哈斯勒合金Ni-Fe-Mn-In的马氏体相变与磁特性研究

利用电弧炉制备了Ni_50-xFe_xMn₃₇In₁₃(x=1, 3, 5) 多晶样品, 通过结构和磁性测量, 系统分析了Ni_50-xFe_xMn₃₇In₁₃(x=1, 3, 5)样品的晶体结构和马氏体相变. 结果表明, 三样品在室温下呈现出了不同的晶体结构. 同时, 随着Fe含量的增加, 样品的马氏体相变温度急剧下降, 而铁磁性却逐渐增强. 研究了Fe3和Fe5样品在反马氏体相变过程中的磁电阻和磁卡效应. 在外加3 T的磁场下, 两样品在反马氏体相变区域所表现出的磁电阻效应分别约为-46%和-15%, 而等温熵变则约为6 J·kg^{-1·K-1和9.5 J}·kg^{-1·K-1. 然而, 伴随非常宽的相变温跨和较小的磁滞损失, Fe3样品在反马氏体相变区域的净制冷量达到96 J}·kg^-1.     

Martensitic transformations in some ferrous and non-ferrous alloys under magnetic field and hydrostatic pressure

Martensitic transformations are extensively influenced by external fields, such as temperature and uniaxial stress, in transformation temperatures, crystallography and amount and morphology of the product martensites. Therefore, to clarify the effect of external fields on martensitic transformations it is very important to understand the essential problems of the transformation, such as thermodynamics, kinetics and the origin of the transformation, whose information is naturally useful in technological applications using the transformation. Magnetic field and hydrostatic pressure are important in such external fields because there exist some significant differences in magnetic moment and atomic volume between the parent and martensitic states. In the present paper, therefore, we summarizz the effects of magnetic field and hydrostatic pressure on martensitic transfonnations in some ferrous and non-ferrous alloys by referring to past and recent works made by our group and many other researchers. The transformation start temperatures of all the ferrous alloys examined increase with increasing magnetic field, but those of non-ferrous alloys, such as Ti-Ni and Cu-Al-Ni shape memory alloys, are not affected. On the other hand, the transformation start temperature decreases with increasing hydrostatic pressure in some ferrous alloys, but increases in Cu-Al-Ni alloys. The magnetic field and hydrostatic pressure dependencies of the martensitic start temperature are in good agreement with those calculated by our proposed equations.

During investigations of ferrous Fe-Ni-Co-Ti shape memory alloy, we found that a magnetoelastic martensitic transformation appears and, in addition, several martensite plates grow nearly parallel to the direction of the applied magnetic field in a specimen of Fe-Ni alloy single crystal.

We further found that the isothermal process in Fe-Ni-Mn alloy changes to athermal under a magnetic field and the athermal process changes to isothermal under hydrostatic pressure. Based on these facts, a phenomenological theory has been constructed, which unifies the two transformation processes.     

Effect of Sb-doping on martensitic transformation and magnetocaloric effect in Mn-rich Mn_(50)Ni_(40)Sn_(10-x)Sb_x(x=1,2,3,and 4) alloys

We investigate the influence of Sb-doping on the martensitic transformation and magnetocaloric effect in Mn_(50)Ni_(40)Sn_(10-x)Sb_x(x = 1, 2, 3, and 4) alloys. All the prepared samples exhibit a B2-type structure with the space group F m3 m at room temperature. The substitution of Sb increases the valence electron concentration and decreases the unit cell volume. As a result, the magnetostructural transformation shifts rapidly towards higher temperatures as x increases.The changes in magnetic entropy under different magnetic field variations are explored around this transformation. The isothermal magnetization curves exhibit typical metamagnetic behavior, indicating that the magnetostructural transformation can be induced by a magnetic field. The tunable martensitic transformation and magnetic entropy changes suggest that Mn_(50)Ni_(40)Sn_(10-x)Sb_x alloys are attractive candidates for applications in solid-state refrigeration.     

