstances, thermoelastic martensitic transformation can be induced by diffusion.     

Shape memory effect and superelasticity in a strain glass alloy

The shape memory effect and superelasticity are usually found in alloys exhibiting spontaneous martensitic transformation. Thus it is hard to imagine that such interesting effects can appear in a system without a martensitic transformation. In this Letter we show shape memory and the superelasticity effect in a nonmartensitic Ti48.5Ni51.5 alloy, which has no martensitic transformation but undergoes a "strain glass" transition. In situ x-ray diffraction experiment showed that the shape memory and superelasticity in strain glass stem from a stress-induced strain glass to martensite transformation and its reverse transformation. The new shape memory and superelasticity in strain glass extends the regime of the shape memory effect and superelasticity and may lead to novel applications.     

Ni-X-In(X=Mn,Fe和Co)合金的缺陷稳定性和磁性能的第一性原理研究

Ni-Mn-In是一种新型的磁控形状记忆合金, 它通过磁场诱导逆马氏体相变实现形状记忆效应. 实验中常围绕化学计量比Ni₂MnIn合金进行成分调整, 以获得适宜的马氏体相变温度与居里温度, 在这个过程中必然会产生多种点缺陷. 本文使用量子力学计算软件包VASP, 在密度泛函理论的框架下通过第一原理计算, 系统地研究了非化学计量比Ni-X-In(X=Mn, Fe 和Co)合金的缺陷形成能和磁性能. 反位缺陷中, In和Ni在X亚晶格的反位缺陷(In_X和Ni_X)的形成能最低, Ni和X反位于Y的亚晶格(Ni_Y和X_Y)得到较高的形成能. 因此, In原子可以稳定立方母相的结构, 而X原子对母相结构稳定性的影响则相反; 空位缺陷中最高的形成能出现在In空位缺陷, 再次肯定了In原子对稳定母相结构的作用. 此外, 详细研究了点缺陷周围原子的磁性能以及电荷分布. 本文的计算结果在指导实验中的成分设计和开发新型磁控形状记忆合金方面具有重要意义.     

Scaling relationships in sharp conical indentation of shape memory alloys

Based on dimensional analysis and finite element calculations, several scaling relationships in the indentation of shape memory alloys with a sharp conical indenter were obtained. These scaling relationships illustrate the dependence of the indentation response on the material properties of shape memory alloys, such as phase transition and plastic deformation. It is shown that the yield stress and strain-hardening exponent of transformed martensite play important roles in the indentation response, in addition to the phase transition properties. Additionally, the general relationships between indentation hardness and phase transition stress, maximum transition strain, martensite yield stress and the strain-hardening exponent of shape memory alloys were obtained. The results show that the indentation hardness of shape memory alloys is not proportional to the phase transition stress or to the martensite yield stress, and cannot be used directly to measure the phase transition stress or the yield stress of shape memory alloys.     

A macro-mechanical constitutive model of shape memory alloys

It is of practical interest to establish a precise constitutive model which includes the equations describing the phase transformation behaviors and thermo-mechanical processes of shape memory alloy (SMA). The microscopic mechanism of super elasticity and shape memory effect of SMA is explained based on the concept of shape memory factor defined by the author of this paper. The conventional super elasticity and shape memory effect of SMA are further unified as shape memory effect. Shape memory factor is redefined in order to make clear its physical meaning. A new shape memory evolution equation is developed to predict the phase transformation behaviors of SMA based on the differential relationship between martensitic volume fraction and phase transformation free energy and the results of DSC test. It overcomes the limitations that the previous shape memory evolution equations or phase transformation equations fail to express the influences of the phase transformation peak temperatures on the phase transformation behaviors and the transformation from twinned martensite to detwinned martensite occurring in SMA. A new macro-mechanical constitutive equation is established to predict the thermo-mechanical processes realizing the shape memory effect of SMA from the expression of Gibbs free energy. It is expanded from one-dimension to three-dimension with assuming SMA as isotropic material. All material constants in the new constitutive equation can be determined from macroscopic experiments, which makes it more easily used in practical applications. Supported by the National Natural Science Foundation of China (Grant No. 95505010), the National High Technology Research and Development Program of China (Grant No. 2006AA03Z109), the China Postdoctoral Science Foundation (Grant No. 20080430933), the Open Foundation of Institute of Engineering Mechanics of National Seism Bureau of China (Grant No. 2007B02), and the Harbin Talent Foundation of Scientific and Technical Innovation (Grant No. RC2009QN-017046)     

Reversible and irreversible martensitic transformations in Fe-Pd and Fe-Pd-Co alloys

Ferromagnetic Fe-Pd shape memory alloys (SMA) undergo a martensitic phase transformation during cooling from a parent FCC phase to a tetragonal FCT martensite. This transformation is thermoelastic and reversible giving rise to the shape memory effect. On further cooling an irreversible FCT to BCT transformation occurs that makes impossible the memory effect. Nevertheless, the transformation from reversible to irreversible phase has been not complete since a volume fraction of reversible phase in the alloy is retained even after cooling below the temperature of appearance of the irreversible phase. The addition of Co lowers the temperature of the reversible and irreversible phase transformations but also reduces the amount of transformed irreversible martensite after cooling to 10 K.     

