哈斯勒合金Ni-Mn-Sn的马氏体相变与反磁热性质

通过结构以及磁性测量,研究了哈斯勒合金Ni₅₀Mn_25+xSn_25-x (x=11,12)的马氏体相变和磁热性质.结果表明,与样品在奥氏体相的磁性不同,由于在马氏体相中反铁磁交换作用的增强,导致铁磁和反铁磁在马氏体状态下共存.此外,通过Maxwell方程,研究了两样品在不同磁场变化下马氏体相变温度附近的反磁热性质,并阐明了该系列合金产生大的正磁熵变(ΔS_M)不仅与其在降温过程中发生马氏体相变所导致的磁跃变(ΔM)有关,而且与发生马氏体相变所经历的温度区间有密切的联系. 关键词： 哈斯勒合金 Ni-Mn-Sn 马氏体相变 正磁熵变     

热磁预处理对Ni-Mn-Ga单晶磁学和力学性能的影响

研究了预先热磁处理对Ni_503Mn_287Ga₂₁单晶的磁学和力学性能的影响.首先将样品加热到居里温度之上让其冷却,冷却方式分为两种：一种是施加一定大小的磁场从高于居里温度冷却至室温,另一种是在样品经历顺磁-铁磁相变后但还未发生奥氏体-马氏体相变前施加相同大小和方向的磁场并冷却至室温.室温时的拉伸-压缩实验结果表明单晶样品在经历前一种处理后,其可逆应变、磁化强度的变化 （ΔM）比后一种处理的相应值要小很多.在后一种热磁处理的样品中,顺磁-铁磁相变发生后形成了自发磁畴,但这种磁畴不具有择优取向.在顺磁-铁磁相变结束后施加磁场,容易导致择优的马氏体准单畴出现,从而表现出大的可逆应变和ΔM.但对于前者,我们认为样品从居里温度降到室温过程中,其中的磁畴在相同的磁场作用下获得择优生长,形成大磁畴,导致磁诱导的强各向异性.这种择优取向的大磁畴在随后马氏体相变期间影响着马氏体的自发排列方式,不利于马氏体准单畴的出现,结果导致较小的可逆应变和ΔM. 关键词： 磁和力学锻炼 Ni-Mn-Ga单晶 铁磁和马氏体相变     

The influence of microstructure on the martensitic transformation in Cu–Zn–Al melt-spun ribbons

The martensitic transformation was investigated in a set of twin roller melt-spun Cu–Zn–Al shape memory alloys, solidified at tangential wheel speeds between 20 and 40 m/s. The resulting microstructures were analyzed using X-ray diffraction, optical and transmission electron microscopy techniques. The characteristic martensitic transformation temperature, M _S, was determined for each condition by conventional resistometric methods. The ribbons are homogeneous in shape and for each quenching rate they exhibit a quite uniform M _S temperature. By proper thermal treatments, the different factors affecting M _S could be separately examined and from temperature measurements, the contribution of L2₁ antiphase boundaries evaluated. A calculation of this contribution using pair interchange energies is in good agreement with the experimental results.     

Magnetic entropy change involving martensitic transition in NiMn-based Heusler alloys

Our recent progress on magnetic entropy change (ΔS) involving martensitic transition in both conventional and metamagnetic NiMn-based Heusler alloys is reviewed. For the conventional alloys, where both martensite and austenite exhibit ferromagnetic (FM) behavior but show differentmagnetic anisotropies, a positive ΔS as large as 4.1 J·kg^-1·K^-1 under a field change of 0–0.9 T was first observed at martensitic transition temperature T_M ~ 197 K. Through adjusting the Ni:Mn:Ga ratio to affect valence electron concentration e/a, T_M was successfully tuned to room temperature, and a large negative ΔS was observed in a single crystal. The -ΔS attained 18.0 J·kg-1·K-1 under a field change of 0–5 T. We also focused on the metamagnetic alloys that show mechanisms different from the conventional ones. It was found that post-annealing in suitable conditions or introducing interstitial H atoms can shift the T_M across a wide temperature range while retaining the strong metamagnetic behavior, and hence, retaining large magnetocaloric effect (MCE) and magnetoresistance (MR). The melt-spun technique can disorder atoms and make the ribbons display a B2 structure, but the metamagnetic behavior, as well as the MCE, becomes weak due to the enhanced saturated magnetization of martensites. We also studied the effect of Fe/Co co-doping in Ni₄₅(Co_1-xFe_x)5Mn36.6In13.4 metamagnetic alloys. Introduction of Fe atoms can assist the conversion of the Mn–Mn coupling from antiferromagnetic to ferromagnetic, thus maintaining the strong metamagnetic behavior and large MCE and MR. Furthermore, a small thermal hysteresis but significant magnetic hysteresis was observed around T_M in Ni₅₁Mn_49-xIn_x metamagnetic systems, which must be related to different nucleation mechanisms of structural transition under different external perturbations.     

