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.     

Microstructure changes in two phase β+ γ Co-Ni-Al ferromagnetic shape memory alloys in relation to Al/Co ratio

The microstructure of Co_{35 + x}-Ni_{40 - x}-Al₂₅ (x = 0, 2.5, 5.0) ferromagnetic shape memory alloys annealed at 1200 °C and water quenched has been investigated by optical (OM) and analytical transmission electron microscopy (TEM). The microstructure consists of elongated grains of martensite and γ phase. Annealing twins were found frequently in the γ phase. The volume fraction of γ phase has been determined to be about 40%. TEM observations show twinned L1₀ martensite with {111}-type twinning plane and tetragonality c/a = 0.85 in all investigated alloys. Determination of the composition of β phase, allows to calculate Al/Co and e/a ratio in the range 7.68–8.40 in correlation with its Ms temperatures between 66 and 167 °C, respectively. An increase in the Al/Co ratio together with a decrease of Ni content in β phase causes a decrease of the e/a ratio, which promotes a decrease of martensitic transformation temperatures.     

The large low-field magnetic entropy changes in Ni43Mn46Sn11−xSbx alloys

A series of Ni₄₃Mn₄₆Sn_11−xSb_x (x=0, 1, and 3) alloys were prepared by an arc melting method. The martensitic transition shifts to higher temperature with the increasing Sb content. The isothermal magnetization curves and Arrott plots around martensitic transition temperatures show a typical metamagnetic behavior. Under a low applied magnetic field of 10 kOe, large magnetic entropy changes around the martensitic transition temperature are 10.4, 8.9, and 7.3 J/kg K, for x=0, 1, and 3, respectively. The origin of the large magnetic entropy changes and potential application for Ni₄₃Mn₄₆Sn_11−xSb_x alloys as working substances in magnetic refrigeration are discussed.     

Magnetic properties of nonstoichiometric Ni<Subscript>2</Subscript>MnIn Heusler alloys

Results from studies of the crystal structure, resistivity, susceptibility, and magnetization of nonstoichiometric Ni₅₀Mn_{50 − x} In _x Heusler alloys are presented. Anomalous effects discovered in temperature dependences can be interpreted as the influence of the frustrated magnetic state exhibited by manganese moments in the martensitic phase. A field-induced phase transition to the austenitic phase was observed for several concentrations around room temperature.     

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)     

Ferromagnetic resonance in Ni-Mn-Ga thin films and thin-film tubes

We report on FMR experiments performed for the first time on thin Ni-Mn-Ga films clamped to the mica substrates and then fully released from them. The aim is to evaluate the role of magnetoelastic coupling in stressed Ni-Mn-Ga Heusler alloy films that undergo martensitic transformation. The experimental results show that the difference in the effective magnetization 4π(M_eff ^tubes-M_eff ^films) is negligible in the austenite phase and it increases to about 1–1.5 kG at temperatures well below the martensitic transformation. The data suggests that magnetoelastic coupling in the martensite phase of Ni-Mn-Ga thin films is typical of normal thin magnetic films with magnetostriction of about 50 ppm.     

Crystal quality boosts responsiveness of magnetic shape memory single crystals

Magnetic shape memory alloys are promising materials to replace giant magnetostrictive materials and piezoelectrical ceramics in actuating devices due to the large magnetically induced strains. Ni-Mn-Ga is the most intense studied system due to its relatively high operational temperatures and the huge magnetically induced strains reported. Up to now the application of these materials is still limited by the operational temperature range. Additionally twin boundary mobility suffers from structural defects increasing the magnetic fields needed for significant and reproducible strains. The sample quality is affected by crystal inhomogeneity, porosity and impurities. Here new results are reported for the Ni-Mn-Ga class based on a set of single crystals grown by the SLARE method, recently developed by Mecklenburg et al. Single crystalline samples of Ni_49.7Mn_29.3Ga₂₁ of tetragonal martensitic structure exhibit a magnetic field induced strain of more than 4% below 170 mT and 6.5% at only 340 mT. Furthermore the operational temperature regimen could be expanded up to 65 °C.     

