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.     

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.     

Field and temperature induced colossal strain in Gd5(SixGe1−x)4

Gd₅(Si_xGe_1−x)₄, known for its giant magnetocaloric effect, also exhibits a colossal strain of the order of 10,000 ppm for a single crystal near its coupled first-order magnetic-structural phase transition, which occurs near room temperature for the compositions 0.41≤x≤0.575. Such colossal strain can be utilised for both magnetic sensor and actuator applications. In this study, various measurements have been carried out on strain as a function of magnetic field strength and as a function of temperature on single crystal Gd₅Si₂Ge₂ (x=0.5), and polycrystalline Gd₅Si_1.95Ge_2.05 (x=0.487) and Gd₅Si_2.09Ge_1.91 (x=0.52). Additionally a giant magnetostriction/thermally induced strain of the order of 1800 ppm in polycrystalline Gd₅Si_2.09Ge_1.91 was observed at its first order phase transition on varying temperature using a Peltier cell without the use of bulky equipment such as cryostat or superconducting magnet.     

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.     

Magnetocaloric effect in Gd6Co1.67Si3 compound with a second-order phase transition

The magnetic properties and the magnetic entropy change AS have been investigated for Gd6Co1.67Si3 compounds with a second-order phase transition. The saturation moment at 5 K and the Curie temperature TC are 38.1μB and 298 K, respectively. The AS originates from a reversible second-order magnetic transition around TC and its value reaches 5.2 J/kg.K for a magnetic field change from 0 to 5T. The refrigerant capacity （RC） of Gd6Co1.67Si3 are calculated by using the methods given in Refs.[12] and [21], respectively, for a field change of 0 5T and its values are 310 and 440 J/kg, which is larger than those of some magnetocaloric materials with a first-order phase transition.     

Scaling analysis of the magnetocaloric effect in Gd5Si2Ge1.9X0.1 (X=Al, Cu, Ga, Mn, Fe, Co)

The field dependence of the magnetic entropy change has been studied for a series of doped Gd₅Si₂Ge₂ alloys, which possess a magnetic phase transition that is either entirely second order or a combination of primarily second-order mixed to a very minor degree with a first-order transition arising from a magneto-structural phase change. By analyzing the field scaling of the refrigerant capacity as well as of the reference temperatures used for constructing a universal scaling curve, a procedure for estimating the values of the critical exponents for the alloys was developed. For the cases where the transition is entirely second order, the results obtained from this procedure are comparable to the values obtained from the Kouvel–Fisher method. For the case of Fe-doped alloys which partially possess a first-order phase change, the Kouvel–Fisher method is inapplicable. However, their critical exponents determined by our developed procedure can be used to estimate the Curie temperature of the orthorhombic majority phase.     

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.     

Determination of Curie temperature by Arrott plot technique in Gd5(SixGe1−x)4 for x>0.575

Determination of Curie temperature by plotting magnetic moment vs. temperature curves requires a small applied field, which influences the measurement and temporarily disturbs the temperature of the sample especially for highly magnetocaloric materials. The Arrott plot technique was therefore used in order to determine the Curie temperature for a magnetocaloric Gd₅Si_2.7Ge_1.3 (x=0.675) single crystal sample. This technique was compared with other methods such as the inflection point technique and the line projection method. The results show how applied magnetic field influences the determination of Curie temperature. Using the Arrott plot the second-order transition Curie temperature for Gd₅Si_2.7Ge_1.3 was determined to be 304 K.     

Magnetic entropy change and large refrigerant capacity of Ce6i2Si3-type GdCoSiGe compound

Magnetic entropy change (Δ S_M) and refrigerant capacity (RC) of Ce₆Ni₂Si₃-type Gd₆Co_1.67Si_2.5Ge_0.5 compounds have been investigated. The Gd₆Co_1.67Si_2.5Ge_0.5 undergoes a reversible second-order phase transition at the Curie temperature T_C = 296 K. The high saturation magnetization leads to a large Δ S_M and the maximal value of Δ S_M is found to be 5.9 J/kg,cdot,K around T_C for a field change of 0--5 T. A broad distribution of the Δ S_M peak is observed and the full width at half maximum of the Δ S_M peak is about 101 K under a magnetic field of 5 T. The large RC is found around T_C and its value is 424 J/kg.     

Critical phenomena of amorphous Nd4(Fe0.75Cr0.25)77.5B18.5 alloys

The magnetic behavior of amorphous Nd₄(Fe_0.75Cr_0.25)_77.5B_18.5 alloys was investigated in the critical region. The Curie temperature T_C and critical exponents β, γ and δ are found to be 141 K, 0.45±0.02, 1.64±0.08 and 4.66±0.10, respectively. The data are fitted to a magnetic equation of state characteristic of a second-order phase transition over a rather wide range of temperatures both above and below T_C. It is noted that the values of the exponents are in disagreement with those derived for a three-dimensional Heisenberg ferromagnet and show an enhancement. This anomalous critical behavior may originate from magnetic inhomogeneity.     