Large low-field inverse magnetocaloric effect near room temperature in Ni50−x Mn37+x In13 Heusler alloys

Low field inverse magnetocaloric effect (IMCE) associated with first-order martensitic transition in Ni_50−x Mn_37+x In₁₃ (x=3,4,5) alloys was investigated. By tuning the composition of Ni/Mn, large change in the magnetization occurring between martensite and austenite phases in a narrow temperature interval was achieved, which results in large IMCE. Under low magnetic field change of 2 T, a large positive magnetic entropy change (ΔS _M ) of 23.5 J/kg K with a net refrigeration capacity of 53 J/kg was obtained near room temperature (308 K) in the x=3 alloy. The results show that a small variation in Ni/Mn ratio significantly influences the martensitic transition temperature and the associated magnetic and magnetocaloric properties.     

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.     

Structure, magneto-structural transitions and magnetocaloric properties in Ni50−xMn37+xIn13 melt spun ribbons

Melt spun Ni_50−xMn_37+xIn₁₃ (2≤x≤5) ribbons were investigated for the structure, microstructure, magneto-structural transitions and inverse magnetocaloric effect (IMCE) associated with the first-order martensitic phase transition. The influence of excess Mn in Ni site (or Ni/Mn content) on the martensite transition and the associated magnetic and magnetocaloric properties are discussed. It was found that with the increase in Mn content, the martensitic transition shifted from 325 to 240 K as x is varied from 2 to 4, and the austenite phase was stabilized at room temperature. The x=5 ribbon did not show the martensitic transition. For the x=3 ribbon, the structural and magnetic transitions are close together unlike in the x=4 ribbon in which they are far (∼60 K) apart. The zero field cooled and field cooled curves support the presence of exchange bias blocking temperature due to antiferromagnetic interactions in the ribbons. A large change in the magnetization between the martensite and austenite phases was observed for a small variation in the Ni/Mn content, which resulted in large IMCE. A large positive magnetic entropy change (ΔS_M) of 32 J/kg K at room temperature (∼ 300 K) for a field change of 5 T with a net refrigeration capacity of 64 J/kg was obtained in the Ni₄₇Mn₄₀In₁₃ ribbon.     

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.     

Lattice instability of Ni2MnGa

Anomalies have been detected in the temperature behavior of the physical properties of Ni₂MnGa in the temperature interval preceding the martensitic transformation, which is attributed to TA ₂ phonon mode condensation at T=T _I>T _m (T _m is the martensitic transition temperature). Fiz. Tverd. Tela (St. Petersburg) 39, 557–559 (March 1997)     

Mössbauer study of the martensitic transformation in a Ni–Fe–Ga shape memory alloy

We present the results of an extensive Mössbauer study of the magnetic and martensitic transformation at room temperature of a polycrystalline alloy with a Ni₅₅Fe₁₉Ga₂₆ nominal composition. From calorimetric measurements, we have determined the martensitic transformation temperature of T _M ≈ 240 K, in good agreement with the one obtained by magnetic characterization. This sample has a Curie temperature of T _C ≈ 287 K. Additional Curie temperatures, belonging to a γ phase, have been also detected. Mössbauer spectroscopy performed at different temperatures monitored all these transformations and the fitting of the obtained spectrum at the highest temperature allow us to give percentages of the different phases in the sample.     

