Mn_（50）Ni_（39）Sn_（11-x）Al_x合金的磁相变及磁卡效应

Ni-Mn基铁磁Heusler合金的巨大磁卡效应使其在磁制冷方面具有良好的应用前景.磁熵变是磁卡效应的重要量度,根据麦克斯韦关系,磁熵变不仅与马氏体相变前后磁矩的变化大小△Msf有关,而且与马氏体相变温度跨度（Martensitic Transition Temperature Range,MTTR）有关.本文中,我们制备了Mn50Ni39Sn11△xAlx（x=0,1,2）系列合金样品,发现随着Al含量的升高,虽然△Msf减小,但MTTR随Al含量增加的减少更快,使得（△Msf/MTTR）值增大,从而获得较大的磁熵变△SM.以上结果表明除增大△Msf外,降低MTTR值也是提高材料磁卡效应的有效方法.     

Ni_（50-x）Mn_（10＋x）Ga_（30）Cu_（10）系列Heusler合金的结构、马氏体相变和磁性研究

通过实验和第一性原理研究了Ni50-xMn10＋xGa30Cu10（x=0-10）系列Heusler合金的结构、马氏体相变和磁性.实验研究发现,当用Mn原子在化学上替换Ni原子,合金的晶格参数随成分线性增大,相应体系的马氏体相变温度线性降低;理论分析认为,体系合金的单胞尺寸和电子浓度的共同作用使马氏体相变温度随成分变化线性降低直至消失;体系中Mn对Ni原子的替换使交互作用较强的Ni（A,C）-Mn（B）原子对逐渐形成,这增强了磁性原子间总的交换耦合作用,实验观测到体系合金的居里温度随成分逐渐上升.基于KKR-CPA-LDA的第一性原理计算结果表明,在体系合金中Mn原子磁矩始终与Ni原子磁矩保持铁磁排列,且Mn原子为体系分子磁矩的主要贡献者,因此体系合金的分子磁矩随Mn原子数量线性增加,这与实验结果相一致.     

Ga对β基Co-Ni-Al铁磁性形状记忆合金马氏体和磁性转变的影响

借助光学金相、示差热分析、振动样品磁强计和x-射线能谱分析等分析方法，研究Ga含量对Co41Ni32-Al27-xGax合金马氏体相变和Curie点的影响。研究结果表明：合金马氏体相变温度与Ga含量成正比，在1573和1623K淬火时，X增加1，马氏体相变温度提高25K，但Ga含量对Curie点影响不大；在1573K淬火时，具有高有序度的马氏体相比B2结构相的Curie点高32K，说明结构有序度对Curie点影响较大；淬火温度升高会显著提高合金的马氏体相变温度和Curie点，当淬火温度从1573K升高到1623K时，马氏体相变温度升高43～69K，Curie点平均升高41K；随着Ga含量的增加，合金的熔点降低，在1623K淬火时Co41Ni32Al18Ga9合金发生部分熔化。     

Fe对Ni-Mn-Ga形状记忆合金相变和力学性能的影响

研究了Fe含量对Ni56Mn25 xFexGa19(x=0～10)合金的微观组织结构、相变行为、力学性能和记忆特性的影响规律.当x 4时,Ni56Mn25–xFexGa19合金仍然保持着单一的四方结构马氏体相;当x 6时,合金呈现为马氏体相和面心立方γ相组成的双相结构.相对于马氏体相,γ相为富Ni和富Fe相,其含量随Fe含量的增加而增加.随着Fe含量增加,合金的马氏体相变温度逐渐降低,其峰值温度从x=0时的356℃降低至x=10时的170℃,这主要归因于马氏体相尺寸因素和电子浓度的综合作用.通过添加Fe替代Mn在合金中引入的γ相可提高合金的强度和塑性,但最大形状记忆回复应变从x=0时的5.0%降低到x=6时的2.0%.     

Ni50.3Mn27.3Ga22.4磁性形状记忆合金薄膜的磁性能研究

采用磁控溅射方法制备Ni50.3Mn27.3Ga22.4磁性形状记忆合金薄膜。系统研究薄膜的马氏体相变行为、磁场增强相变应变特性以及温度对磁感生应变的影响。试验结果表明,经823 K退火1 h的Ni50.3Mn27.3Ga22.4薄膜室温下处于奥氏体态,马氏体相变开始温度为271.5 K。当沿膜面方向施加0—0.8 T磁场时,Ni50.3Mn27.3Ga22.4薄膜的马氏体相变应变量随磁场强度的增大而增大,呈现出磁场增强马氏体相变应变效应。试验还发现,饱和磁感生应变显著依赖于测试温度。当测试温度低于拟马氏体相变结束温度时,饱和磁感生应变随温度的升高先缓慢增大,在马氏体相变开始温度附近磁感生应变值发生跳跃式增加,然后随测试温度的进一步升高而降低。     

