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.     

Glass formation,magnetic properties and magnetocaloric effect of ternary Ho–Al–Co bulk metallic glass

A ternary Ho–Al–Co system with high glass-forming ability (GFA) was developed and fully glassy rods with diameters up to 1 cm can be produced for the best glass former of Ho₅₅Al_27.5Co_17.5 alloy. The thermal stability and low-temperature magnetic properties of the Ho₅₅Al_27.5Co_17.5 bulk metallic glass (BMG) were studied. The magnetic transition temperature of this alloy is ∼14 K as determined by the thermomagnetic measurement. Two indicators, i.e. isothermal magnetic entropy change (ΔS_M) and the relative cooling power (RCP), were adopted to evaluate the magnetocaloric effect (MCE) of the alloy under a low magnetic field up to 2 T, which can be generated by permanent magnets. The values of |ΔS_M| and RCP are 7.98 J kg⁻¹ K⁻¹ and 191.5 J kg⁻¹, respectively. The Ho₅₅Al_27.5Co_17.5 BMG with good MCE and high GFA provides an attractive candidate for magnetic refrigeration applications, like hydrogen liquefaction and storage.     

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.     

Field-induced structural transition and the related magnetic entropy change in Ni43Mn43Co3Sn11 alloy

Magnetic properties and magnetic entropy change ΔS were investigated in Heusler alloy Ni₄₃Mn₄₃Co₃Sn₁₁. With decreasing temperature this alloy undergoes a martensitic structural transition at T_M=188 K. The incorporation of Co atoms enhances ferromagnetic exchange for parent phases. Austenitic phase with cubic structure shows strong ferromagnetic behaviors with Curie temperature T_C^A at 346 K, while martensitic phase shows weak ferromagnetic properties. An external magnetic field can shift T_M to a lower temperature at a rate of 4.4 K/T, and a field-induced structural transition from martensitic to austenitic state takes place at temperatures near but below T_M. As a result, a great magnetic entropy change with positive sign appears. The size of ΔS reaches 33 J/kg K under 5 T magnetic field. More important is that the ΔS displays a table-like peak under 5 T, which is favorable for Ericsson-type refrigerators.     

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.     

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.     

Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

Large reversible magnetocaloric effect in spinel MnV2O4 with minimal Al substitution

Magnetocaloric effect of MnV_1.95Al_0.05O₄ was studied by the magnetization and heat capacity measurements. MnV_1.95Al_0.05O₄ is a cubic spinel structure with ferromagnetism of second order in nature and performs reversible magnetic entropy around the magnetic transition temperature. The large magnetic entropy changes −ΔS_M∼5.2 and 8.2 J/kg K and the adiabatic temperature changes ΔT_ad∼1.5 and 2.6 K are revealed for the magnetic field changes of 2 and 4 T near the Curie temperature (T_C) of 59.6 K, respectively. The relative cooling power (RCP) are about 82.2 and 177.2 J/kg K for magnetic field changes 2 and 4 T, respectively. Compared with the parent compound, although the −ΔS_M and ΔT_ad become smaller, the refrigeration working temperature span and the RCP have been improved.     

Field induced sign reversal of magnetocaloric effect in Gd2In

We report the magnetocaloric effect in the metamagnetic compound Gd₂In obtained from magnetization measurement. Gd₂In was previously reported to have two magnetic transitions: (i) a paramagnetic to ferromagnetic transition below 190 K and (ii) a ferromagnetic to an antiferromagnetic state below 105 K. The low temperature antiferromagnetic state is unstable under an applied magnetic field and undergoes metamagnetic transition to a ferromagnetic like state. We observe conventional positive magnetocaloric effect (the magnetic entropy change, ΔS_M<0) around 190 K at all applied fields. The magnetocaloric effect is found to be inverse (negative) at low fields around 105 K (ΔS_M>0), however it turns positive at higher fields (ΔS_M<0). The observed anomaly is found to be related to the field induced transition which drives the system from an antiferromagnetic to a ferromagnetic state.     

Magnetic properties of half-metallic semi Heusler Co1−xCuxMnSb compounds

A study of the half-metallic character of the semi Heusler alloys Co_1−xCu_xMnSb (0?x?0.9) is presented. We investigated the saturation magnetization M_S at temperatures from 5 K to room temperature and the temperature dependence of the DC magnetic susceptibility χ above Curie temperature T_C. The magnetic moments at 5 K, for most compositions are very close to the quantized value of 4 μ_B for Mn³⁺ ion, the compound with 90% Co substituted by Cu is still ferromagnetic with M_S (5 K)=3.78 μ_B/f.u. These results emphasize the role of Co atoms in maintaining the ferromagnetic order in the material. The Curie temperature is decreased from 476 K to about 300 K as the Cu content increases from 0% to 90%. Above T_C, the χ⁻¹ vs T curves follow very well the Curie–Weiss law. The effective moment μ_eff and paramagnetic Curie temperature θ are derived. A comparison between the values of M_S at 5 K and μ_eff shows a transition from localized to itinerant spin system in these compounds.     

The influence of gallium on magnetocaloric effect in Gd60Tb40 alloys

The influences of gallium substitution for terbium in Gd₆₀Tb₄₀ on the phase formation, Curie temperature and magnetic entropy change have been investigated. A series of Gd₆₀Tb_40−xGa_x with x=0, 1, 3 and 5 alloys were prepared by arc-melting method. The X-ray diffraction (XRD) analysis reveals that a small amount of Ga substitution for terbium in Gd₆₀Tb₄₀ can form the solid solution (Gd, Tb). The Curie temperature (T_c) increases from 270 K for Gd₆₀Tb₄₀ to 297 K for Gd₆₀Tb₃₇Ga₃, while the maximum magnetic entropy changes ΔS_{M, max} decreases from 5.15 J/K kg for Gd₆₀Tb₄₀ to 3.32 J/K kg for Gd₆₀Tb₃₇Ga₃ with increasing the Ga content.     

