Grain oriented NiMnSn and NiMnIn Heusler alloys ribbons produced by melt spinning: Martensitic transformation and magnetic properties

We outline the microstructural, martensitic transformation and magnetic properties of Heusler alloys with starting compositions Ni₅₀Mn₃₇Sn₁₃, Ni₅₀Mn₃₆In₁₄, and Mn₅₀Ni₄₀In₁₀, produced by melt spinning. The ribbons were obtained in argon environment at a high wheel linear speed of 48 m s⁻¹ (typical dimensions: 1.2-2.0 mm in width, 4-12 mm in length, and 7-12 μm in thickness). EDS microanalysis showed that the resulting average elemental chemical composition is slightly shifted with respect to the starting one. Ribbons are fully crystalline and tend to show a highly ordered columnar-like microstructure with grains running through the entire ribbon thickness; the larger dimension of the grains is perpendicular to the ribbon plane. As-spun alloys were single-phase with ferromagnetic bcc L2₁ austenite as high-temperature parent phase. At low temperatures austenite transforms into a structurally modulated martensite with a lattice symmetry that depends on the system (7 M orthorhombic for Ni₅₀Mn₃₇Sn₁₃, 10 M monoclinic for Ni₅₀Mn₃₆In₁₄, and 14 M monoclinic for Mn₅₀Ni₄₀In₁₀). Magnetization isotherms measured in the temperature interval where martensite thermally transforms into austenite confirmed the occurrence of field-induced reverse martensitic transition in the alloys studied.     

Effect of Fe substitution on the phase stability and magnetic properties of Mn-rich Ni-Mn-Ga ferromagnetic shape memory alloys

The influence of Fe additions on the martensitic transformation and magnetic properties of Mn-rich Ni-Mn-Ga alloys was investigated by substituting either 1 at% Fe for each atomic species or by substituting Ni with varying amounts of Fe. The magnetic structure of the alloys was studied using ⁵⁷Fe Mössbauer spectroscopy. Mössbauer spectra revealed typical paramagnetic features in Mn-rich Ni-Mn-Ga-Fe alloys owing to the preferential site occupancy of Fe atoms at Ni sites. The evolution of the magnetic properties and phase stability has been correlated with the chemical and atomic ordering in these alloys.     

Intermartensitic transformation and magnetic field effect in NiMnInSb ferromagnetic shape memory alloys

Partially substituting Sb for In, we found an irreversible transformation of martensite to intermartensite at 90 K in Ni₅₀Mn₃₄In₁₂Sb₄ alloy during heating. The reverse transformation of martensite and intermartensite to the parent phase induced by a magnetic field has been investigated. The results indicate that, if a sufficiently high magnetic field is applied, the intermartensite state is no longer necessary as an intermediate state. Thus, a difference of the transformation originating from magnetic and from thermal energies has been found. In this competition, lattice distortions play an important role to promote the occurrence of the intermediate intermartensitic path.     

Effect of Al doping on the martensitic transition and magnetic entropy change in Ni-Mn-Sn alloys

Effect of Al doping on the martensitic transition and magnetic entropy change in Mn₅₀Ni₄₀Sn_10−xAl_x was investigated. The experimental results show that the martensitic transition temperatures increase with the increase of Al content due to cell contraction, while the martensitic transition temperature range decreases rapidly. Mn₅₀Ni₄₀Sn₈Al₂ alloy has the largest value of  (3.14 J/kg K) for the magnetic field changing from 0 to 10 kOe, which is nearly twice as large as that of Mn₅₀Ni₄₀Sn₁₀ alloy. It is demonstrated that a larger can be obtained due to the sharper magnetization change around martensitic transition.     