Effect of Mn incorporation for Ni on the properties of melt spun off-stoichiometric compositions of NiMnGa alloys

The investigation addresses the effect of Mn incorporation for Ni on the properties of a series of Ni_77−xMn_xGa₂₃ (x=22-29; at%) ferromagnetic shape memory alloys prepared in the form of ribbons by a melt spinning technique. Phase transformation studies in these ribbons by differential scanning calorimetry revealed that austenitic start and martensitic start temperatures decreased with the increase in Mn content. The Curie temperature (T_C) of these alloys determined from thermal variation of magnetisations was found to rise with increasing Mn content. The martensitic transformation temperatures were above T_C in low Mn containing (x=22 and 23) alloys. Morphology observed through transmission electron microscopy manifested complex martensitic features in the alloy with x=22 while x=29 had an austenitic phase. The alloys with intermediate Mn content (x=24, 25) had overlapping magnetic and martensitic transformations close to room temperature. The thermal lag between austenitic and martensitic characteristic temperatures in these alloys has been corroborated to their structural state. X-ray diffraction indicated a predominant martensite phase and austenite phase in low and high Mn containing alloys respectively. In-situ diffraction studies during thermal cycle indicate martensite-austenite transformations.     

低温时效处理对铁磁形状记忆合金Mn2NiGa的结构、相变和磁性能的影响

对在较低温度范围的时效处理铁磁形状记忆合金Mn₂NiGa的结构、相变和磁性进行了研究.研究发现,母相基体析出了细小的析出相,引起了晶格扭曲和畸变,导致了系统内产生了很大的内应力.在其浓度超过晶格的容忍度之后,提升了体系的马氏体相变温度,使母相在时效温度下转变成马氏体相,并在其中测量到高达900 Oe的矫顽力.由于这种马氏体相的逆相变温度大幅提高,外推获得其居里温度在530 K附近.细小析出相的粗化使内应力消失,样品又回到母相状态.观察到细小析出相粗化的两个阈值温度,分别为423 K和 关键词： 铁磁形状记忆合金 2NiGa')" href="#">Mn₂NiGa 时效处理 内应力     

Annealing effect on phase transformation in nano structured Ni–Mn–Ga ferromagnetic shape memory alloy

Nano structured Ni_52.6Mn_23.7Ga_24.3 alloy was prepared using the ball milling technique. High martensitic transition temperatures are observed in the range between 336 and 367 K. The X-ray diffraction profile revealed that annealed Ni–Mn–Ga powder at 1073 K displays mixture phases of austenite and martensite. Annealing at 1173 K induces phase transformation from mixture phase to Heusler L2₁ structure, which confirms the high-temperature shape memory effect. On the contrary, the milled sample shows no evidence of shape memory effect. Furthermore, annealing at higher temperature (1273 K) shows the accumulation of oxidation, which leads to the loss of shape memory effect. The grain size increases with increasing annealing temperature and causes deterioration in the soft magnetic properties.     

Ni-Fe-Ga磁致形状记忆合金中间马氏体相变

采用差示扫描量热和x射线衍射技术研究Ni-Fe-Ga磁致形状记忆合金的马氏体相变行为.结 果发现,在多晶Ni565_56.5Fe190_19.0Ga245_{2 4.5}和Ni563_56.3Fe170_17.0 Ga267_26.7合金中除马氏体相变外,还观察到一次完整的、正相变和逆相 变对应出现、单 纯由温度诱发的中间马氏体相变.该中间马氏体相变与马氏体相变均为热弹性相变. 关键词： Ni-Fe-Ga 中间马氏体相变 磁致形状记忆合金     