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 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 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.     

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.     

Understanding the magnetic ground state of rare-earth intermetallic compound Ce4Sb3: Magnetization and neutron diffraction studies

Magnetization and neutron diffraction studies have been performed on Ce₄Sb₃ compound (cubic Th₃P₄-type, space group I4¯3d, no. 220). Magnetization of Ce₄Sb₃ reveals a ferromagnetic transition at ∼5 K, the temperature below which the zero-field-cooled and field-cooled magnetization bifurcate in low applied fields. However, a saturation magnetization (M_S) value of only ∼0.93μ_B/Ce³⁺ is observed at 1.8 K, suggesting possible presence of crystal field effects and a paramagnetic/antiferromagnetic Ce³⁺ moment. Magnetocaloric effect in this compound has been computed using the magnetization vs. field data obtained in the vicinity of the magnetic transition, and a maximum magnetic entropy change, −ΔS_M, of ∼8.9 J/kg/K is obtained at 5 K for a field change of 5 T. Inverse magnetocaloric effect occurs at ∼2 K in 5 T indicating the presence of antiferromagnetic component. This has been further confirmed by the neutron diffraction study that evidences commensurate antiferromagnetic ordering at 2 K in zero magnetic field. A magnetic moment of ∼1.24μ_B/Ce³⁺ is obtained at 2 K and the magnetic moments are directed along Z-axis.     

Magnetocaloric properties of (La0.67−xGdx)Sr0.33MnO3 polycrystalline nanoparticles

In this paper, magnetic property and magnetocaloric effect (MCE) in nanoparticles perovskite manganites of the type (La_0.67−xGd_x)Sr_0.33MnO₃ (x=0.10, 0.15, 0.20) synthesized by using an amorphous molecular alloy as precursor have been reported. From the magnetic measurements as function of temperature and magnetic applied field, we have discovered that the Curie temperature (T_C) of the prepared samples is found to be strongly dependent on Gd content. The Curie temperature of samples is 358.4, 343.2, and 285.9 K for x=0.1, 0.15, and 0.2, respectively. A large magnetocaloric effect close to T_C has been observed with a maximum of magnetoentropy change in all the samples, ∣ΔS_M∣_max of 1.96 and 4.90 J/kg K at 2 and 5 T, respectively, for a substitution rate of 0.15. In addition, the maximum magnetic entropy change observed for samples with different concentration of Gd, exhibits a linear dependence with the applied high magnetic field. These results suggest that (La_0.67−x Gd_x)Sr_0.33MnO₃ (x=0.10, 0.15, 0.20) compounds could be a suitable candidate as working substance in magnetic refrigeration near room temperature.     

Influence of Dy addition on the magnetocaloric effect of La0.67Ca0.33Mn0.9V0.1O3 ceramics

The influence of partial substitution of La by Dy on the magnetocaloric response of (La_1−xDy_x)_0.67Ca_0.33Mn_0.9V_0.1O₃, where x=0.03, 0.15 and 0.25 is studied. Rietveld refinement of X-ray diffraction pattern using GSAS method shows that the compounds adopt the orthorhombic structure with Pnma space group. The systematic change in lattice parameters and magnetic phase transition indicates the substitution effect of Dy. From the magnetization isotherms at different temperatures, magnetic entropy change close to their respective transition temperatures (T_C) has been evaluated. The maximum value of entropy change near T_C is found to be about 4.8 J/kg K at 187.5 K for LCMVDy_0.03, 2.45 J/kg K at 107.5 K for LCMVDy_0.15 and 2.15 J/kg K at 92.5 K for LCMVDy_0.25 at 4 T. Dy addition produces a reduction in T_C and in magnitude of the magnetic entropy change. Even though the entropy change decreases with increasing Dy substitution the refrigerant temperature range, ΔT, is found to be 10 K for LCMVDy_0.03, 31 K for LCMVDy_0.15 and 35 K for LCMVDy_0.25 compounds [90%] at 4 T. The field dependence of the magnetic entropy change is also analyzed showing the power law dependence, ΔS_M∞Hⁿ where n=0.75(2) for LCMVDy_0.03, n=0.80(4) for LCMVDy_0.15 and n=0.92(8) for LCMVDy_0.25 compounds at their respective transition temperatures. The relative cooling power and its field dependance are also analyzed.     

Synthesis and physical characterization of superconductivity-magnetism crossover compound RuSr2EuCeCu2O10−δ

We carefully studied the nonsuperconducting sample of the magneto-superconducting RuSr₂(Eu_1−xCe_x)Cu₂O_10−δ series with composition RuSr₂EuCeCu₂O_10−δ. This compound seems to exhibit a complex magnetic state as revealed by host of techniques like resistivity, thermopower, magnetic susceptibility, and MR measurements. The studied compound exhibited ferromagnetic like M(H) loops at 5, 20, and 50 K, and semiconductor like electrical conduction down to 5 K, with −MR^7 T of up to 4% at low temperatures. The −MR^7 T decreases fast above 150 K and monotonically becomes close to zero above say 230 K. Below, 150 K −MR^7 T decreases to around 3% monotonically down to 75 K, with further increase to 4% at around 30 K and lastly having a slight decrease below this temperature. The thermopower S(T) behavior closely followed the −MR^7 T steps in terms of d(S/T)/dT slopes. Further, both MR^7 T steps and d(S/T)/dT slopes are found in close vicinity to various magnetic ordering temperatures (T_mag) of this compound.