富镍镨掺杂镍钛形状记忆合金的微结构、相变特性与硬度

采用真空熔炼法向NiTi二元合金中掺杂Pr稀土元素,制备了多组分原子分数的Ni₅₀Ti_50-xPr_x（x=0,0.1,0.3,0.5,0.7,0.9）合金。研究了Pr元素的添加对NiTi合金金相组织、相变温度和硬度的影响。结果表明,Ni₅₀Ti_50-xPr_x合金由NiTi基体与NiPr夹杂相组成,其中Ni₅₀Ti_49.5Pr_0.5合金的马氏体相变温度达73 ℃,合金的热滞窄至37 ℃,维氏硬度约为2850 MPa。Pr元素的添加显著降低了NiTi合金的马氏体相变温度,同时,与其他NiTi基合金相比,NiTiPr合金保持了较窄的热滞和较高的硬度。     

Cu添加对La0.7Ce0.3Fe11.54-xCuxMn0.16Si1.3合金及其氢化物磁性能的影响

La(Fe, Si)₁₃系合金是具有一级相变大磁热效应的磁制冷合金,被认为是极具应用前景的磁热效应材料之一。本文采用高频感应悬浮炉制备了添加不同Cu元素比例的La_0.7Ce_0.3Fe_11.54-xCu_xMn_0.16Si_1.3(x=0, 0.05, 0.1, 0.15)合金。并利用粉末XRD衍射仪,扫描电镜(SEM)对合金的相组成、微观组织结构进行了研究,采用多功能振动样品磁强计VersaLab对合金的磁性能进行了分析。添加Cu元素后,合金的居里温度提高,但氢化后添加Cu的合金居里温度反而偏低。随着Cu元素提高磁热性能下降,但La_0.7Ce_0.3Fe_11.44Cu_0.1Mn_0.16Si_1.3H_1.68合金的最大等温磁熵变仍高达8.5 J/kg.K(0 ~ 2 T),相对制冷能力RCP提高(118 J/kg),磁滞明显降低。     

DESIGN AND PREPARATION OF IN SITU Pb-RICH PARTICLES/Al BASE METALLIC GLASS MATRIX COMPOSITE

在Al--Pb二元难混溶合金的基础上添加其它的合金元素Ni, Y和Co, 优化设计了新的 Al_82.87Pb_2.5Ni_4.88Y_7.8Co_1.95多元难混溶合金. 开展了该多元难混溶合金的快速凝固实验, 对制备的薄带样品进行了结构表征、热稳定性分析以及显微组织形成的研究. 结果表明, 合金熔体在快速冷却过程中发生了液-液相分离, 生成富Al和富Pb两液相; 随后, 富Al基体液相发生玻璃转变, 形成铝基非晶合金基体, 而富 Pb液相凝固结晶后以球形晶态粒子形式均匀分布于铝基非晶基体中. 研究表明, 利用难混溶合金液-液相变原理, 通过快速凝固技术可以设计和制备原位球晶粒子/非晶合金基复合材料.     

Cu元素对TiNiNb合金阻尼性能的影响

采用差示扫描量热仪（DSC）研究了不同原子百分比含量Cu元素（5％,15％,25％）取代Ni对TiNiNb合金马氏体相变温度的影响,并利用单悬臂法（动态机械分析仪）测试了这3种合金的阻尼性能。结果表明,Cu元素对TiNiNb合金相变过程没有明显的影响,在试验温度范围内,合金经历了一阶段的热弹性马氏体相变;Cu含量的增多促进了该合金相变温度的增加,使得相变主要发生在80℃～98℃之间（加热过程）;在马氏体相区,Cu含量高,材料的阻尼性能越好。     

La元素对MoSi2涂层的宽温域氧化行为影响

采用包渗法在稀土 La₂O₃ 掺杂钼合金基体上制备 MoSi₂ 涂层,并就 La 元素对 MoSi₂ 涂层宽温域氧化行为的影响机制进行了系统研究。 结果表明:钼镧合金基 MoSi2 涂层组织结构较为致密,主要物相为 MoSi₂ 相。 不同温度下 La 元素对 MoSi₂ 涂层的抗氧化性能的影响不同,1600 ℃高温静态氧化条件下,La 元素的存在促进了涂层与基体的化学反应,加剧了 MoSi₂ 抗氧化主体层的消耗速度,使得 MoSi₂ 涂层的高温抗氧化性能有所下降;800 ℃ 中温静态氧化条件下, La 元素对 MoSi₂ 涂层抗氧化性能影响不明显;500 ℃低温静态氧化条件下,La 元素的加入加速了涂层中 Si 元素的扩散, 使得涂层表面能较快形成一层致密的氧化层,“Pest”效应得到抑制,从而显著提升涂层的低温抗氧化性能。     