Strain glass behaviour of Ni–Co–Mn–Sn ferromagnetic shape memory alloys

We report the direct experimental observations of the glassy behaviour in Ni–Co–Mn–Sn ferromagnetic shape memory alloys by doping sufficient substitutional point defect Co into the Ni sites (9 at%). The results showed that high level of Co doping had caused the complete suppression of the martensitic transformation and introduction of a strain glass transition in Ni–Co–Mn–Sn alloys. The strain glass transition was definitively characterized by the dynamic mechanical anomalies following the Vogel–Fulcher relationship and the signature nonergodicity of the frozen glass using a zero‐field‐cooled/field‐cooled heating measurement of static strain. The findings clarified the cause of vanishing of the martensitic transformation in Ni–Co–Mn–Sn alloy with high Co doping levels and the generality of glassy state in Ni–Mn based ferromagnetic shape memory alloys with high level of foreign elements doping. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Ni4Ti3沉淀相对NiTi形状记忆合金相变行为的影响

采用第二近邻修正型嵌入原子势的分子动力学方法,建立了共格沉淀相与半共格沉淀相块状/柱状模型,模拟了温度诱发相变和应力诱发相变,分析了Ni₄Ti₃沉淀相对Ni Ti形状记忆合金相变行为的影响．结果表明,Ni₄Ti₃沉淀相本征应变诱发的弹性应力场对相变中马氏体变体类型、形核位置、分布等有重要影响.在温度诱发相变时,共格沉淀相促进部分马氏体变体的形核生长,能显著提高Ni Ti超弹性形状记忆合金的马氏体相变开始温度;在应力诱发相变时,Ni₄Ti₃沉淀相使马氏体早于无沉淀相区域形核,导致了相变应力降低、抑制了马氏体解孪,减小了应力-应变曲线的滞回环.     

The effect of Si content on the martensitic transfor-mation temperature of Ni55.5e18Ga26.5-xSix alloys

This paper investigates the effects of substitution of Si for Ga on the martensitic transformation behaviours in Ni-Fe-Ga alloys by using optical metallographic microscope and differential scanning calorimetry (DSC) methods. The structure type of Ni_55.5Fe₁₈Ga_26.5-xSi_x alloys is determined by x-ray diffraction (XRD), and the XRD patterns show the microstructure of Ni-Fe-Ga-Si alloys transformed from body-centred tetragonal martensite (with Si content x = 0) to body-centred cubic austenite (with x = 2) at room temperature. The martensitic transformation temperatures of the Ni_55.5Fe₁₈Ga_26.5-xSi_x alloys decrease almost linearly with increasing Si content in the Si content range of x ≤ 3. Thermal treatment also plays an important role on martensitic transformation temperatures in the Ni-Fe-Ga-Si alloy. The valence electronic concentrations, size factor, L2₁ degree of order and strength of parent phase influence the martensitic transformation temperatures of the Ni-Fe-Ga-Si alloys. An understanding of the relationship between martensitic transformation temperatures and Si content will be significant for designing an appropriate Ni-Fe-Ga-Si alloy for a specific application at a given temperature.     

Combined experimental and theoretical study on the effect of Nb content on martensitic transformation of NbRu shape memory alloys

The effect of Nb content on the martensitic transformation of NbRu high-temperature shape memory alloys is investigated by experiments and first-principles calculations. We calculate the lattice parameters, density of states, charge density, and heats of formation of Nb_50+xRu_50-x β phase. The results show that an increase in Nb content increases the stability of Nb_50+xRu_50-x β phase, leading to a significant decrease of the β to β' martensitic transformation temperature. In addition, the mechanism of the effects of Nb content on phase stability and martensitic transformation temperature is studied on the basis of electronic structure.     

Phase transition in a multiferroic Ni-Mn-Ga single crystal

ABSTRACT

We studied martensitic phase transformation, crystal structure and twinned microstructure of resulting martensite of a Ni-Mn-Ga single crystal as essential conditions for magnetic shape memory effect. Thermal dependence of electric resistivity, magnetic susceptibility and dilatation measurements were measured to characterise kinetics of the transformation. With the help of XRD analysis and optical microscopy we evaluated the hierarchical twinning microstructure in the 10M martensite.     

The effect of Si content on the martensitic transformation temperature of Ni55.5Fe18Ga26.5-xSix alloys

This paper investigates the effects of substitution of Si for Ga on the martensitic transformation behaviours in Ni-Fe-Ga alloys by using optical metallographic microscope and differential scanning calorimetry (DSC) methods. The structure type of Ni55.5Fe18Ga26.5-xSix alloys is determined by x-ray diffraction (XRD),and the XRD patterns show the microstructure of Ni-Fe-Ga-Si alloys transformed from body-centred tetragonal martensite (with Si content x = 0) to body-centred cubic austenite (with x = 2) at room temperature. The martensitic transformation temperatures of the Ni55.5Fe18Ga26.5-xSix alloys decrease almost linearly with increasing Si content in the Si content range of x ≤ 3. Thermal treatment also plays an important role on martensitic transformation temperatures in the Ni-Fe-Ga-Si alloy. The valence electronic concentrations,size factor,L21 degree of order and strength of parent phase influence the martensitic transformation temperatures of the Ni-Fe-Ga-Si alloys. An understanding of the relationship between martensitic transformation temperatures and Si content will be significant for designing an appropriate Ni-Fe-Ga-Si alloy for a specific application at a given temperature.     

