Effect of Fe-substitution on microstructure, hysteresis behaviour and magnetocaloric effect in Gd5Si2Ge2 Alloys

Effect of Fe-substitution on the phase formation, partitioning behaviour of Fe in the co-existing phases, magneto-structural transition, magnetic entropy change and associated hysteresis losses has been investigated in Gd₅Si₂Ge₂ alloy. The virgin alloy crystallizes in monoclinic Gd₅Si₂Ge₂-type phase, while Fe-substituted alloys form mixed monoclinic Gd₅Si₂Ge₂-type and orthorhombic Gd₅Si₄-type phases. Electron probe microanalysis reveals that Fe does not dissolve in the matrix, but influences the magneto-structural transitions. Magneto-structural characterization of the Fe-containing alloys reveals that the Fe-substitution suppresses the structural transition observed at 273 K in virgin alloy. A maximum magnetic entropy change, ΔS_M of 6.5 J/kg-K at 273 K was observed for a field change of 2 T in Gd₅Si₂Ge₂ alloy. The Fe-substituted alloys exhibit lower value of ΔS_M but with reduced hysteresis losses.     

金属间化合物DyMn2Ge2的自发磁相变和场诱导的磁相变

在10—800K的温度范围内用X射线衍射方法测量了DyMn₂Ge₂化合物的晶格常数与温度的变化关系,观察到高温时DyMn₂Ge₂由顺磁状态到反铁磁状态的自发磁相变伴随着晶格常数a的负的磁弹性异常现象.在4.2K—200K的温度范围内测量了DyMn₂Ge₂的交流磁化率.在交换相互作用的分子场模型近似下,从理论上分析讨论了DyMn₂Ge₂的低温自发磁相变和场诱导的磁相变.计算了DyMn₂Ge₂单晶的磁化强度与温度的变化关系以及不同温度下外磁场沿晶轴c方向时的磁化曲线.理论分析和计算结果表明,温度低于33K时在DyMn₂Ge₂中观察到的场诱导的一级磁相变为由亚铁磁状态(Fi)到中间态(IS)相变. 关键词： 稀土-过渡族金属间化合物 磁结构 磁相变     

Magnetic field and temperature-induced first-order transition in Gd5(Si1.5Ge2.5): a study of the electrical resistance behavior

Magnetic field (0–4 T) and temperature dependencies (4.2–320 K) of the electrical resistance of Gd₅(Si_1.5Ge_2.5), which undergoes a reversible first-order ferromagnetic↔paramagnetic phase transition, have been measured. The electrical resistance of Gd₅(Si_1.5Ge_2.5) indicates that the magnetic phase transition can be induced by both temperature and magnetic field. The temperature dependence of the electrical resistance, R(T), for heating at low temperatures in the zero magnetic field has the usual metallic character, but at a critical temperature of T_cr=216 K the resistance shows a 20% negative discontinuity due to the transition from the low-temperature high-resistance state to the high-temperature low-resistance state. The R(T) dependence for cooling shows a similar but positive 25% discontinuity at 198 K. The isothermal magnetic field dependence of the electrical resistance from 212T224 K indicates the presence of temperature-dependent critical magnetic fields which can reversibly transform the paramagnetic phase into the ferromagnetic phase and vice versa. The critical magnetic fields diagram determined from the isothermal magnetic field dependencies of the electrical resistance of Gd₅(Si_1.5Ge_2.5) shows that the FM↔PM transition in zero magnetic field on cooling and heating occurs at 206 and 213 K, respectively. The full isothermal magnetic filed hysteresis for the FM↔PM transition is 2 T, and the isofield temperature gap between critical magnetic fields is 7 K.     

Structure and magnetic entropy change of suck-cast Gd60Co26Al6Ge8 alloy

The Gd₆₀Co₂₆Al₆Ge₈ alloy has been prepared by the copper-mold suck-casting and its phase component has been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). It is shown that this alloy consists of primary crystalline Gd₅Ge₃ phase and amorphous matrix. The glass transition temperature (T_g) and crystallization temperatures (T_x) occur at 292 and 320 °C, respectively. The maximal magnetic entropy change (ΔS_M) under 0-5 T field is about 7.6 J (kg⁻¹ K⁻¹) at 155 K and the refrigeration capacity (RC) is about 768 J kg⁻¹, which makes Gd₆₀Co₂₆Al₆Ge₈ bulk metallic glass matrix composite a promising candidate for magnetic refrigerant.     

