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.     

Magnetic coupling between Gd and Pr ions and magnetocaloric effect in Gd0.5Pr0.5Al2 compound

In this work, we report the theoretical and experimental investigations on the magnetic and magnetocaloric properties for Gd_0.5Pr_0.5Al₂ compound in different magnetic fields. The magnetization features indicate that Gd_0.5Pr_0.5Al₂ is ferrimagnetic at low temperatures. We also present data from X-ray magnetic circular dichroism (XMCD) experiments for this compound, with which we have confirmed that the magnetic moments of the Pr ions are antiparallel to the magnetic moments of the Gd ions. The magnetocaloric parameters, ΔT_S and ΔS_T, were obtained from calorimetric data and both curves present normal and inverse magnetocaloric effect. A theoretical model for ferrimagnetic coupling, including the crystalline electrical field anisotropy, was used to describe the ΔT_S and ΔS_T experimental results.     

Magnetocaloric effects in (Gd1−xTbx)Co2

The structures and magnetocaloric effects of (Gd_1−xTb_x)Co₂ (x=0, 0.25, 0.4, 0.5, 0.6, 0.7, 0.8, and 1) pseudobinary compounds were investigated by X-ray powder diffraction and magnetic properties measurement. The results show that the T_c of the alloy is near room temperature when X=0.6. The magnetic entropy changes of the compounds increase from 1.7 to 3.6 J/kg K with increasing the content of Tb under an applied field up to 2 T. All the compounds exhibit second order magnetic change. As a result, the values of their ΔS_M are lower than that of some large magnetocaloric effect materials.     

Large relative cooling power of Gd52.5Co16.5Al31 magnetic bulk metallic glass

The magnetocaloric effect and thermal stability have been investigated on the new bulk metallic glass (BMG) Gd_52.5Co_16.5Al₃₁ alloy. The extent of supercooled liquid region is 70 K, which is wider than that of any other Gd-Co-Al ternary BMGs. The magnetic entropy change (ΔS_M) and relative cooling power (RCP) of 9.8 J/kg K and 9.1×10² J/kg are obtained, respectively, under a field change of 5 T. The large ΔS_M and RCP values make Gd_52.5Co_16.5Al₃₁ BMG attractive potential candidate for the magnetic refrigeration application.     

Probing local magnetic cluster development in (CuZr)93−xAl7Gdx bulk metallic glasses by Al NMR

We report magnetization properties of (CuZr)_93−xAl₇Gd_x bulk metallic glasses from temperature dependent ²⁷Al nuclear magnetic resonance spectroscopy and magnetic susceptibility measurements. Significant non-linear line broadening of ²⁷Al spectra commencing at high temperatures is attributed to the development of a local magnetic susceptibility distribution that prevails over a finite temperature range. Magnetization measurements confirm the linewidth enhancement due to strong frustrated magnetic short-range order. This study provides insight into the nature of magnetic development and frustration in paramagnetic systems.     

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 of GdCo2−xAlx compounds

The structure, magnetic property and magnetocaloric effect of GdCo_2−xAl_x (x=0, 0.06, 0.12, 0.18, 0.24, 0.4) compounds have been investigated by X-ray diffraction (XRD) and magnetic measurement techniques. The experimental results show that the GdCo_2−xAl_x (x≤0.4) compounds are single phase with a Laves-phase MgCu₂-type structure. The Curie temperature T_c initially increases, and then decreases with increasing Al content. The maximum value of T_c, 418 K, is reached for the compound with x=0.06. The magnetic entropy change, which is determined from the temperature and field dependence of the magnetization by the Maxwell relation, decreases almost linearly with increasing Al content.     

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.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Amorphization Induced High Magneto-Caloric Effect of Gd55Al20Ni25 Ternary Alloy

We report the amorphization induced high magneto-caloric effect （MCE） of recently developed Gd55Al15Ni30 bulk metallic glass （BMG）. The magnetic properties of the Gd55Al15Ni30 BMG are investigated in comparison with that of its crystalline counterpart. It is found that amorphization can increase the saturation magnetization and decrease the hysteresis of Gd55Al15Ni30 alloys, which indicate the possible enhancement of MCE. The magnetic entropy changes and the refrigerant capacity of the BMG as well as the crystalline samples is calculated directly from isothermal magnetic measurements. The results show the amorphization induced high MCE of the alloy and the excellent refrigerant efficiency of Gd55Al15Ni30 bulk metallic glass.     

Near room temperature magnetocaloric properties of melt-spun Gd100−xBx (x=0, 5, 10, 15, and 20 at%) alloys

The magnetocaloric properties of melt-spun Gd-B alloys were examined with the aim to explore their potential application as magnetic refrigerants near room temperature. A series of Gd_100−xB_x (x=0, 5, 10, 15, and 20 at%) alloys were prepared by melt spinning. With the decrease in Gd/B ratio, Curie temperature (T_C) remains constant at ∼293 K, and saturation magnetization, at 275 K, decreases from ∼100 to ∼78 emu/g. Negligible magnetic hysteresis was observed in these alloys. The peak value of magnetic entropy change, (−ΔS_M)_max, decreased from ∼9.9 J/kg K (0-5 T) and ∼5.5 J/kg K (0-2 T) for melt-spun Gd to ∼7.7 J/kg K (0-5 T) and ∼4.0 J/kg K (0-2 T), respectively for melt-spun Gd₈₅B₁₅ and Gd₈₀B₂₀ alloys. Similarly, the refrigeration capacity (q) decreased monotonously from ∼430 J/kg (0-5 T) for melt-spun Gd to ∼330 J/kg (0-5 T) for melt-spun Gd₈₀B₂₀ alloy. The near room temperature magnetocaloric properties of melt-spun Gd_100−xB_x (0≤x≤20) alloys were found to be comparable to few first-order transition based magnetic refrigerants.     