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     

The influence of Al substitution on the phase transitions and magnetocaloric effect in Ni43Mn46Sn11−xAlx alloys

The effects of Al substitution on the phase transitions and magnetocaloric effect of Ni₄₃Mn₄₆Sn_11−xAl_x (x=0-2) ferromagnetic shape memory alloys were investigated by X-ray diffraction and magnetization measurements. With the increase of Al content, the cell volume decreases due to the smaller radius of Al, and the martensitic transformation temperature increases rapidly, while the Curie temperature of austenitic phase shows a small increase. A large positive and a negative magnetic entropy change were observed near the first-order martensitic transition and the second-order magnetic transition, respectively. The magnetic entropy changes, hysteresis behavior, and refrigerant capacity near the two transitions are compared.     

Magnetostructural transition in NiCuCoMnGa alloys

The effects of the addition of Co on the martensitic transformation and Curie transition temperatures of polycrystalline Ni46-xCu4CoxMn33.sGa16.5 （x = 0, 1, 3, 5） alloys are investigated. An abrupt decrease in the martensitic transformation temperature and an obvious increase in the Curie transition temperature of austenite （TA） are observed when Co is doped in the NiCuMnGa alloy. As a result, the composition range for obtaining the magnetostructural transition is extended. Furthermore, the effect of a strong magnetic field on the magnetostructural transition is analyzed. This study offers a possible method to extend the composition range for obtaining magnetostructural transition in Heusler alloys.     

Effects of pre-deformation on the martensitic transformation and magnetocaloric property in Ni-Mn-Co-Sn ribbons

This paper investigates the martensitic transformation and magnetocaloric effect in pre-deformed Ni-Mn-Co-Sn ribbons.The experimental results show that the reverse martensitic transformation temperature T M increases with the increasing pre-pressure,suggesting that pre-deformation is another effective way to adjust T M in ferromagnetic shape memory alloys.Large magnetic entropy changes and refrigerant capacities are obtained in these ribbons as well.It also discusses the origin of the enhanced martensitic transformation temperature and magnetocaloric property in pre-deformed Ni-Mn-Co-Sn ribbons.     

Martensitic transformations and magnetic properties of nonstoichiometric alloys of the Ni-Mn-In system

Martensitic transformations and magnetic properties of Ni_89-x Mn _x In₁₁ (42 ≤ x ≤ 44) alloys have been investigated. Critical temperatures of magnetic and structural phase transitions in the studied alloy system have been determined. It has been shown that the martensitic transformation induced by the magnetic field is observed in all alloys. Temperature dependences of the spontaneous magnetization of austenite and martensite as well as the magnitude of the critical field, in which martensitic transformation occurs, have been determined.     

Pressure effects on magnetic properties and martensitic transformation of Ni–Mn–Sn magnetic shape memory alloys

The mechanism for the effects of pressure on the magnetic properties and the martensitic transformation of Ni-Mn- Sn shape memory alloys is revealed by first-principles calculations. It is found that the total energy difference between paramagnetic and ferromagnetic austenite states plays an important role in the magnetic transition of Ni-Mn-Sn under pressure. The pressure increases the relative stability of the martensite with respect to the anstenite, leading to an increase of the martensitic transformation temperature. Moreover, the effects of pressure on the magnetic properties and the martensitic transformation are discussed based on the electronic structure.     

Si掺杂的铁磁形状记忆合金Co50Ni21Ga29Six的物性研究

成功生长了Co₅₀Ni₂₁Ga₂₉:Si(x=1,2)单晶样品,对其磁性,马氏体相变及其相关性质进行了细致的测量.发现掺Si成分的单晶具有非常迅速的马氏体相变行为、2.5％的大相变应变、大于100 ppm的磁感生应变和4.5％的相变电阻.进一步研究指出,在CoNiGa合金中掺入适量Si元素,能够降低材料的马氏体相变温度,减小相变热滞后,提高材料的居里温度,并使得磁性原子的磁矩有所降低.尤其重要的是Si元素的添加能够增大材料马氏体的磁晶各向异性能,改善马氏体变体的迁移特性,从而获得更大的磁感生应变. 关键词： 铁磁形状记忆合金 Heusler合金 50Ni₂₁Ga₂₉Si_x')" href="#">Co₅₀Ni₂₁Ga₂₉Si_x     