Ni48Co1Mn37In14- x Al x 磁性记忆合金马氏体相变、力学性能和耐腐蚀性能

采用电弧熔炼的材料制备方法，研究了微量的主族元素Al掺杂对Ni₄₈Co₁Mn₃₇In_14-xAl_x (0≤x≤2)磁性形状记忆合金显微组织、晶体结构、马氏体相变、力学性能和耐腐蚀性能的影响。结果表明：用Al替代部分In，合金的晶粒尺寸明显减小，掺杂2at%的Al元素，平均晶粒尺寸缩小到10 μm左右，大约为未掺杂样品的三十五分之一；当Al掺杂量在0.25at%~2at%时，金属Al完全固溶到基体中，而且Al在合金中的固溶度随掺杂量的增加有所提升，当Al掺杂量为2at%时，Al在基体中的固溶度接近2at%；随着Al对In的取代，室温下合金由L2₁立方奥氏体与单斜6M马氏体的两相结构转变为单一的6M调制马氏体相结构，晶胞体积逐渐减小，马氏体相变温度呈现上升趋势；合金抗压强度不断增大，Ni₄₈Co₁Mn₃₇In₁₂Al₂的抗压缩断裂强度与Ni₄₈Co₁Mn₃₇In₁₄相比提高了160%，压缩应变也由5.46%增加到6.36%；适量的Al替代In后，合金在人工海水中的耐腐蚀性能总体呈现不断增强的趋势，Ni₄₈Co₁Mn₃₇In₁₂Al₂合金的耐腐蚀性能明显高于Ni₄₈Co₁Mn₃₇In₁₄合金，且其耐腐蚀性接近于304不锈钢。     

半哈斯勒型磁制冷合金的研究进展

半哈斯勒型合金是近些年来受到国内外广泛关注的室温磁制冷材料之一。由于其原料较为低廉,因此其工业应用前景非常看好。依据其化学成分可大致分为co基、Ni基和Fe基三大类。合金化是调整这些合金相变温度和磁性能的重要手段。通过元素替换、掺杂以及化学计量比的变化不仅可以使半哈斯勒合金的磁性转变温度降低至室温附近,并且可以使其和结构相变温度之间的偏差尽量减小,从而为产生一级磁相变和巨磁热效应创造条件。预计今后几年合金化仍将是半哈斯勒型磁制冷合金研究的重要和热门方向之一。此外,合金的脆性和相变滞后也是值得关注的重要问题。     

Nb、Ta等元素对Zr基大块非晶非晶形成能力及耐腐蚀性影响机理研究

  用计算机编程构造了Zr基非晶合金包含二十面体原子团簇的Zr₂Ni晶体相.用Zr₂Ni晶体相中以Ni原子为中心的二十面体原子团簇模拟Zr基非晶中二十面体团簇.应用实空间的递归方法计算了合金元素取代二十面体原子团簇中心和顶角位置原子时的局域态密度、二十面体原子团簇中中心Ni原子与其近邻合金元素Nb、Ta、Ti、V的总键级积分及团簇的费米能级.结果表明,Nb、Ta、Ti和V取代Zr原子后使其与Ni的键级积分有所降低,使合金的非晶形成能力下降,但Nb、Ta对合金的非晶形成能力影响不大;Nb、V取代Zr使费米能级升高,可使Zr基非晶容易钝化,提高耐蚀性;Ta对Zr基非晶的耐蚀性影响不大.而Ti使Zr基非晶的钝化能力下降.综合合金元素对非晶形成能力和耐腐蚀性的影响,Nb是最有益的合金元素,即在Zr基非晶中,通过加入少量的Nb元素,可以制备出具有较高耐腐蚀性的大块非晶.     

高温热压法制备La(Fe, Si)13Hy系磁制冷材料的磁热性能研究

La(Fe, Si)₁₃H_Y系合金是一种极具发展潜力的室温磁制冷材料,但该材料易粉化,如何成型并保持大磁热效应成为了亟需解决的问题。本文采用中频感应炉熔炼La_0.8Ce_0.2Fe_11.51Mn_0.19Si_1.3母合金并退火,之后制备成粉末。合金粉末在650 ℃, 850 ℃和1050 ℃不同温度下热压成型,将热压块体合金加工成薄片后进行饱和氢化。利用X射线衍射仪、扫描电子显微镜、VersLab对样品的相组成、微观结构、磁热性能进行了研究。在1050 ℃下热压样品的孔隙率最低,最大体积磁熵变最高,达到了144.7 mJ/cm^₃?K。1050 ℃热压样品氢化后居里温度提高至室温附近,仍保持了一级磁相变的大磁热效应,且没有裂痕产生,保持了完整性。     