Neutron diffraction study of the U(Pd1−xFex)2Ge2 magnetic structure

The neutron diffraction and magnetic susceptibility studies have shown that the magnetic structure of UPd₂Ge₂ changes dramatically even under very low iron doping. Though the general magnetic structure of pure UPd₂Ge₂ and of 1%Fe-doped samples is the same, the temperature intervals of existence of different magnetic phases are different. The values of transition temperatures, where (i) the ‘square’ modulated longitudinal spin-density wave (LSDW) structure with the propagation vector k=(0; 0; ) starts to transform into the sinusoidal modulated LSDW structure and (ii) the commensurate phase transforms into incommensurate one, shift under the 1%Fe doping to the higher temperatures (from 50 to 65 K and from 80 to 90 K, respectively). In the pure and 1%Fe-doped UPd₂Ge₂, the magnetic transition from the commensurate to incommensurate phase is accompanied by the drastic decrease of the propagation vector k_z. In the 2%Fe-doped sample, besides the Néel point of T_N=135 K, we have found two additional characteristic temperatures of 65 and 93 K. Below 65 K, the material has a simple antiferromagnetic (AF) structure with the propagation vector k=(0; 0; 1) and, at 65 K<T<T_N, the magnetic structure is LSDW with sinusoidal modulation. Over almost the total region 65 K<T<T_N, the LSDW magnetic structure is incommensurate. Only at about 93 K, the propagation vector passes the commensurate value of , whereas at 65<T<93 K and at 93 K<T<T_N. We have found that the magnetic susceptibility and the uranium magnetic moment are sensitive to the transition. With increasing iron concentration to x0.15, the simple AF structure with k=(0; 0; 1) develops over all temperature region up to the Néel point. Below T_N, the uranium magnetic moments are always parallel to the tetragonal c-axis.     

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.     

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.     

Electronic and magnetic phase transitions in (Sm0.65Sr0.35)MnO3 induced by temperature and magnetic field

Temperature (4.2–260 K) and magnetic field (0–50 kOe) dependencies of the DC electrical resistance, DC magnetization, and AC magnetic susceptibility of (Sm_0.65Sr_0.35)MnO₃ prepared from high purity components have been studied. (Sm_0.65Sr_0.35)MnO₃ undergoes a temperature-induced transition between low-temperature ferromagnetic metallic and high-temperature paramagnetic insulating-like states. A magnetic field strongly affects this transition resulting in a metallic state and “colossal” magnetoresistance in the vicinity of the metal↔insulator transition. Magnetic and electric properties of (Sm_0.65Sr_0.35)MnO₃ are different compared to those reported earlier for similar composition, which is attributable to the purity of the starting materials and/or different process of synthesis. The character of phase transformations observed in (Sm_0.65Sr_0.35)MnO₃ is compared to that reported for Gd₅(Si_xGe_4−x) intermetallic alloys with a true first order phase transition.     

Magnetic phase transitions in Nd7Rh3 single crystal

Magnetic phase transitions in rare earth intermetallic compound Nd₇Rh₃ have been investigated using a single crystal. Measurement results of magnetization, magnetic susceptibility, specific heat, and electrical resistivity reveal that Nd₇Rh₃ has two magnetic phase transitions at T_N=34 K, T_t2=9.1 K and a change of the magnetic feature at T_t1=6.8 K in the absence of an external magnetic field. Antiferromagnetic orderings exist in all the three magnetic states; a large magnetic anisotropy between the c-axis and the c-plane is observed. In the magnetic phase below T_t2, an irreversible field-induced magnetic phase transition takes place in the c-plane; after removing external magnetic field, a coexistence state of ferro- and antiferromagnetic ordering or a ferrimagnetic state having a remanent magnetization M_R is stabilized. The M_R decays to a certain value for several hours after the first process; a magnetic field cooling effect was also observed in the c-plane below T_t2. In the antiferromagentic state above T_t2, the irreversibility disappears and an ordinary antiferromagnetic state takes place. As the origin of this phenomenon, a kind of martensitic structural transition that is observed in Gd₅Ge₄ can be considered.     