Influence of Cr on microstructure and elastocaloric effect in Ni–Mn–In–Co–Cr polycrystalline alloys

Ni–Mn-based metamagnetic shape memory alloys have been proposed as potential elastocaloric refrigerants. The intrinsic brittleness of the alloys has limited their cooling application. Introducing a soft second phase is an effective way to reduce the brittleness. From the viewpoint of application, the effect of second phase on elastocaloric effect should be illustrated. In this paper, we have investigated the microstructure, martensitic transformation and elastocaloric effect of Ni₄₅Mn_37-xIn₁₃Co₅Cr_x ($x=0,1\text{ and }2$) polycrystalline alloys. Single-phase and precipitates-containing microstructures are obtained for the undoped and doped alloys, respectively. The precipitates in Cr-doped alloys enhances the fracture strength but significantly hinders the martensitic transformation. Balancing the fracture strength and martensitic transformation, the Ni₄₅Mn₃₆In₁₃Co₅Cr alloy with small amount of precipitates along grain boundaries exhibits large cooling effects of 4–6 K in the temperature range of 317–353 K.     

Strain characteristics and superelastic response of single crystals

The intermartensitic transformation, in a two-step complete thermoelastic martensitic transformation in Ni_53.2Mn_22.6Ga_24.2 single crystals, provides a much larger strain than that of the martensitic transformation. With a biasing magnetic field, the intermartensitic transformation strain is inhibited and the martensitic transformation strain is enhanced. Compressive stress–strain characteristics can be affected greatly by a static magnetic field. At low deformation temperature, the irreversible transformation strain induced by the stress becomes reversible, when a static magnetic field is applied. Further, the magnitude of the stress necessary for rearrangement of martensitic variants is dependent on the direction of the biasing magnetic field. Moreover, a well-defined character of the twin-boundary motion, similar to the soliton motion, has been observed upon loading or unloading.     

Nanoscopic size effects on martensitic transformations in shape memory alloys

The effect of the grain size and transverse film size in nano-and micrometer ranges on the parameters of martensitic transitions in shape memory alloys is theoretically considered in the framework of the theory of diffuse martensitic transitions. A quantitative analysis of the size effects is performed including not only the thermodynamic aspect of the martensitic transformation but also its kinetic aspect, which is particularly sensitive to structural and size factors. This complex approach makes it possible to explain the following three basic facts associated with the influence of a decreased grain size or transverse film size on the parameters of the martensitic transition in shape memory alloys: a decrease in the critical (characteristic) transition temperature, an increase in the transition temperature smearing, and the existence of a critical grain size or film thickness below which the martensitic transformation in alloys is blocked.     

Mn/Cr掺杂对Ni-Fe-Ga合金相变和磁性转变的影响

系统研究了Mn和Cr元素掺杂对Ni_(55)Fe_(18)Ga_(27)合金马氏体相变温度和居里温度的影响.研究表明:随着Mn含量的增加,Ni_(55-x)Mn_xFe_(18)Ga_(27)系列合金的马氏体相变温度逐渐降低,居里温度有所增加;Ni_(55)Fe_(18-x)Mn_xGa_(27)系列合金的马氏体相变温度也逐渐降低,但居里温度变化并不明显.随着Cr含量的增加,Ni_(55-x)Cr_xFe_(18)Ga_(27)系列合金的马氏体相变温度明显降低,居里温度则小幅度降低;Ni_(55)Fe_(18-x)Cr_xGa_(27)系列合金的马氏体相变温度和居里温度均有规律的降低.     

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.     