热处理对NiAlMn高温形状记忆合金相变行为的影响

研究了热处理和热循环Ni－Al－30Mn高温形状记忆合金相变行为的影响。结果表明：（1）在600－1100℃固溶淬火时，随固溶温度升高，该合金的马氏体相变温度升高；在1000℃固溶淬火后，马氏体相变开始温度和马氏体逆相变结束温度为分别为465℃和549℃，（2）在1000℃固溶处理处理和400℃时效处理后，该合金可获得良好的相变特性；热循环使相变行为的稳定性提高。（3）该合金的淬火组织由马氏体和γ相组成，其中马氏体的体积约占60％，马氏体的硬度高于γ相，时效处理后合金的相组成未变，硬度有所增加。     

Heusler合金Mn2 NiSi的形状记忆行为和磁性

采用基于密度泛函理论的第一性原理,对 Heusler合金 Mn2 NiSi的电子结构和磁性进行了研究。计算结果表明：从立方结构到四方结构的相变降低了总能量,表明马氏体相是更加稳定的。随着温度的降低, Mn2 NiSi经历了从奥氏体到马氏体的转变,体积几乎不变,表明了该合金具有形状记忆行为。磁基态是亚铁磁,Mn（A）和 Mn（B）磁矩是反平行排列的、并且不等。奥氏体相和马氏体相的总磁矩分别是9．64×10－24 A·m2和2．60×10－24 A·m2。在这两种结构中,Mn（A）和 Mn（B）是 Mn2 NiSi 总磁矩的主要贡献者。根据态密度解释了马氏体相变和磁性的产生。     

Heusler合金Mn_2NiSi的形状记忆行为和磁性

采用基于密度泛函理论的第一性原理,对Heusler合金Mn2NiSi的电子结构和磁性进行了研究。计算结果表明:从立方结构到四方结构的相变降低了总能量,表明马氏体相是更加稳定的。随着温度的降低,Mn2NiSi经历了从奥氏体到马氏体的转变,体积几乎不变,表明了该合金具有形状记忆行为。磁基态是亚铁磁,Mn(A)和Mn(B)磁矩是反平行排列的、并且不等。奥氏体相和马氏体相的总磁矩分别是9.64×10-24A·m2和2.60×10-24A·m2。在这两种结构中,Mn(A)和Mn(B)是Mn2NiSi总磁矩的主要贡献者。根据态密度解释了马氏体相变和磁性的产生。     

第一性原理研究Mn2RhZ(Z=In,Sn, Sb)Heusler合金的磁性形状记忆效应

运用基于密度泛函理论的第一性原理,对3种 Heusler合金Mn₂RhZ(Z=In, Sn, Sb)的原子占位、晶体结构、晶格畸变和磁学性质等性能进行了研究.结果表明, Hg₂CuTi型结构3种Heusler合金相比Cu₂MnAl型结构表现得更为稳定;在由立方结构至四方结构的变形中,Mn₂RhZ(Z=In, Sn, Sb)分别在c/a=1.38,1.29,1.29处出现总能量的最小值,分别对应稳定的马氏体相;Mn₂RhZ(Z=In, Sn, Sb)的总磁矩主要源于Mn原子磁矩,奥氏体相下Mn₂RhSb合金中的2个Mn原子磁矩呈现反平行耦合,表现出铁磁性,而在奥氏体、马氏体相下Mn₂RhZ(Z=In, Sn)以及马氏体相下Mn₂RhSb合金表现出亚铁磁结构,因而Mn₂RhZ(Z=In, Sn, Sb)是潜在的具有磁性形状记忆效应的合金材料.     