Effect of heat treatment procedure on magnetic and magnetocaloric properties of Ni43Mn46In11 melt spun ribbons

The effect of heat treatment on the structural, magnetic and magnetocaloric properties of Ni₄₃Mn₄₆In₁₁ melt-spun ribbons was systematically investigated using X-ray powder diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM), magnetic force microscope (MFM) and magnetic measurements. From the XRD studies, tetragonal and cubic phases were detected at room temperature for as-spun, quenched and slow-cooled ribbons. Furthermore, it was observed, upon annealing martensite transition temperatures increased when compared to the as-spun ribbon. To avoid magnetic hysteresis losses in the vicinity of the structural transition region, the magnetic entropy changes-ΔS _m of the investigated ribbons were evaluated from temperature-dependent magnetisation-M(T) curves on cooling for different applied magnetic fields. The maximum ΔS _m value was found to be 6.79 J kg^?1 K^?1 for the quenched ribbon in the vicinity of structural transition region for a magnetic field change of 50 kOe.     

Enhanced magnetoresistance through magnetic-field-induced phase transition in Ni2MnGa co-doped with Co and Mn

We report the observation of giant negative magnetoresistance up to −46% at 60 kOe magnetic field in Ni_1.68Co_0.32Mn_1.20Ga_0.80 alloy, which is about 5 times larger than that reported in Ni-Mn-Ga alloys. The significant change in resistivity during martensitic transformation originates from the altered electronic structure due to the change of magnetic state. The magnetic-field-induced phase transition from partially antiferromagnetic martensite to ferromagnetic austenite is responsible for the enhanced magnetoresistance.     

Effect of Sn doping on the martensitic and premartensitic transitions in Ni2MnGa

The effect of Sn doping at the Ga site of Ni₂MnGa is investigated through magnetic and magneto-transport measurements. Clear signatures of martensitic and premartensitic transitions are observed in the pure as well as in 5% Sn doped alloy. For 10% Sn doping, the martensitic transition vanishes, while the premartensitic transition remains visible at low temperature. All the samples are found to have a ferromagnetic ground state with saturation moment decreasing with increasing Sn concentration. The magnetocaloric effect near the martensitic transition in the pure and 5% Sn doped samples is found to be positive. However, the entropy change is found to decrease with increasing magnetic field, which is particularly prominent in the undoped sample. The samples also show negative magnetoresistance with anomalies at the martensitic and premartensitic transition points.     

Effect of Al substitution for B on magnetic and structural properties of Co-based melt-spun ribbons

This paper reports structural and magnetic properties of rapidly quenched Co₆₄Fe₄Ni₂B_19−xSi₈Cr₃Al_x (x=0, 1, 2, 3) amorphous ribbons prepared by the single roller melt spinning process. Thermal analysis of the ribbons shows that the replacement of B by Al causes a decrease in the crystallization temperature. Structural studies of the samples have been carried out by transmission electron microscopy and X-ray diffraction. With optimum amount of Al in the alloy, the as-cast material has better soft magnetic properties. The highest maximum permeability (3.55×10⁵), saturation magnetization (523.7 mT) and the lowest coercivity (0.8174 A/m) were obtained in the sample with x=2.     

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.     

Phase transitions and the magnetocaloric effect in Mn rich Ni–Mn–Ga Heusler alloys

In Mn rich polycrystalline Heusler alloys, Ni₅₀Mn_25+−xGa_25−x, prepared by Arc melting, it is found that the structural/first-order magnetic transition temperature T_m increases as the Mn content increases. The Curie temperature T_c is higher than that of Ni rich alloys (Ni_50+xMn_25−xGa₂₅ ) of the same series, and is less affected by composition x. Magnetic entropy change of |ΔS_M| also increases as Mn content increases, while behaviour of the field dependence of ΔS_M is similar to that of single crystal Ni_52.6Mn_23.1Ga_24.3.     

Photoemission study of the (1 0 0) surface of Ni2MnGa and Mn2NiGa ferromagnetic shape memory alloys

The (1 0 0) surface of Ni₂MnGa and Mn₂NiGa ferromagnetic shape memory alloys have been studied by photoelectron spectroscopy and low energy electron diffraction (LEED). It is shown that by sputtering and annealing, it is possible to obtain a clean, ordered and stoichiometric surface that shows a four-fold 1 × 1 LEED pattern at room temperature. For both Ni₂MnGa and Mn₂NiGa, the surface becomes Ni-rich and Mn deficient after sputtering. However, as the annealing temperature is increased Mn segregates to the surface and at sufficiently high annealing temperature the Mn deficiency caused by sputtering is compensated. The (1 0 0) surface of Ni₂MnGa is found to have Mn-Ga termination. The valence band spectra of both Ni₂MnGa and Mn₂NiGa exhibits modifications with surface composition. For the stoichiometric surface, the origin of the spectral shape of the valence band is explained by calculations based on first principles density functional theory.     