Mn含量对Mn基Heusler合金磁及磁热性能影响

选用Mn基Heusler合金为研究对象。通过电弧熔炼和热处理制备样品,并用甩带法制成薄带形状。采用X射线衍射仪和振动样品磁强计等分析仪器测试了样品的晶体结构、磁及磁热性能,分析了Mn含量对材料晶体结构、磁和磁热性能的影响。研究发现,Mn2-xSn0.5Ga0.5合金在常温下为六方结构,在室温附近仅发生一次二阶磁性转变,无明显磁滞和热滞。居里温度和饱和磁化强度对Mn含量非常敏感,随着Mn含量升高,居里温度和饱和磁化强度均出现下降,由Mn1.2Sn0.5Ga0.5的304 K和64.1 emu/g分别降至Mn2Sn0.5Ga0.5的262 K和46.7 emu/g,这表明合金中的磁矩呈亚铁磁形态分布。由于没有磁滞和热滞,室温附近较大的工作温度区间,因此,该材料在磁制冷领域具有很好的应用前景。     

First-Principles Investigation on Phase Stability,Elastic and Magnetic Properties of Boron Doping in Ni-Mn-Ti Alloy

The all-d-metal Ni-Mn-Ti Heusler alloy has giant elastocaloric effect and excellent mechanical properties, which is different from the conventional Ni-Mn-based Heusler alloys. In this work, the preferred site occupation, phase stability, martensitic transformation, magnetic properties, and electronic structure of the B-doped Ni₂Mn_1.5Ti_0.5 alloys are systematically investigated by the first-principles calculations. The results show that B atoms preferentially occupy the octahedral interstitial. The doped B atoms tend to exist in the (Ni₂Mn_1.5Ti_0.5)_1-xB_x (x = 0.03, 0.06, 0.09) alloy in the form of aggregation distribution, and the martensitic transformation temperature decreases with the increase in the B content. For octahedral interstitial doping, the toughness and plasticity of the (Ni₂Mn_1.5Ti_0.5)_1-xB_x alloys decrease, but the strength and rigidity are greatly enhanced. This is because a small part of the d-d hybridization in ternary Ni-Mn-Ti alloy is replaced by the p-d hybridization in Ni-Mn-Ti-B alloy.     

Giant magnetocaloric effect in a Heusler Mn50Ni40In10 unidirectional crystal

A modified high-pressure optical zone-melting technique was used to grow a Mn-rich Heusler Mn₅₀Ni₄₀In₁₀ unidirectional crystal. Experimental results showed that the produced unidirectional crystal underwent a magnetic transition in austenite, followed with a martensitic transformation from a ferromagnetic austenite to a ferromagnetic martensite upon cooling. Under a magnetic field change of 30 kOe, the total effective refrigeration capacities (RC_total) reached as high as 231.58 J/kg when the magnetic field was applied along parallel to the crystal growth direction, or 246.79 J/kg when the magnetic field was applied along perpendicular to the crystal growth direction. It was suggested that this unidirectional crystal growing technique may provide an effective approach to enhance the magnetocaloric effect of Mn-rich Heusler materials.     

Crystal structural transformation accompanied by magnetic transition in MnCo1−xFexGe alloys

The effects of Fe-doping on the crystal structure and martensitic transformation (MT) temperature in MnCoGe alloy have been investigated by using x-ray diffraction, calorimetry and magnetic measurements. Substitution of Fe for Co atoms can stabilize the parent phase and significantly lower the MT temperature of the MnCoGe alloy. By tuning the Fe content, the magnetostructural transition from paramagnetic parent phase (i.e. austenite) with a Ni₂In-type hexagonal structure to ferromagnetic TiNiSi-type martensite can be realized in a temperature window determined by the Curie temperature of the austenite and that of the martensite. A large difference in magnetization between the austenite and martensite, accompanied by the magnetostructural coupling, gives rise to the magnetic-field-induced temperature shift of MT, which makes the MnCo_1−xFe_xGe alloys being a new kind of potential magnetic functional materials used as the magnetic-field-driven actuator or magnetic refrigeration material.     