Advances in single crystal growth and annealing treatment of electron-doped HTSC

High quality electron-doped HTSC single crystals of Pr_2−xCe_xCuO_4+δ and Nd_2−xCe_xCuO_4+δ have been successfully grown by the container-free traveling solvent floating zone technique. The optimally doped Pr_2−xCe_xCuO_4+δ and Nd_2−xCe_xCuO_4+δ crystals have transition temperatures T _c of 25 K and 23.5 K, respectively, with a transition width of less than 1 K. We found a strong dependence of the optimal growth parameters on the Ce content x. We discuss the optimization of the post-growth annealing treatment of the samples, the doping extension of the superconducting dome for both compounds as well as the role of excess oxygen. The absolute oxygen content of the as-grown crystals is determined from thermogravimetric experiments and is found to be ≥ 4.0. This oxygen surplus is nearly completely removed by a post-growth annealing treatment. The reduction process is reversible as demonstrated by magnetization measurements. In as-grown samples the excess oxygen resides on the apical site O(3). This apical oxygen has nearly no doping effect, but rather influences the evolution of superconductivity by inducing additional disorder in the CuO₂ layers. The very high crystal quality of Nd_2−xCe_xCuO_4+δ is particularly manifest in magnetic quantum oscillations observed on several samples at different doping levels. They provide a unique opportunity of studying the Fermi surface and its dependence on the carrier concentration in the bulk of the crystals.     

Structural and magnetic phases of Bi<Subscript>1−x</Subscript>A<Subscript>x</Subscript>FeO<Subscript>3−</Subscript><Subscript>δ</Subscript> (A = Sr,Pb) perovskites

The Bi_1−xA_xFeO_{3− δ} (A = Sr, Pb) systems have been studied using the X-ray, neutron powder diffraction and magnetization measurements in a magnetic field up to 14 T. It was found that around x ∼ 0.06 the crystal symmetry changes from a rhombohedral (space group R3c) to pseudo-tetragonal. In the composition range 0.07 ≤ x ≤ 0.14 the phases with different symmetry of the unit cell coexist independent of synthesis conditions. The neutron powder diffraction shows that the iron ions have average oxidation state close to 3+. The magnetic structure for Bi_0.5Sr_0.5FeO_{3− δ} is found to be G-type antiferromagnetic with magnetic moment of about 3.8 μ_B/Fe³⁺. The weak ferromagnetic state due to magnetoelectric interactions was revealed in the lightly doped rhombohedrally distorted compositions. No evidence for a spontaneous magnetization was observed for the pseudo-tetragonal phases. These compositions show irreversible nonlinear magnetization vs. field behavior apparently due to small local deviations from the collinearity of the magnetic moments.     

Characterization of preferential orientation of martensitic variants in a single crystal of NiMnGa

We report the detailed observation of martensitic variants in NiMnGa single crystals. The variants that are twinned with each other in different ways can be clearly identified in our single crystals by optical observation. We also investigated the preferential orientation of the martensitic variants in NiMnGa single crystals. We observed the motion of the variant boundary in response to application of a magnetic field. This observation can be used to explain phenomenologically the magnetic-field-induced strain. In the single crystal with composition Ni₅₂Mn₂₄Ga₂₄, martensite with seven modulated layers (7M) shows preferentially oriented variants. A completely recoverable two-way shape-memory behavior was also observed by measuring the free sample in three different directions during a complete temperature cycle. It was found that the largest strains in the [001] and [010] directions occur in different temperature ranges.     

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.     

Mesoscopic structure of Ni<Subscript>2 + <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ga alloys in the concentration range corresponding to a coupled magnetic-structural phase stransition

The Ni_{2 + x} Mn_{1 − x} Ga magnetic shape memory alloys at concentrations x = 0.18–0.36 have been studied using small-angle polarized neutron scattering in magnetic fields 0 < H ≤ 5.7 kOe. In this concentration range, the alloy undergoes a coupled magnetic-structural phase transition. At x < 0.18, the martensitic phase transition occurs, as usual, in the ferromagnetic state, i.e., T _m < T _C (T _m and T _C are the temperatures of the martensitic and magnetic phase transitions, respectively). However, at x > 0.27, the relationship between the characteristic temperatures is changed, i.e., T _m > T _C. The small-angle polarized neutron scattering data indicate that, in the concentration range under investigation, there occurs a complex transformation of the magnetic and atomic structures. All phase transitions exhibit a temperature hysteresis of scattering and polarization, which is characteristic of first-order phase transitions. A comparative analysis of the mesoscopic structures of the Ni_{2 + x} Mn_{1 − x} Ga and Ni_{2 + x + y} Mn_{1 − x} Ga_{1 − y} alloys studied using the small-angle polarized neutron scattering technique has been carried out.     