全d族Ni–(Co)–Mn–Cu–Ti合金马氏体相变、力学性能和磁性能的第一性原理计算

全 d 族 Ni–Mn–Ti 基 Heusler 合金作为一种新型的智能材料,因其丰富的物理性质被广泛关注。与传统 Ni–Mn 基合金不同,Ni–Mn–Ti 基 Heusler 合金的d–d轨道杂化取代p–d 轨道杂化,提高了合金的塑韧性,解决了传统Ni–Mn 基合金固有脆性大、力学性能差的问题。由于卓越的机械性能和相变过程中较高的熵变,Ni–Mn–Ti 基合金在超弹性和弹热制冷方面具有广阔的研究前景。Cu掺杂和Cu–Co共掺Ni–Mn–Ti 合金的研究很少,本文旨在为Ni–Mn–Ti 基合金的成分设计提供理论支持。本文通过第一性原理计算对Ni₂Mn_1.5?xCu_xTi_0.5 (x = 0.125, 0.25, 0.375, 0.5) 和 Ni_2?yCo_yMn_1.5?xCu_xTi_0.5 [(x = 0.125, y = 0.125, 0.25, 0.375, 0.5) 和 (x = 0.125, 0.25, 0.375, y = 0.625)]合金系的马氏体相变,力学性能和磁性能进行了系统研究。Ni–(Co)–Mn–Cu–Ti合金马氏体的形成能始终低于奥氏体的形成能,表明合金均能发生马氏体相变。Ni₂Mn_1.5?xCu_xTi_0.5 和 Ni_2?yCo_yMn_1.5?xCu_xTi_0.5 (y < 0.625)合金的奥氏体和非调制马氏体都是反铁磁态的,当y = 0.625时, Ni_2?yCo_yMn_1.5?xCu_xTi_0.5合金的奥氏体由反铁磁态转变为铁磁态,而马氏体保持反铁磁态,马氏体相变时合金会伴随磁性的突变,即发生磁—结构耦合现象,这是合金具有磁热效应的物理基础。掺Cu能降低Ni–(Co)–Mn–Ti合金的热滞后和各向异性。提高Mn的含量并且降低Ti的含量能提高Ni–Mn–Cu–Ti合金抗剪切和抗正应力的能力,但会降低韧性。就延展性而言,Ni–Mn–Cu–Ti 和 Ni–Co–Mn–Ti合金强于Cu–Co共掺合金。     

Internal friction behaviors of Ni-Mn-In magnetic shape memory alloy with two-step structural transformation

The internal friction (IF) behaviors of dual-phase Ni52Mn32In16 alloy with two-step structural transformation were investigated by dynamic mechanical analyzer. The IF peak for the martensite transformation (MT) is an asymmetric shoulder rather than those sharp peaks for other shape memory alloys. The intermartensitic transformation (IMT) peak has the maximum IF value. As the heating rate increases, the height of the IMT peak increases and its position is shifted to higher temperatures. In comparison with the IMT peak, the MT peak is independent on the heating rate. The starting temperatures of the IMT peak are strongly dependent on frequency, while the MT peak is weakly dependent. Meanwhile, the heights of both the MT and IMT peak rapidly decrease with increasing the frequency. This work also throws new light on their structural transformation mechanisms.     

First-principles exploration of the stabilization mechanism of long-period stacking ordered structures in high performance Al alloys

Long-period stacking ordered(LPSO) structures, like 9 R, 12 R, 15 R and 18 R phases etc., play a key role in improving the mechanical properties of Al alloys. In the present study the Gaussian-Like distribution(GLD)model was utilized to investigate the effects of solute atoms(Cu, Fe, Ga, Ge, Li, Mg, Sc, Si, Sn, Sr, Ti, Y, Zn) on these phase stabilizations in Al alloys by first-principles calculations. The interaction energies between solute atoms and these phases were strictly calculated. The results suggested that the solute segregations showed different characteristics in these phase structures, and solute atoms(Ga, Ge, Si, Sn, Sr, Y) tended to segregate to the stacking fault(SF) planes of them, and Sr atom was the easiest to promote the stabilization of 15 R phase compared to other structures. High solute concentrations promoted the stabilizations of these phases, while high temperature inhibited their stabilizations. In the light of the degrees of reducing the intrinsic stacking fault energies(ISFEs), the solute atoms can be ranked by:(a) For 9 R and 12 R phases, Sr Y Sn Sc;(b) For15 R and 18 R phases, Sr Y Sc Sn. Thus, it may be concluded that Sr and Y atoms are hopeful to become the underlying candidates for exploring and exploiting high-performance Al alloys with LPSO structures.     

Low-cost (ZrCu)50-xTax high temperature shape memory alloys showing excellent shape memory effect

ZrCu-based alloys, as one of the most potential high-temperature shape memory alloys, show quite high martensitic transformation temperature, relatively low price for the raw materials, and good casting fluidity. In this work, the martensitic transformation (MT) and shape memory effect of (ZrCu)_50-xTa_x high-temperature shape memory alloys were systematically investigated. Both X ray diffraction and SEM backscattered electron image demonstrated the coexistence of the main phase monoclinic martensite phase and the second phase Ta₂Cu. SEM results also revealed that increasing Ta content resulted in a larger volume fraction of Ta₂Cu phase. Differential scanning calorimetry results showed that the MT temperatures remarkably increased with Ta addition. The ductility of the (ZrCu)_50-xTa_x alloys was reduced to some degree with increasing Ta content. The shape memory effect was improved significantly, in which (ZrCu)₉₈Ta₂ alloy showed the 6.19% maximum recovery strain during 8% pre-strain under compression at 25 ?°C.     