替代掺杂的MnNiGe1-xGax合金中马氏体相变和磁-结构耦合特性

研究了MnNiGe_1-xGa_x (x=0–0.30) 系列合金中成分、结构、马氏体相变性质和磁性的相互关系. 在较小的成分范围内, Ga取代Ge元素可有效地将马氏体相变温度降低近400 K. Ga的引入削弱了体系中的共价成键作用, 马氏体相显示出磁交换作用的增强. 相图显示, 掺杂使马氏体相变先后穿过T_N 和T_C 两个磁有序温度, 居里温度窗口效应在体系有存在的可能, 磁性对相变温度的成分关系有所影响. 实验观察到合金变磁转变的特性及相变行为对制备方法的敏感性. 这些特性的发现, 有利于进一步优化这类材料的磁结构和相变特性, 获得具有应用价值的新材料. 关键词： MM’X合金 马氏体相变 磁有序温度 变磁转变     

Effect of cobalt doping on thermoelastic martensitic transformations and physical properties of magnetic shape memory alloys Ni50 − x Co x Mn29Ga21

The magnetic and thermoelastic martensitic transformations and physical properties (magnetization, electrical resistivity, thermoelectric power, relative elongation, and thermal expansion coefficient) of multicomponent magnetic shape memory alloys Ni_{50 ? x} Co _x Mn₂₉Ga₂₁ (x = 0, 1, 2, 3, 10 at %) have been investigated. The critical temperatures of thermoelastic martensitic transformation and magnetic transitions have been determined. It has been found that the alloy with 10 at % Co undergoes a martensitic transformation in the temperature range of 6–10 K.     

Influence of Ni/Mn ratio on magnetostructural transformation and magnetocaloric effect in Ni_(48-x)Co_2Mn_(38+x)Sn_(12)(x = 0, 1.0, 1.5, 2.0,and 2.5) ferromagnetic shape memory alloys

An investigation on the magnetostructural transformation and magnetocaloric properties of Ni_(48-x)Co_2Mn_(38+x)Sn_(12)(x = 0, 1.0, 1.5, 2.0, and 2.5) ferromagnetic shape memory alloys is carried out. With the partial replacement of Ni by Mn in the Ni_(48)Co_2Mn_(38)Sn_(12) alloy, the electron concentration decreases. As a result, the martensitic transformation temperature is decreased into the temperature window between the Curie-temperatures of austenite and martensite. Thus, the samples with x = 1.5 and 2.0 exhibit the magnetostructural transformation between the weak-magnetization martensite and ferromagnetic austenite at room temperature. The structural transformation can be induced not only by the temperature,but also by the magnetic field. Accompanied by the magnetic-field-induced magnetostructural transformation, a considerable magnetocaloric effect is observed. With the increase of x, the maximum entropy change decreases, but the effective magnetic cooling capacity increases.     

Fe-Ni合金马氏体相变缺陷的正电子湮没研究

本文中用正电子湮没技术研究了Fe-Ni系合金的马氏体相变。实验结果表明,含镍量28.22—31.30wt％的六种退火态合金,正相变后,产生了大量的缺陷,使正电子湮没平均寿命及多普勒加宽线型参数S值分别约增加30％和20％。对28.93wt％Ni和31.30wt％Ni两种马氏体亚结构不同的合金,观测了正电子湮没参数与处理温度之间的关系,发现:缺陷主要产生在爆发马氏体形成阶段;在等时退火曲线上形成两个明显的台阶,是由于空位和位错恢复引起的。 关键词：     

Phase transitions and thermal expansion in Ni<Subscript>51–<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>36 + <Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript>13</Subscript> alloys

Thermal expansion and structural and magnetic phase transitions in alloys of the Ni–Mn–Sn system have been investigated. The spontaneous martensitic transformation in Ni_51–xMn_{36 + x}Sn₁₃ (0 ≤ x ≤ 3) alloys is found to be accompanied by high jumps in the temperature dependences of the linear thermal expansion. The relative change in the linear sizes of these alloys at the martensitic transformation is ~1.5 × 10^–3. There are no anomalies in the magnetic-ordering temperature range in the temperature dependences of the coefficient of linear thermal expansion. The differences in the behavior of linear thermal expansion at the martensitic transformation in Ni_51–xMn_{36 + x}Sn₁₃ (0 ≤ x ≤ 3) and Ni₄₇Mn₄₀Sn₁₃(x = 4) alloys have been established.