Magnetic characteristics of the intermetallic system Gd2Ni17−xAlx

The magnetic behaviour of the intermetallic compounds Gd₂Ni_17?xAl_x, (0?x?2) has been investigated both in the ferrimagnetic and paramagnetic regions. The unusual temperature dependence of the intensity of magnetization may be interpreted as a second order phase transition of order-order type, i.e. from colinear to non-colinear ferrimagnetic structure.     

Study of the [(Co45Fe45Zr10)x(Al2O3)100−x/a-Si:H]m multilayer nanostructure by polarized neutron reflectometry

Polarized neutron reflectometry was used to investigate the amorphous multilayer nanostructures [(Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100−x/a-Si:H]_m, whose magnetic properties are dependent on the concentration of the magnetic constituent (x=34, 47 and 60 at%) as well as on the thicknesses of the metal-dielectric (Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100−x and semiconductor a-Si:H layers. The average magnetization of the individual magnetic layer is found to be inhomogeneous with the magnetically active central part and two magnetically dead parts at the interfaces.     

Magnetic properties of GdxY1−xNi5 alloys

Magnetic measurements have been performed on single crystals of Yni₅ and GdNi₅ and on polycrystalline samples of Gd_xY_1?xNi₅. YNi₅ is a Pauli paramagnet, the susceptibility of which is enhanced by exchange and slightly temperature dependent (χ = 23 × 10^?4 emu/mole at 4.2 K). In GdNi₅, where the anisotropy is very weak, a polarization of the d band opposite to the Gd magnetization is observed. At 4.2 K, this polarization is 0.16 ± 0.02μ_B/Ni. The decrease of this polarisation with decreasing magnetic interactions has been studied in Gd_xY_1?xNi₅-type alloys. It is concluded that the polarization is more homogeneous than that of cobalt observed in Gd_xY_1?xCo₂.     

The analysis of the magnetic properties in the intermetallic YxGd1−xNi3 compounds

In the paper an influence of Gd/Y substitution on the magnetic properties and exchange interactions of the Y_xGd_1−xNi₃ (x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0) polycrystalline compounds have been studied. The partial replacement of Gd by Y atoms is reflected in decreasing of the Curie temperature (T_C) as well as decreasing of effective the magnetic moment (μ_eff). It has been shown that such a behaviour strongly depends on the magnetic interactions. Exchange coupling parameters of R–R (A_RR), T–T (A_TT) and R–T (A_RT) have been evaluated from M(T) magnetization curves (2–300 K, 2 T) based on the mean field theory (MFT) calculation. The magnetocaloric effect (MCE) has been estimated from the family of magnetic isotherms. The magnetic entropy indicates relatively small change with the Gd/Y substitution. The value of ΔS_m(T,H) is higher for Gd-rich compounds and, respectively, decreases with Gd/Y substitution.     

Magnetic properties and room-temperature magnetocaloric effect in the doped antipervoskite compounds Ga1−xAlxCMn3 (0≤x≤0.15)

We report the effects of Al doping on the structure, magnetic properties, and magnetocaloric effect of antiperovskite compounds Ga_1−xAl_xCMn₃ (0≤x≤0.15). Partial substitutions of Al for Ga enhance the Curie temperature (from 250 K for x=0.0 to 312 K for x=0.15) and the saturation magnetization. On increasing the doping level x, the maximum values of the magnetic entropy change (−ΔS_M) decreases while the temperature span of −ΔS_M vs. T plot broadens. Furthermore, the relative cooling power (RCP) is also studied. For 20 kOe, the RCP value tends to saturate at a high doping level (for x=0.12, 119 J/kg at 296 K). However, at 45 kOe, the RCP value increases quickly with increasing x (for x=0.15, 293 J/kg at 312 K). Considering the relatively large RCP and inexpensive raw materials, Ga_1−xAl_xCMn₃ may be alternative candidates for room-temperature magnetic refrigeration.     

Magnetic and magnetocaloric properties of Gd1−xScxNi2 solid solutions

Magnetic and heat capacity measurements have been carried out on the polycrystalline Gd_1−xSc_xNi₂ solid solutions (0≤x≤1), which crystallize in the cubic C15 Laves phases superstructure (space group F4?3m). These solid solutions are ferromagnetic with a Curie temperature below 76 K. Their Curie temperature decreases from 75.4 K for GdNi₂ to 13.6 K for Gd_0.2Sc_0.8Ni₂. At high temperatures, all solid solutions, except ScNi₂, are Curie-Weiss paramagnets. The Debye temperature as well as phonon, conduction electron and magnetic contributions to the heat capacity have been determined from heat capacity measurements. The magnetocaloric effect has been estimated both in terms of isothermal magnetic entropy change and adiabatic temperature change for selected solid solutions in magnetic fields up to 3 T.     

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.     

Magnetic properties of (Gd1−xCex)Al2 compounds

Measurements of magnetization and magnetic susceptibility have been made on both polycrystal and single crystal (Gd_1?xCe_x)Al₂ ternaries. The Ce moment is smaller than the expected value for free Ce³⁺ and couples antiparallel with the Gd moment, Ferromaagnetism remains up to x=0.95, and T_c decreases with x. The Curie constant is in good agreement with the value that each atom is in free 3+ ion. The magnetocrystalline anisotropy constant K₁ is so small and of the order of 10^-17 erg/f.u. Results were analyzed in terms of the molecular field approximation including the cubic crystalline field.