Transformation behavior of Ni-Mn-Ga/Si(100) thin film composites with different film thicknesses

A series of Ni_51.4Mn_28.3Ga_20.3/Si(100) thin film composites with different film thicknesses varying from 0.1 to 5 μm have been prepared by magnetron sputtering and subsequently annealed. X-ray powder diffraction patterns of the films show the features associated with the lattice-modulated martensitic phase and/or cubic austenite at room temperature. 220-fiber texture was confirmed by the X-rays measurements made at 150 °C. While the Curie temperature is almost film thickness independent, the martensitic transformation temperature shows a strong descended dependence in the submicron range. The substrate curvature measurements demonstrate that the forward and reverse martensitic transformation in the films is accompanied by the reversible relaxation and accumulation of residual stress, originally created by the thermal treatment due to the difference in thermal expansion of the film and substrate. The values of residual stresses measured by both substrate curvature and X-rays diffraction methods at constant temperatures are found to be dependent on the film thickness. This behavior appears in correlation with the thickness dependence of the transformation temperature.     

Behavior of the nickel-titanium alloys with the shape memory effect under conditions of shock wave loading

The behavior of the Ti_51.1Ni_48.9 and Ti_49.4Ni_50.6 alloys with shape memory effects has been studied under submicrosecond shock wave loading in the temperature range from −80 to 160°C, which includes both the regions of the stable state of the specimens in the austenite and martensite phases and the regions of thermoelastic martensitic transformations. The grain size of the studied alloys varies from initial values 15–30 to 0.05–0.30 μm. The dependences of the dynamic elastic limit on the temperature and on the elemental composition are similar to the dependences of the yield stress of these alloys under low strain rate loading. The rarefaction shock wave formation as a consequence of the pseudoelastic behavior of the alloy during a reversible martensitic transformation has been revealed. A decrease in the grain size leads to an increase in the dynamic elastic limit and decreases the temperatures of martensitic transformations.     

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.     

Microwave and MM-wave magnetoelectric interactions in ferrite-ferroelectric bilayers

Measurements of the strength of magnetoelectric (ME) interactions at microwave and millimeter-wave frequencies have been carried out on layered ferrite-piezoelectric oxides. An electric field E applied to the composite produces a mechanical deformation, resulting in a field shift δH_E or a frequency shift δf_E in the resonance. A stripline structure or a cavity resonator was used. The strength of ME coupling is obtained from data on δH_E or δf_E vs. E. Studies were performed at 1–110 GHz on bilayers of single crystal nickel zinc ferrite or hexagonal ferrites and single crystal lead magnesium niobate-lead titanate, lead zinc niobate-lead titanate or polycrystalline lead zirconium titanate. The coupling strength has been found to be dependent on the nature of piezoelectric phase, magnetic field orientation and volume for both phases. The ME coupling strength is on the order of 1–2 Oe cm/kV (or 3–6 MHz cm/kV) and is an order of magnitude stronger than in polycrystalline ferrite-piezoelectric bilayers. The high frequency ME effect is of importance for dual electric and magnetic field tunable ferrite-piezoelectric devices.     

Effect of deformation on structure and mechanical behavior of polycrystalline Ni-Mn-Ga alloys

Deformation of polycrystalline Ni-Mn-Ga alloys was studied for both the L2₁ parent phase and 10 M martensitic state. The effect of deformation by compression up to the fracture on mechanical behavior and structure change was studied for the inhomogeneous as-cast state and after annealing at 900^○C for 50 hours. The structure, after deformation of the parent phase, observed by TEM reveals the presence of 10 M and 14 M martensite in the matrix, whereas the deformation of 10 M martensite does not show the change of the structure type. The stress-strain curves were analyzed and compared with the earlier published results.     

Ni2MnGa单晶马氏体相变过程摩擦耗能的热动力学计算

根据相界面摩擦原理，在推导出计算Ni₂MnGa系统热动力学参量的一般表示式的基础上，结合马氏体相变温度分别在室温以下、室温附近、室温以上三种非正配分比Ni₂MnGa单晶自发相变应变和交流磁化率随温度变化的测量结果，计算了三种样品马氏体相变过程中界面摩擦所消耗的能量.结果进一步表明正是相变过程中的界面摩擦导致了相变的热滞后，而三种样品马氏体相变过程的摩擦耗能和相变热滞后存在较大差别的原因在于三种样品马氏体相变生成物具有不同的结构. 关键词： 马氏体相变 应变 界面摩擦     

Effect of alloying on the structure and phase transformations in Ni-Mn alloys alloyed by titanium

The crystal structure of NiMn alloy alloyed by titanium in a wide range of temperatures and compositions has been investigated using resistivity measurements, transmission electron microscopy, electron diffraction, and X ray diffraction. It is found that alloying by titanium not only decreases the martensitic transformation temperature but also changes the martensite crystal structure. The martensitic transformation temperatures are determined and the diagram of martensitic transformations for Ni₅₀Mn_{50 ? x} Ti _x alloys is constructed.