Influence of sample geometry on determination of magnetocaloric effect for Gd60Co30Al10 glassy ribbons using direct and indirect methods

Rare-earth based metallic glasses with high saturation magnetization show a sizeable magnetocaloric effect (MCE) and are subject of extensive research concerning magnetic refrigeration materials. In this work, the magnetic phase transition from paramagnetic to ferromagnetic of Gd₆₀Co₃₀Al₁₀ metallic glass has been characterized and three different methods were applied for the determination of its magnetocaloric specific parameters: (a) direct measurement of the adiabatic temperature change by exposing the material to an adiabatically applied magnetic field; (b) determination of the magnetization M(H,T) and calculation of the temperature dependent magnetic field induced entropy change ΔS_m by application of the Maxwell relation and (c) measuring the total heat capacity C_p(H,T) in zero and non-zero magnetic field. Gd₆₀Co₃₀Al₁₀ glassy ribbons were prepared by melt spinning, a technique that offers very high cooling rates due to the low dimensionality of the sample. Depending on the particular method of measurement, pieces of these glassy ribbons form samples with different appropriate total volume and dimensions. We show that the combination of the pronounced two-dimensionality of the ribbon pieces (aspect ratio ∼100) together with the very high magnetic permeability principally can cause strong internal demagnetizing fields that cannot be neglected when evaluating the intrinsic MCE parameters obtained from different methods.     

Research on splitting phenomenon of isochronal martensitic transformation in T91 ferritic steel

T91 steel is a representative type of ferritic heat-resistant steel currently used in power plant components, and is a potential candidate for structural steel in nuclear reactors. The isochronal martensitic transformation behaviors during continuous cooling after austenitization in T91 ferritic steel were systematically investigated by high-resolution dilatometry and microstructure observation. The splitting phenomenon of martensitic transformation is accompanied with the precipitation of needle-like M₃C particles, which is suppressed by rapid cooling after austenitization. The appearance of this splitting is ascribed to the concentration gradient caused by the consumption of alloy element in process of the formation of M₃C. This concentration gradient results in the appearance of wide martensitic laths ahead of the generation of normally narrow laths. These two types of martensitic laths possess different M _s (martensitic start transformation) temperatures, which are attributed to the splitting transformation phenomenon.     

Magnetic and structural phase transitions in the shape-memory ferromagnetic alloys Ni2+x Mn1−x Ga

The results of an experimental investigation of the temperature dependences of the magnetic susceptibility and resistivity in the shape-memory ferromagnetic alloys Ni_2+x Mn_1−x Ga (x=0–0.20) are reported. A T−x phase diagram is constructed on the basis of these data. It is shown that partial substitution of Ni for Mn causes the temperatures of the structural (martensitic) T _M and magnetic T _C (Curie point) phase transitions to converge. In the region where T _C =T _M the transition temperature increases linearly with magnetic field in the range from 0 to 10 kOe. The kinetics of a magnetic-field-induced martensitic phase transition is investigated, and the velocities of the martensite-austenite interphase boundary during direct and reverse transitions are measured. A theoretical model is proposed and the T−x phase diagram is calculated. It is shown that there exist concentration ranges where the magnetic and martensitic transitions merge into a first-order phase transition. The theoretical results are in qualitative agreement with experiment. Zh. éksp. Teor. Fiz. 115, 1740–1755 (May 1999)     

Martensitic transformation and magnetocaloric properties of Sn doping Mn-Ni-Ga alloys

The effects of Sn addition on phase transformation behavior and magnetocaloric properties of Mn₅₀Ni₂₅Ga_25−xSn_x (x=0, 0.1, 0.5, 1 and 2 at%) alloys were investigated in this work. The results show that the addition of Sn reduces the structural transformation temperatures. It is found that the second phase exists in the austenite matrix of the as-casted alloys at room temperature. After being annealed at 1073 K for 48 h, the precipitates totally soluted into the matrix. Magnetization measurements indicate that the saturation magnetizations of the alloys increase significantly with increase in Sn contents. In addition, the ΔM/ΔS obviously increases with increase in the Sn contents, implying the higher efficiency shift of the martensitic transformation temperature under the magnetic field.     