Magnetocrystalline anisotropy in RAu2Ge2 (R = La, Ce and Pr) single crystals

Anisotropic magnetic properties of single crystalline RAu₂Ge₂ (R=La, Ce and Pr) compounds are reported. LaAu₂Ge₂ exhibits a Pauli-paramagnetic behaviour whereas CeAu₂Ge₂ and PrAu₂Ge₂ show an antiferromagnetic ordering with Nèel temperatures T_N = 13.5 and 9 K, respectively. The anisotropic magnetic response of Ce and Pr compounds establishes [0 0 1] as the easy axis of magnetization and a sharp spin-flip type metamagnetic transition is observed in the magnetic isotherms with H // [0 0 1]. The transport and magnetotransport behaviour of these compounds, in particular LaAu₂Ge₂, indicate an anisotropic Fermi surface. The magnetoresistivity of CeAu₂Ge₂ apparently reveals the presence of a residual Kondo interaction. A crystal electric field analysis of the anisotropic susceptibility in conjunction with the experimentally inferred Schottky heat capacity enables us to propose a crystal electric field level scheme for Ce and Pr compounds. For CeAu₂Ge₂ our values are in excellent agreement with the previous reports on neutron diffraction. The heat capacity data in LaAu₂Ge₂ show clearly the existence of Einstein contribution to the heat capacity.     

Magnetocaloric and barocaloric effects in a Gd5Si2Ge2 compound

The first-order phase transition in Gd₅Si₂Ge₂ is sensitive to both magnetic field and pressure. It may indicate that the influences of the magnetic field and the pressure on the phase transition are virtually equivalent. Moreover, theoretical analyses reveal that the total entropy change is almost definite at a certain Curie temperature no matter whether the applied external field is a magnetic field or a pressure. The entropy change curve can be broadened dramatically under pressure, and the refrigerant capacity is improved from 284.7 J/kg to 447.0 J/kg.     

Magnetoelastic properties of ErMn6Sn6 intermetallic compound

The thermal expansion and magnetostriction of polycrystalline sample of the ErMn₆Sn₆ intermetallic compound with hexagonal HfFe₆Ge₆-type structure are investigated in the temperature range of 77 K to above 400 K. The thermal expansion measurement of the sample shows anomalous behavior around its T_N=340 K. The isofield curves of volume magnetostriction also reveal anomalies at paramagnetic-antiferromagnetic and antiferromagnetic-ferrimagnetic phase transitions. In the antiferromagnetic state, the transition to ferrimagnetism can be induced by an applied magnetic field. The threshold field for the metamagnetic transition H_th increases from 0.18 T at 84 K to about 1 T around 220 K, and then decreases monotonously to T_N. This behavior is well consistent with that observed earlier on magnetization curves attributed to exchange-related metamagnetic transition rather than the anisotropy-related one. Furthermore, the low H_th values suggest that the Mn-Mn coupling in ErMn₆Sn₆ is not so strong. The experimental results obtained are discussed in the framework of two-magnetic sublattice by bearing in mind the lattice parameter dependence of the interlayer Mn-Mn exchange interaction in this layered compound. From the temperature dependence of magnetostriction values and considering the magnetostriction relation of a hexagonal structure, we attempt to determine the signs of some of the magnetostriction constants for this compound.     

Nature of unusual spontaneous and field-induced phase transitions in multiferroics RMn2O5

Complex magnetic, magnetoelectric and magnetoelastic studies of spontaneous and field-induced phase transitions in TmMn₂O₅ were carried out. In the vicinity of spontaneous phase transition temperatures (35 and 25 K) the magnetoelectric and magnetoelastic dependences demonstrated the jumps of polarization and magnetostriction induced by the field ∼150 kOe. These anomalies can be attributed to the influence of magnetic field on the conditions of incommensurate-commensurate phase transition at 35 K and the reverse one at 25 K. In b-axis dependences the magnetic field-induced spin-reorientation phase transition was also observed below 20 K. Finally the magnetoelectric anomaly associated with metamagnetic transition is observed below the temperature of rare-earth subsystem ordering at relatively small critical fields of 5 kOe. This variety of spontaneous and induced phase transitions in RMn₂O₅ stems from the interplay of three magnetic subsystems: Mn³⁺, Mn⁴⁺, R³⁺. The comparison with YMn₂O₅ highlights the role of rare earth in low-temperature region (metamagnetic and spin-reorientation phase transitions), while the phase transition at higher temperatures between incommensurate and commensurate phases should be ascribed to the different temperature dependences of Mn³⁺ and Mn⁴⁺ ions. The strong correlation of magnetoelastic and magnetoelectric properties observed in the whole class of RMn₂O₅ highlights their multiferroic nature.     