Fracture mechanism of a Ni–Mn–Ga ferromagnetic shape memory alloy single crystal

Ni–Mn–Ga ferromagnetic shape memory alloys (FSMAs) have shown large magnetic-field-induced strains up to 10%. The fracture behavior of these materials under thermal and magnetic cycling has not been reported so far. An Ni–Mn–Ga single crystal exhibiting both thermal and magnetic shape memory effect was investigated in the present study. Coexistence of differently oriented martensite twinned variants and its effect on the magnetization and fracture mechanism were studied. Fracture behavior of this alloy was found to be strongly related to the martensitic transformation while the fracture surface was parallel to one of the {1 1 2} martensite twin planes. Different orientations of martensite variants were responsible for the formation of the crack network leading to fracture.     

Heusler合金Mn2NiGe磁性形状记忆效应的第一性原理预测

运用基于密度泛函理论的第一性原理,对Hg₂CuTi型Mn₂NiGe的四方变形、晶体结构、磁性、电子结构、压力响应等进行了计算.计算结果表明: 1)在由立方结构至四方结构的转变中,在c/a约为1.34处存在一个稳定的马氏体相;2)在奥氏体态和马氏体态下,Mn原子均是Mn₂NiGe总磁矩的主要贡献者,但Mn(A),Mn(B)原子磁矩的值不等且呈反平行耦合,因而Mn₂N 关键词： 第一性原理 磁性形状记忆 四方变形 马氏体相变     

Alloying and magnetic disordering effects on phase stability of Co2 YGa (Y=Cr,V, and Ni) alloys: A first-principles study

The alloying and magnetic disordering effects on site occupation, elastic property, and phase stability of Co$_{2}Y$Ga ($Y={\rm Cr}$, V, and Ni) shape memory alloys are systematically investigated using the first-principles exact muffin-tin orbitals method. It is shown that with the increasing magnetic disordering degree $y$, their tetragonal shear elastic constant $C'$ (i.e., $(C_{11}-C_{12})/2$) of the $L2_{1}$ phase decreases whereas the elastic anisotropy $A$ increases, and upon tetragonal distortions the cubic phase gets more and more unstable. Co$_{2}$CrGa and Co$_{2}$VGa alloys with $y\geq0.2$ thus can show the martensitic transformation (MT) from $L2_{1}$ to $D0_{22}$ as well as Co$_{2}$NiGa. In off-stoichiometric alloys, the site preference is controlled by both the alloying and magnetic effects. At the ferromagnetism state, the excessive Ga atoms always tend to take the $Y$ sublattices, whereas the excessive Co atom favor the $Y$ sites when $Y={\rm Cr}$, and the excessive $Y$ atoms prefer the Co sites when $Y={\rm Ni}$. The Ga-deficient $Y={\rm V}$ alloys can also occur the MT at the ferromagnetism state by means of Co or V doping, and the MT temperature $T_{\rm M}$ should increase with their addition. In the corresponding ferromagnetism $Y={\rm Cr}$ alloys, nevertheless, with Co or Cr substituting for Ga, the reentrant MT (RMT) from $D0_{22}$ to $L2_{1}$ is promoted and then $T_{\rm M}$ for the RMT should decrease. The alloying effect on the MT of these alloys is finally well explained by means of the Jahn-Teller effect at the paramagnetic state. At the ferromagnetism state, it may originate from the competition between the austenite and martensite about their strength of the covalent banding between Co and Ga as well as $Y$ and Ga.     

Antiphase boundary-like stacking fault in α″-martensite of disordered crystal structure in β-titanium shape memory alloy

The ordering and antiphase boundary (APB)-like fault found in the α″-martensite of β-Ti shape memory alloys are studied. Long-range chemical ordering was not found, but APB-like faults were observed in every martensite plate studied by transmission electron microscopy. These faults have morphology similar to the APBs observed in ordered phases. The superlattice reflections observed in some previous works were a consequence of multiple diffractions. APB-like faults were not observed in the parent phase, leading to the conclusion that the faults were introduced by the martensite transformation. The fault took the form of a wavy tube running perpendicular to the habit plane. The fault was a ‘transformation-induced APB’ with an additional small displacement due to the pre-existing athermal ω phase. The displacement vector was determined to be [–3/50, ?23/50, 1/2]. Geometrical aspects of the formation of APB-like faults are also discussed.