Magnetocaloric properties of as-quenched Ni50.4Mn34.9In14.7 ferromagnetic shape memory alloy ribbons

The temperature dependences of magnetic entropy change and refrigerant capacity have been calculated for a maximum field change of Δ H=30 kOe in as-quenched ribbons of the ferromagnetic shape memory alloy Ni_50.4Mn_34.9In_14.7 around the structural reverse martensitic transformation and magnetic transition of austenite. The ribbons crystallize into a single-phase austenite with the L2₁-type crystal structure and Curie point of 284 K. At 262 K austenite starts its transformation into a 10-layered structurally modulated monoclinic martensite. The first- and second-order character of the structural and magnetic transitions was confirmed by the Arrott plot method. Despite the superior absolute value of the maximum magnetic entropy change obtained in the temperature interval where the reverse martensitic transformation occurs (|\varDelta S_M^max|=7.2 J kg^-1 K^-1)(|\varDelta S_{\mathrm{M}}^{\max}|=7.2\mbox{ J}\,\mbox{kg}^{-1}\,\mbox{K}^{-1}) with respect to that obtained around the ferromagnetic transition of austenite (|\varDelta S_M^max|=2.6 J kg^-1 K^-1)(|\varDelta S_{\mathrm{M}}^{\max}|=2.6\mbox{ J}\,\mbox{kg}^{-1}\,\mbox{K}^{-1}), the large average hysteretic losses due to the effect of the magnetic field on the phase transformation as well as the narrow thermal dependence of the magnetic entropy change make the temperature interval around the ferromagnetic transition of austenite of a higher effective refrigerant capacity (RC^magn_eff=95J kg^-1\mathrm{RC}^{\mathrm{magn}}_{\mathrm{eff}}=95\mbox{J}\,\mbox{kg}^{-1} versus RC^struct_eff=60J kg^-1)\mathrm{RC}^{\mathrm{struct}}_{\mathrm{eff}}=60\mbox{J}\,\mbox{kg}^{-1}).     

哈斯勒合金Ni50Mn35In15的马氏体相变及其磁热效应

利用电弧炉熔炼了Ni₅₀Mn₃₅In₁₅多晶样品,根据磁性测量对其马氏体相变和磁热效应进行了系统研究.结果表明,随着温度的降低,样品在室温附近先后发生了二级磁相变与一级结构相变特征的马氏体相变,导致它的磁化强度产生突变. 同时通过低温下的磁滞回线的测量发现样品存在交换偏置行为,表明低温下马氏体相中铁磁和反铁磁共存. 此外,根据Maxwell方程,计算了样品在马氏体相变温度附近的磁熵变,当温度为309K,磁场改变5 T时,样品的磁熵变可达22.3J/kgK. 关键词： 哈斯勒合金 50Mn₃₅In₁₅')" href="#">Ni₅₀Mn₃₅In₁₅ 马氏体相变 磁热效应     

Magnetocaloric effect in polycrystalline La0.65Ba0.3M0.05MnO3 (M=Na, Ag, K) manganites

The effects of monovalent doping on the crystallographic, magnetic and magnetocaloric properties of La_0.65Ba_0.3M_0.05MnO₃ (M=Na, Ag, K) powder samples, elaborated using the solid state reaction method at high temperature, have been investigated. In our three samples the Mn⁴⁺ amount remains constant equal to 40%. The Rietveld refinement of the X-ray powder diffraction shows that all our synthesized samples are single phase and crystallize in the distorted rhombohedral system with R3¯c space group. All our studied samples undergo a paramagnetic–ferromagnetic transition with decreasing temperature. Using the Arrott plot, the second-order transition Curie temperature T_C for M=Na, Ag and K is found to be 310, 300 and 290 K, respectively. The magnetic entropy change, deduced from isothermal magnetization curves, exhibits a maximum |ΔS_M^Max| of about 2.65, 2.82 and 2.66 J/kg K for M=Na, Ag and K, respectively, in a magnetic applied field change of 5 T. Although these values are modest, the magnetocaloric effect extends over a large temperature range leading to an important value of the relative cooling power (RCP). The RCP values exhibit a nearly linear dependence with the magnetic applied field. The refrigeration capacity in a magnetic applied field of 1 T is found to be 28.8, 27.8 and 25.6 J/kg for M=Na, Ag and K compounds.     