Magnetic properties of Mn3B4 under high magnetic field

The magnetic properties of antiferromagnetic compound Mn₃B₄ were examined using pulsed magnetic field up to 470 kOe. It was found that Mn₃B₄ shows a clear metamagnetic transition under 360 kOe at 4.2K. The present results are not explained by the magnetic structure proposed by Neov and a modified magnetic structure is proposed to understand the present magnetization curve. The magnetic phase diagram in the H-T plane is shown.     

Giant magnetocaloric effect in the Gd5Ge2.025Si1.925In0.05 compound

The magnetocaloric properties of the Gd 5 Ge 2.025 Si 1.925 In 0.05 compound have been studied by x-ray diffraction,magnetic and heat capacity measurements.Powder x-ray diffraction measurement shows that the compound has a dominant phase of monoclinic Gd5Ge2Si2-type structure and a small quantity of Gd 5(Ge,Si) 3-type phase at room temperature.At about 270 K,this compound shows a first order phase transition.The isothermal magnetic entropy change(△SM) is calculated from the temperature and magnetic field dependences of the magnetization and the temperature dependence of MCE in terms of adiabatic temperature change(△Tad) is calculated from the isothermal magnetic entropy change and the temperature variation in zero-field heat-capacity data.The maximum S M is 13.6 J·kg-1·K-1 and maximum △Tad is 13 K for the magnetic field change of 0-5 T.The Debye temperature(θD) of this compound is 149 K and the value of DOS at the Fermi level is 1.6 states/eV·atom from the low temperature zero-field heat-capacity data.A considerable isothermal magnetic entropy change and adiabatic temperature change under a field change of 0-5 T jointly make the Gd5Ge2.025Si1.925 In 0.05 compound an attractive candidate for a magnetic refrigerant.     

STRUCTURE, MAGNETIC PROPERTIES AND GIANT MAGNETORESISTANCE OF YMn6Sn6-xGax (x=0-0.6) COMPOUNDS

Structure, magnetic and transport properties of YMn₆Sn_6-xGa_x (0≤x≤0.6) compounds with a HfFe₆Ge₆-type structure were investigated. It was found that the Ga substitution leads to a contraction of the unit-cell volume. A transition from an antiferromagnetic to a ferromagnetic (or ferrimagnetic) state can be observed for samples (0.1≤x≤0.2) with increasing temperature. The antiferro-ferromagnetic transition for samples with x≤0.2 can also be induced by an external field. The required field is very low, and decreases with increasing Ga concentration. More Ga concentration (x≥0.3) leads to the samples being ferromagnetic in the whole temperature range below the Curie temperature. The Ga substitution weakens the interlayer magnetic coupling between the Mn spins. Corresponding to the metamagnetic transition, a magnetoresistance as large as 32% under a field of 5 T was observed at 5 K for the sample with x=0.2.     

Magnetocaloric effect in high-energy ball-milled Gd5Si2Ge2 and Gd5Si2Ge2/Fe nanopowders

Evolution of structure and magnetocaloric properties in ball-milled Gd₅Si₂Ge₂ and Gd₅Si₂Ge₂/0.1 wt% Fe nanostructured powders were investigated. The high-energy ball-milled powders were composed of very fine grains (70–80 nm). Magnetization decreased with milling time due to decrease in the grain size and randomization of the magnetic moments at the surface. The magnetic entropy change (ΔS_M) was calculated from the isothermal magnetization curves and a maximum value of 0.45 J/kg K was obtained for 32 h milled Gd₅Si₂Ge₂ alloy powder for a magnetic field change of 2 T while it was still low in Fe-contained alloy powders. The thermo-magnetic measurements revealed that the milled powders display distribution of magnetic transitions, which is desirable for practical magnetic refrigerant to cover a wide temperature span.     