Ni48Mn33Ga19合金的马氏体相变和磁性形状记忆效应

铁磁性Heusler型合金Ni2MnGa是近年来开发的新型磁控制功能材料，但其马氏体相变温度通常远远低于室温，不利于实际应用。本文研究了多晶Ni48Mn33Ga19合金的马氏体相变特征，发现该合金的马氏体相变温度已提高到室温以上。在室温下，分别测量了不同条件下制备的试样的磁场诱发应变，提出了增大材料磁致应变的有效方法。     

MAGNETIC--FIELD--CONTROLLED SHAPE MEMORY EFFECT AND SUPERELASTICITY OF Ni53.2Mn22.6Ga24.2 SINGLE CRYSTAL

证实了Ni_53.2Mn_22.6Ga_24.2单晶发生的两步马氏体相变行为是完全热弹性的. 在磁场作用下, 该材料的马氏体相变和中间马氏体相变展现出相同的应变特征, 且具有磁控双向形状记忆效应. 磁场下应力--应变特性的测量结果表明, 磁场不但对压应力诱发马氏体相变过程中变体重取向所需应力的大小有影响, 而且使原来不可逆的形变成为可逆, 这种磁控超弹性特性预示了该合金用作磁控超弹性元器件材料的可能性.     

Influence of anisotropy, the latent heat and the thermal history of alloy on martensitic transformation strain in Ni3Ta single crystal

Transformation characteristics in the single crystal of Ni₃Ta shape memory alloy were studied by the dilatation measurement in the temperature range of room temperature up to 500 °C. The transformation strains were positive in the direction of the b-axes and the c-axes and negative in the direction of a-axes. The martensitic phase transformation takes place without volume change of the sample. Thermal diffusivity of the single crystal measured in two directions b-axes and a-axes was higher than that for polycrystalline material.The latent heat of the martensitic phase transformation influences the temperature distribution inside sample. Absorption (releasing) of the latent heat during heating (cooling) leads to cooling (heating) of the sample in place where the phase transformation takes place. This decrease (increase) of the temperature in the interface between both phases leads to stopping of the phase transformation. This effect is visible on the temperature dependence of the dilatation characteristics. The martensitic phase transformation in Ni₃Ta single crystal took place with hysteresis of 30 °C. This hysteresis changes depending on the thermal history of the sample. Hysteretic behaviour of the Ni₃Ta single crystal was analyzed and compared with behaviour of Ni_53.6Mn_27.1Ga_19.3 alloy where no hysteresis was found.     

Site preference,electronic structure and possible martensitic transformation in Heusler alloys Ni2CoZ (Z = Al,Ga, In,Si, Ge,Sn, Sb)

The site preference, electronic structure, magnetic properties and martensitic transformation in Heusler alloys Ni₂CoZ (Z = Al, Ga, In, Si, Ge, Sn, Sb) have been investigated by first-principles calculations. Different from literature, it is found that these Ni₂CoZ alloys tend to form XA structure (Hg₂CuTi-type), except for Ni₂CoIn, in which L2₁ (Cu₂MnAl-type) structure is preferable. Theoretical calculation reveals that the tetragonal martensitic phase has a lower total energy compared with the cubic austenitic phase, therefore, a structural transition from cubic to tetragonal is likely to happen in these Ni₂CoZ alloys. The largest energy difference is observed in Ni₂CoIn. It is interesting that Ni₂CoSi is paramagnetic in austenitic state, while is ferromagnetic in martensitic state. This leads to a large change in the total moment, which is meaningful for the realization of magnetic field-induced martensitic transformation in this alloy.     

第一性原理在Ni_2MnGa合金研究中的应用

具有铁磁性形状记忆效应的Heusler合金Ni_2MnGa颇具发展潜力,在新型智能材料的研究中备受关注。本文综述了第一性原理在Ni_2MnGa合金的四方变形、声子软化和磁性能等方面的研究进展,Ni、Ti和Co等掺杂元素在Ni_2MnGa合金中的最优占位及其对电子结构、马氏体转变温度TM和居里温度TC的影响。     

In situ TEM observation of two-step martensitic transformation in aged NiTi shape memory alloy

Martensitic transformation was investigated in an aged NiTi alloy with DSC and a temperature controllable TEM specimen stage to observe the influence of Ti₁₁Ni₁₄ precipitates and R-phase on martensitic transformation in situ. The R-phase, conventional martensitic twins, and a new morphology of interwoven austenite/martensitic structure were observed.     

Grain size effect on the martensitic transformation of Ni50Mn25Ga17Cu8 high-temperature shape memory alloy

Single crystal, coarse-grained and fine-grained polycrystals of Ni₅₀Mn₂₅Ga₁₇Cu₈ high-temperature shape memory alloy were prepared. Grain size effect on the martensitic transformation was investigated. Compared with the single crystal, the martensitic transformation temperatures were slightly decreased by coarse grains, but were greatly decreased by fine grains. Strong grain size dependence of the kinetics of the martensitic transformation was monitored. The average activation energy of the transformation required for the fine-grained polycrystal was nearly four times of that for the single crystal.