Magnetic properties and magnetic entropy change in Heusler alloys Ni50Mn35?xCuxSn15

The influence of Cu substitution for Mn on magnetic properties and magnetic entropy change has been investigated in Heusler alloys, Ni₅₀Mn_35−x Cu _x Sn₁₅ (x=2,5 and 10). With increasing Cu content from x=2 to x=5, the martensitic transition temperature, T _M , decreases from 220 K to 120 K. Further increasing Cu up to x=10 results in the disappearance of T _M . For samples Ni₅₀Mn₃₃Cu₂Sn₁₅ and Ni₅₀Mn₃₀Cu₅Sn₁₅, both martensitic and austenitic states exhibit ferromagnetic characteristics, but the magnetization of martensitic phase is notably lower than that of austenitic phase. The magnetization difference, ΔM, across the martensitic transition leads to a considerably large Zeeman energy, μ ₀ΔM⋅H, which drives a field-induced metamagnetic transition. Associated with the metamagnetic behavior, a large positive magnetic entropy change ΔS takes place around T _M . For the sample Ni₅₀Mn₃₃Cu₂Sn₁₅,ΔS reaches 13.5 J/kg⋅K under a magnetic field change from 0 to 5 T.     

Heat capacity and the magnetocaloric effect in Pr0.6Sr0.4Mn1–x Fe x O3 manganite

The heat capacity and the magnetocaloric effect of Pr_0.6Sr_0.4Mn_1–xFe_xO₃(x = 0 and 0.1) manganite have been studied in the temperature range 80–350 K and magnetic fields to 18 kOe. The magnetocaloric effect is estimated using two independent methods: the method of magnetic field modulation (direct method) and from the data on the heat capacity in magnetic field and without magnetic field (indirect method). The substitution of Fe atoms for Mn atoms (x = 0.1) shifts T _C by 167 K to lower temperatures; in this case, the magnetocaloric effect (MCE) is changed insignificantly in magnetic field 18 kOe with ΔS _M = 2.05 and 2.31 J/kg K for x = 0 and 0.10, respectively.

     

Thermal stability,magnetic and magnetocaloric properties of Gd55Co35M10 (M = Si,Zr and Nb) melt-spun ribbons

The thermal stability, magnetic and magnetocaloric properties of Gd₅₅Co₃₅M₁₀ (M = Si, Zr and Nb) melts-pun ribbons were studied. The relatively high reduced glass transition temperature (T_x1/T_m > 0.60) and low melting point (T_m) resulted in excellent glass forming ability (GFA). The Curie temperatures (T_C) of melt-spun amorphous ribbons Gd₅₅Co₃₅M₁₀ for M = Si, Zr and Nb were 166, 148 and 173 K, respectively. For a magnetic field change of 2 T, the values of maximum magnetic entropy change (−ΔS_M)^max for Gd₅₅Co₃₅Si₁₀, Gd₅₅Co₃₅Zr₁₀ and Gd₅₅Co₃₅Nb₁₀ were found to be 2.86, 4.28 and 4.05 J kg⁻¹K⁻¹, while the refrigeration capacity (RC) values were 154, 274 and 174 J kg^–1, respectively. The RC_FWHM values of amorphous alloys Gd₅₅Co₃₅M₁₀ (M = Si, Zr and Nb) are comparable to or larger than that of LaFe_11.6Si_1.4 crystalline alloy. Large values of (−ΔS_M)^max and RC along with good thermal stability make Gd₅₅Co₃₅M₁₀ (M = Si, Zr and Nb) amorphous alloys be potential materials for magnetic cooling operating in a wide temperature range from 150 to 175 K, e.g., as part of a gas liquefaction process.