Cu对Ni50Mn36In14相变和磁性的影响冰

文章研究了Cu替代部分Ni对铁磁性形状记忆合金Ni50Mn36In14相变和磁性的影响规律．研究表明,在Ni50-χcCuχMn36In14中,随着Cu含量的增加,相变温度逐渐降低．Cu含量低于5％时。奥氏体的磁性强于马氏体的磁性,母相和马氏体相的饱和磁化强度的差值△M随着Cu含量的增加而增大．当Cu含量χ=4．5时,△M迅速增加到80emu／g,并在该材料中观察到了磁场驱动的马氏体到奥氏体的转变,显示了该材料作为磁驱动磁电阻材料的潜在应用前景．当Cu含量高于5％时,奥氏体保持铁磁状态,马氏体相由反铁磁状态变为铁磁状态,马氏体的磁性强于奥氏体的磁性,△M大大削弱,磁场驱动性质消失．     

Stress analysis, structure and magnetic properties of sputter deposited Ni-Mn-Ga ferromagnetic shape memory thin films

The residual stress instituted in Ni-Mn-Ga thin films during deposition is a key parameter influencing their shape memory applications by affecting its structural and magnetic properties. A series of Ni-Mn-Ga thin films were prepared by dc magnetron sputtering on Si(1 0 0) and glass substrates at four different sputtering powers of 25, 45, 75 and 100 W for systematic investigation of the residual stress and its effect on structure and magnetic properties. The residual stresses in thin films were characterized by a laser scanning technique. The as-deposited films were annealed at 600 °C for 1 h in vacuum for structural and magnetic ordering. The compressive stresses observed in as-deposited films transformed into tensile stresses upon annealing. The annealed films were found to be crystalline and possess mixed phases of both austenite and martensite, exhibiting good soft magnetic properties. It was found that the increase of sputtering power induced coarsening in thin films. Typical saturation magnetization and coercivity values were found to be 330 emu/cm³ and 215 Oe, respectively. The films deposited at 75 and 100 W display both structural and magnetic transitions above room temperature.     

定向凝固生长对Ni-Mn-Ga-RE (RE=TbSm)合金磁感生应变的影响

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Ga含量对Mn2-xNiGa1+x结构和磁性的影响

系统研究了铁磁性形状记忆合金Mn_{2 -x}NiGa_1+x的结构、磁性和有序化转变. 研究表明: 随着Ga含量的增加, Mn_{2 -x}NiGa_1+x的母相结构由Hg₂CuTi 型逐渐转变到Cu₂MnAl型Heusler结构. 母相的晶格常数先增加后降低, 当x=0.3时达到最大值. 0.3 ≤x ≤0.8时, 材料除呈现Heusler结构的主相之外, 还出现了Ni₂In型六角相. 过渡金属中3d电子之间交换相互作用的减弱, 导致Mn_2-xNiGa_1+x主相的居里温度由Mn₂NiGa的590 K逐渐降低至Ga₂MnNi的220 K左右; 当x=0.6–0.8时, Ni₂In型六角相的居里温度与主相的居里温度出现分离. Ga对Mn的替代引起合金中原子间耦合作用的变化, 导致低温下Mn_{2 -x}NiGa_1+x的饱和磁化强度先增加后降低, 即x≤0.4时呈上升趋势, x>0.4时急剧下降. 差热分析结果显示, 随着x从0增加到1, 样品熔化温度逐渐降低, B2相到Heusler相的转变温度先降低后增加.     