Ab-initio investigation for the microscopic thermodynamics and kinetics of martensitic transformation

Martensitic transformation(MT) path in Fe-based alloys remains uncertain in spite of decades of research. Lots of relevant works, which mostly focused on the simplest Bain path, have been completed by the state-of-the-art firstprinciples methods based on density functional theory. In this work, the element effects on microscopic thermodynamics and kinetics of the MT are investigated in terms of two different paths, including the well-known shear dominated Bogers-Burgers path and a recently proposed shuffle dominated path. Adding common elements, e.g. Ni, Mn, Cr, Si and C, into steel could induce different kinetics of the MT, as reflected by the energy barrier, which further determines the physically realistic MT path for different alloys. Furthermore, the addition of 3 d transition metals may adjust the transformation equilibrium between the tetragonal α martensite and the hexagonal ε martensite, as reflected by their inverse effect on the energy barrier for the α MT and the stacking fault energy relating to the ε formation. An expected correlation between the thermodynamic driving force and the kinetic energy barrier for the MT is confirmed in binary Fe–Ni and Fe–Cr systems with changing the concentration of the alloying elements. These two paths for the MT are elaborately compared and discussed to reveal the nature of atomic movement in the MT, dominated by shear or shuffle.     

Ni,Si,Mn和Ti对高强度铜合金力学性能和导电性能的影响

利用合金化方法，并借助金相、SEM等测试分析手段研究了Ni／Si，Mn／NiSi和Ti对纯铜显微组织、力学性能和导电性能的影响．结果表明，Ti，Ni和Si均有提高合金组织稳定性的作用，但Mn，Ni和Si的加入不能有效地阻碍合金组织在高温下的长大．Ti，Ni和Si的加入还大幅度提高了合金强度．含w(Ni)=6％和w(Si)=1．42％的铜合金的抗拉强度达到了907MPa，同时，合金的导电性也保持在较高水平，达到了强度和导电性的良好匹配．然而：Mn，Ni和si的加入没有明显的强化作用．反而使导电性大幅降低。     

放电等离子烧结Al20Cr20Fe25Ni25Mn10高熵合金的硬度和腐蚀性能研究

采用放电等离子烧结(SPS)技术在不同温度（800、900和200°C）下保温不同时间（4、8和12 min）合成了Al₂₀Cr₂₀Fe₂₅Ni₂₅Mn₁₀高熵合金（HEA）。通过扫描电子显微镜、能谱仪（EDS）、维氏显微硬度计、极化曲线等对合金的微观结构、显微硬度和腐蚀进行了实验研究。X-射线衍射（XRD）表征了所制备合金的成分。EDS结果显示不论烧结参数如何变化,合金均由原始合金元素组成。XRD、EDS和扫描电子显微镜的结果说明所制备的合金具有球形微观结构,呈现出面心立方结构相,这是基于固溶机制形成的。这表明SPS合金具有HEAs的特征。在1000°C保温 12 min生产的合金显微硬度最高,为HV 447.97,热处理后其硬度降至HV 329.47。同一合金表现出优异的耐腐蚀性能。烧结温度升高,Al₂₀Cr₂₀Fe₂₅Ni₂₅Mn₁₀合金可具有更高的密度、显微硬度和耐腐蚀性。     

Regulating microstructures and mechanical properties of Al-Fe-Ni alloys

Mechanical properties of Al-Fe-Ni eutectic alloys have been investigated based on the nominal mass fraction of eutectic phase,and the added Fe/Ni mass ratio.The X-Ray diffraction,scanning electron microscopy equipped with energy dispersive spectroscopy and transmission electron microscope have been used to identify phase composition,characterize microstructure and crystal structure of Al_9FeNi phase,respectively.The results demonstrate that the nominal mass fraction of eutectic phase control the presence of primary phase.The tensile strength slightly increases,and the ductility deteriorates sharply as the volume fraction of primary phase increases.The Fe/Ni mass ratio has the profound effect on the microstructures(i.e.,size and shape) of primary phase.When the Fe/Ni ratio is approaching to 1,the primary phase becomes rod-like shape,which can enhance the ductility of alloys over the flake-like phase.The increasing cooling rate can effectively reduce the eutectic grains size and primary phase fraction,and further significantly improve mechanical properties of the alloys.     

Phase stability in high entropy alloys: Formation of solid-solution phase or amorphous phase

The alloy design for equiatomic multi-component alloys was rationalized by statistically analyzing the atomic size difference, mixing enthalpy, mixing entropy, electronegativity, valence electron concentration among constituent elements in solid solutions forming high entropy alloys and amorphous alloys. Solid solution phases form and only form when the requirements of the atomic size difference, mixing enthalpy and mixing entropy are all met. The most significant difference between the solid solution forming high entropy alloys and bulk metallic glasses lies in the atomic size differen ce. These rules provide valuable guidance for the future development of high entropy alloys and bulk metallic glasses.