The double-phase transition of ErFe4Ge2. An XRPD study

High-quality powder XRD data of the compound ErFe₄Ge₂ collected in the ESRF beam line BM16, are presented for the entire magnetically ordered regime (T_N=44 K). The data analysis reveals the occurrence of a double symmetry breaking at the magnetic transition. This experiment has allowed us to distinguish between structural and magnetic satellites, both present in the neutron patterns, and to demonstrate the interdependence of structural and magnetic transitions. The high-temperature (HT) phase disproportionates by a first-order transition into two distinct phases: P4₂/mnm (T_c, T_N=44 K)→Cmmm (majority LT phase)+Pnnm (minority IT Phase) which coexist in proportions varying with temperature down to 4 K. The phase diagram comprises three temperature regions: (a) the HT range with T>T_N for the tetragonal P4₂/mnm phase; (b) the IT (intermediate temperature) range, 20 K<T<T_N, where the two phases coexist in strongly variable proportions and the Pnnm phase reaches its highest concentration (≈31%) around 30 K and (c) the LT (low temperature) range, 1.5–20 K, where the Cmmm phase is dominating (up to 95%). We suggests that this phenomenon is the result of competing magneto-elastic mechanisms involving the Er crystal field anisotropy, the Er–Er, Er–Fe and the Fe–Fe exchange interactions and their coupling with the lattice strains.     

Microstructural changes in Fe-doped Gd5Si2Ge2

Gd₅Si₂Ge₂-based alloys can exhibit a giant magnetocaloric effect (GMCE); this gives them the potential for use in cooling technologies. It has also been reported that a small addition of iron reduces the hysteresis losses in Gd₅Si₂Ge₂-based alloys, thus increasing the net refrigerating capacity. In this investigation, we have been the first to look at the effect on the microstructure and magnetic properties of Gd₅Si₂Ge₂ resulting from a wide range of substitutions of Si by Fe. The macrostructures of the arc-melted buttons revealed some very unusual surface morphologies, and the analytical results revealed a gradual substitution of the Gd₅(Si,Ge,Fe)₄-type phase by a Gd₅(Si,Ge,Fe)₃-type phase and the presence of three grain-boundary phases, two of which contain substantial amounts of iron. The magnetic measurements indicated that larger amounts of iron reduced the hysteresis losses, but at the same time reduced the Curie temperatures to below lower values that would make the material useful in practice.     

Valence fluctuation in Ce2Co3Ge5 and crystal field effect in Pr2Co3Ge5

Polycrystalline samples of ternary rare-earth germanides R₂Co₃Ge₅ (R=La, Ce and Pr) have been prepared and investigated by means of magnetic susceptibility, isothermal magnetization, electrical resistivity and specific heat measurements. All these compounds crystallize in orthorhombic U₂Co₃Si₅ structure (space group Ibam). No evidence of magnetic or superconducting transition is observed in any of these compounds down to 2 K. The unit cell volume of Ce₂Co₃Ge₅ deviates from the expected lanthanide contraction, indicating non trivalent state of Ce ions in this compound. The reduced value of effective moment (μ_eff≈0.95 μ_B) compared to that expected for trivalent Ce ions further supports valence-fluctuating nature of Ce in Ce₂Co₃Ge₅. The observed temperature dependence of magnetic susceptibility is consistent with the ionic interconfiguration fluctuation (ICF) model. Although no sharp anomaly due to a phase transition is seen, a broad Schottky-type anomaly is observed in the magnetic part of specific heat of Pr₂Co₃Ge₅. An analysis of C_mag data suggests a singlet ground state in Pr₂Co₃Ge₅ separated from the singlet first excited state by 22 K and a doublet second excited state at 73 K.     

Magnetocaloric effect in the La0.8Ce0.2Fe11.4−xCoxSi1.6 compounds

The effects of substitution of Co for Fe on the magnetic and magnetocaloric properties of La_0.8Ce_0.2Fe_11.4−xCo_xSi_1.6 (0, 0.2, 0.4, 0.6, 0.8 and 1.0) compounds have been investigated. X-ray diffraction shows that all compounds crystallize in the NaZn₁₃-type structure. Magnetic measurements show that the Curie temperature (T_C) can be tuned between 184 and 294 K by changing the Co content from 0 to 1. A field-induced methamagnetic transition occurs in samples with x=0, 0.2 and 0.4. The magnetic entropy changes of the compounds have been determined from the isothermal magnetization measurements by using the Maxwell relation.     

Giant magnetoresistance in the Ge-rich magnetocaloric compound,Gd5(Si0.1Ge0.9)4

We have measured the zero-field electrical resistivity in the temperature range 5–295 K and magnetoresistance in magnetic fields of up to 12 T of Gd₅(Si_0.1Ge_0.9)₄. The resistivity changes drastically at the magnetostructural first-order transition (T_C≅80 K on heating). This transition can be induced reversibly by the application of an external magnetic field above T_C, producing a concomitant giant magnetoresistance (GMR) effect, Δρ/ρ≅−50%. This study demonstrates that (in addition to giant magnetocaloric and magnetoelastic effects) GMR can be tuned between ∼20 and ∼290 K in Gd₅(Si_xGe_1−x)₄ with x⩽0.5 by simply adjusting the Si : Ge ratio.