Unusual magnetization suppression induced by higher magnetic field in (La0.83Bi0.17)0.67Ca0.33MnO3

Magnetization behavior of (La_0.83Bi_0.17)_0.67Ca_0.33MnO₃ has been investigated in the temperature range from 100 to 180 K. A metamagnetic transition was observed in the temperature region, where the magnetization was measured after a zero-field-cooling from room temperature to a selected temperature. Experimental results show that, after a higher magnetization route, the field-increasing branches of the magnetization curves shows an unusual training effect: below a magnetic field H₀, the applied magnetic field enhances the value of magnetization; however, above H₀ the magnetic field suppresses the value, and the behavior cannot be totally attributed to the enhancement effect of the applied magnetic field on ferromagnetic phase fraction. It is proposed that, in the two-phase coexistence region, the higher magnetic field promotes the phase separation and leads to both the fraction of ferromagnetic domain and the stabilization of antiferromagnetic domain increase.     

Magnetic properties and magnetic structures of Sr3−xCaxRu2O7

We have measured magnetization curves and powder neutron diffraction of double-layered Ruddlesden-Popper type ruthenate Sr_3−xCa_xRu₂O₇ (x=1.5, 2.0 and 3.0). The field dependence of the magnetization revealed that the transition field of metamagnetic transition along the b-axis shifted to lower fields and that the transition became broad with increasing Sr content. The slope of the magnetization curve also increased with increasing Sr content below the metamagnetic transition. These results indicate that an itinerant component is partly introduced by the Sr substitution. From the magnetic reflection, on cooling below T_N, an additional reflection was observed at (0 0 1) for each x, and the amplitude increased with decreasing temperature. The observed diffraction patterns are very similar to those of Ca₃Ru₂O₇. We conclude that the magnetic structure of the antiferromagnetic ordered phase is basically the same structure with that of Ca₃Ru₂O₇.     

Metamagnetic behavior of an organometallic polymer: [{Fe(C13H17N3)2}SO4·6H2O]n

The organic polymer of (C₁₃H₁₇N₃)_n has been demonstrated to show metamagnetic behavior when the polymer is combined with iron (II) sulfate. The resulting iron-bonded polymer exhibits the field-induced phase transition from an antiferro- to a ferromagnetic phase at relatively weak magnetic field strength (< 600 Oe) in the temperature range of 1.9–300 K. This iron-bonded polymer [{Fe(C₁₃H₁₇N₃)₂}SO₄·6H₂O]_n is the first example of magnetic polymer which has a backbone frame of organic polymer and shows magnetically ordered state even at room temperature.     

Very high upper critical fields of F-doped Fe-based layered superconductors NdO0.88F0.12FeAs and CeO0.88F0.12FeAs

Using the solid state reaction method, we have synthesized the polycrystalline F-doped NdO_0.88F_0.12FeAs and CeO_0.88F_0.12FeAs with the superconducting transition temperatures at about 48 and 40 K, respectively. To obtain the upper critical field H _c2 of Nd(Ce)O_0.88F_0.12FeAs samples, we measured the electrical resistivity under magnetic field up to 14 T. Based on the Werthamer-Helfand-Hohenberg (WHH) relation together with the H _c2(T) curves in a relatively high field, we estimated that these superconductors have a rather high upper critical field of about 115 T for Nd-based and 107 T for Ce-based samples, indicating the similarities between these ReO_1−x F _x FeAs (Re = rare earth element) superconductors and high T _c cuprate superconductors. Recommended by Prof. Nie Yuxin, Executive Editor of Science in China Series G-Physics, Mechanics & Astronomy Supported by the National Basic Research Program of China (973 Program)(Grant No. 2006CB9213001) and the National Natural Science Foundation of China (Grant No. 10774181)     

Specific character of metamagnetic transitions in Fe2P

Temperature and field dependences of magnetization in the fields directed along the easy axis of magnetization are studied on Fe₂P single crystals under pressure. It is shown that the first-order magnetic transition from ferromagnetism to paramagnetism (FM-PM) usually observed in sufficiently strong fields can be resolved into two sequential transitions in weak fields (H ? 600 Oe): 1) from the PM state to the intermediate metamagnetic phase and 2) transition to the low-temperature magnetic phase. The temperatures of these transitions undergo a specific evolution under pressure. A theoretical model, in which the characteristic features of magnetic behaviour of Fe₂P are associated with the successive additional ordering of magnetic components of its composition, is proposed.     