Martensitic phase transition with magnetocaloric effect and double-shifted exchange bias in the martensitic phase for Ni48Mn39Sn13-xGex alloys

Ni₄₈Mn₃₉Sn_13-xGe_x (x?=?1, 2) Heusler alloys have been prepared, and the martensitic phase transition (MPT), magnetocaloric effect and exchange bias (EB) have been explored. At room temperature, the structure of both samples presents L2₁ type, and the MPT shifts to a higher temperature, while the Curie temperature (T_C) of the austenitic phase decreases with the increase of the Ge content. The maximum magnetic entropy change of Ni₄₈Mn₃₉Sn_13-xGe_x with x?=?2 reaches about 14.67?J/kg?K under the magnetic field of 5?T during reverse MPT. In addition, an interesting phenomenon is the enhancement of EB with the increase of the Ge content, especially the abnormal presence of the double-shifted hysteresis loop has been realized in Ni₄₈Mn₃₉Sn_13-xGe_x with x?=?2, which can be interpreted by the fact that the antiferromagnetic (AFM) regions couple with proximal ferromagnetic (FM) regions in the opposite way at low temperature.     

等温退火对辐照诱发的非晶TiNiCu合金微观组织结构的影响

 TiNiCu记忆合金在美国Argonne国家实验室IVEM Tandem National Facility加速器产生的400keV Xe+离子辐照到0.4dpa时发生非晶化转变。通过电子显微镜研究了非晶化的TiNiCu合金的回复和再结晶过程。退火加热的速度是10℃/min。在280℃时非晶环附近出现电子衍射斑点以及明场像中出现少量析出相，表明回复和再结晶开始。退火到550℃出现多晶环，650℃时有片状马氏体变体生成，750℃时有很锐利的多晶环出现，表明再结晶过程基本完成。经标定再结晶晶粒仍然是TiNiCu记忆合金。再结晶组织与辐照前TiNiCu 合金的显微组织相比有较大差异。     

等温退火对辐照诱发的非晶TiNiCu合金微观组织结构的影响

TiNiCu记忆合金在美国Argonne国家实验室IVEM Tandem National Facility加速器产生的400keV Xe+离子辐照到0.4dpa时发生非晶化转变。通过电子显微镜研究了非晶化的TiNiCu合金的回复和再结晶过程。退火加热的速度是10℃/min。在280℃时非晶环附近出现电子衍射斑点以及明场像中出现少量析出相,表明回复和再结晶开始。退火到550℃出现多晶环,650℃时有片状马氏体变体生成,750℃时有很锐利的多晶环出现,表明再结晶过程基本完成。经标定再结晶晶粒仍然是TiNiCu记忆合金。再结晶组织与辐照前TiNiCu 合金的显微组织相比有较大差异。     

Magnetic properties, phase evolution, and microstructure of melt spun Sm(Co1−zZrz)xCy (x=5-9; y=0-0.15; z=0.03 and 0.06) ribbons

Magnetic properties, phase evolution, and microstructure of melt spun Zr-substituted Sm(Co_1−zZr_z)_xC_y (x=5-9; y=0-0.15; z=0.03 and 0.06) ribbons quenched at the wheel speed of 40 m/s have been studied. The x-ray diffraction analysis showed that the main phases, found in Sm(Co_0.97Zr_0.03)_x ribbons, were 1:5 phase for x=5-5.5; 1:5 and 1:7 phases for x=6; 1:7 phase for x=6.5-7.5; 1:7 and 2:17 phases for x=8; and only 2:17 phase for x=8.5-9, respectively. For Sm(Co_0.97Zr_0.03)_x ribbons, the attractive magnetic properties of remanent magnetization (B_r) of 5.5 kG, intrinsic coercivity (_iH_c) of 9.5 kOe, and energy product ((BH)_max) of 7.0 MGOe were obtained for Sm(Co_0.97Zr_0.03)_6.5 ribbons. Furthermore, a slight amount of C addition in Sm(Co_0.97Zr_0.03)_x ribbons could not only effectively refine the grain size from 200 to 500 nm for C-free ribbon to 10-70 nm for C-added ribbons, but also bring extremely fine fcc-Co grains (2-10 nm), leading to the strengthened exchange coupling effect between the magnetic grains. As a result, magnetic properties were further improved. In this study, the optimal magnetic properties of B_r=6.3 kG, _iH_c=10.5 kOe, and (BH)_max=9.0 MGOe were achieved for Sm(Co_0.97Zr_0.03)₇C_0.1 nanocomposites.