The magnetic properties across the martensitic transition in the Co38Ni34Al28 alloy

The magnetic properties of the Co₃₈Ni₃₄Al₂₈ alloy have been studied. The alloy exhibits a first order austenite-martensite phase transition in the temperature region between 155 and 247 K. A strain of 0.07% is produced across this phase transition. The Arrott plots obtained from the isothermal magnetic field dependence of magnetization indicate the presence of spontaneous magnetization both in the austenite and martensite phases, confirming the ferromagnetic character of the alloy up to room temperature. The temperature dependence of the high field magnetization indicates the presence of spin wave excitations, spin wave excitation gap and spin wave-spin wave interactions in the martensite phase. The magnetic anisotropy energy constant for the Co₃₈Ni₃₄Al₂₈ alloy is estimated both with the help of the standard law of approach to saturation of magnetization, and also from the field dependence of magnetization using the field for technical saturation of magnetization. The temperature dependences of these energy terms are compared. The estimated values of the magnetic anisotropy constant seem to be in agreement with the magnitude of the spin wave excitation gap estimated from the temperature dependence of high field magnetization.     

Unconventional magnetic and transport properties in Gd1−xLaxMn2Ge2 with two-dimensional arrangement of Mn atoms

In this paper, we present our recent experimental results of magnetic and transport properties of Gd_1−xLa_xMn₂Ge₂ intermetallic compounds with the ThCr₂Si₂-type layered structure. The results obtained indicate that, in GdMn₂Ge₂, a first-order transition from a collinear antiferromagnetic to a collinear ferrimagnetic state appears with decreasing temperature at T_t3, below the Néel temperature T_N. In Gd_1−xLa_xMn₂Ge₂ compounds with x=0.05 and 0.075, after ordering ferrimagnetically at T_t1, two kinds of first-order transitions from a canted ferrimagnetic to a non-collinear antiferromagnetic state and from a non-collinear antiferromagnetic to a reentrant canted ferrimagnetic state occur at T_t2 and T_t3. In Gd_0.925La_0.075Mn₂Ge₂, a field-induced metamagnetic transition from non-collinear antiferromagnetism to canted ferrimagnetism occurs at relatively low fields, accompanied by fractal like multi-step transitions, the so called “devil's stair-case”. Furthermore, a negative giant magnetoresistance (GMR) effect (Δρ/ρ15%) was observed at the field-induced metamagnetic transition. The mechanism of this negative GMR was clarified by comprehensive measurements of the resistivity on single crystals Gd_0.925La_0.075Mn₂Ge₂ and TbMn₂Ge₂. With further increasing x, only canted ferrimagnetism appears with a compensation temperature for 0.10<x<0.40, whereas no compensation behavior appears for x>0.50. The phase diagram obtained indicates that the overall magnetism is controlled by the Mn–Mn intralayer distance in the tetragonal c-plane, reflecting the two-dimensional arrangement of Mn atoms.     

Investigation of magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by magnetic,differential scanning calorimetry and thermal analysis

We investigated magnetocaloric effect in La_0.45Pr_0.25Ca_0.3MnO₃ by direct methods (changes in temperature and latent heat) and indirect method (magnetization isotherms). This compound undergoes a first-order paramagnetic to ferromagnetic transition with T_C=200 K upon cooling. The paramagnetic phase becomes unstable and it transforms into a ferromagnetic phase under the application of magnetic field, which results in a field-induced metamagnetic transition (FIMMT). The FIMMT is accompanied by release of latent heat and temperature of the sample as evidenced from differential scanning calorimetry and thermal analysis experiments. A large magnetic entropy change of ΔS_m=−7.2 J kg⁻¹ K⁻¹ at T=212.5 K and refrigeration capacity of 228 J kg⁻¹ are found for a field change of ΔH=5 T. It is suggested that destruction of magnetic polarons and growth of ferromagnetic phase accompanied by a lattice volume change with increasing magnetic field is responsible for the large magnetocaloric effect in this compound.