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.     

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.     

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.     

Critical behavior and magnetic entropy change in the La0.6Sr0.4Mn0.8Fe0.1Cr0.1O3 perovskite

Critical behavior in the La_0.6Sr_0.4Mn_0.8Fe_0.1Cr_0.1O₃ ceramics was studied using magnetization methods. Results show that the paramagnetic–ferromagnetic transition is of second order. Based on the critical behavior analysis using the Banerjee criterion and the Kouvel–Fisher method, we find the critical exponents: β=0.395±0.010, γ=1.402±0.010, and δ=5.208±0.007, for which the magnetic interaction is satisfied within the three-dimensional Heisenberg model. Results indicate the presence of short-range interactions. The magnetic entropy change (−ΔS_M) reached maximum values of 1.75, 1.45, 1.15, 0.8 and 0.43 J Kg⁻¹ K⁻¹ under a magnetic field variation of 5, 4, 3, 2 and 1 T, respectively. Nevertheless, these (−ΔS_M) values are much low for any potential application at this moment. The nature of this phenomenon is discussed in relation to the characteristics of the magnetic phase transition and critical exponents.     

Room temperature magnetic entropy change and magnetoresistance in La0.70(Ca0.30−xSrx)MnO3:Ag 10% (x=0.0−0.10)

The magnetic and magnetocaloric properties of polycrystalline La_0.70(Ca_0.30−xSr_x)MnO₃:Ag 10% manganite have been investigated. All compositions are crystallized in single phase orthorhombic Pbnm space group. Both, the insulator–metal transition temperature (T^IM) and Curie temperature (T_c) are observed at 298 K for x=0.10 composition. Though both T^IM and T_c are nearly unchanged with Ag addition, the MR is increased. The MR at 300 K is found to be as large as 31% with magnetic field change of 1 T, whereas it reaches up to 49% at magnetic field of 3 T for the La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample. The maximum entropy change (ΔS_Mmax) at near its T_c (300.5 K) is 7.6 J kg⁻¹ K⁻¹ upon the magnetic field change of 5 T. The La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample having good MR (31%^1 T, 49%^3 T) and reasonable change in magnetic entropy (7.6 J kg⁻¹.K⁻¹, 5 T) at 300 K can be a potential magnetic refrigerant material at ambient temperatures.     

Spin-glass behavior and magnetocaloric effect in Tb-based bulk metallic glass

A noncollinear-ferromagnetic spin-glass-like state was observed in Tb₅₅Co₂₀Al₂₅ bulk metallic glass due to the strong random magnetic anisotropy. Associated with this behavior, we observed a comparatively large magnetic entropy change (ΔS_m is 9.75 J K⁻¹ kg⁻¹) in a field change of 7 T and a correspondingly high value of the magnetic refrigeration capacity (RC is 540 J kg⁻¹) with almost no hysteresis loss in the vicinity of the so-called Curie temperature. This opens the possibility of using this material for magnetic cooling purposes.     

Structural,magnetic and magnetocaloric properties of AMn1−xGaxO3 compounds with 0≤x≤0.2

Structural, magnetic and magnetocaloric properties of manganites series with the AMn_1−xGa_xO₃ (A=La_0.75Ca_0.08Sr_0.17 and x=0, 0.05, 0.1 and 0.2) composition have been investigated to shed light on Ga-doping influence. Solid-state reaction method was used for preparation. From XRD study, all samples are found single phase and crystallize in the orthorhombic structure with the Pnma space group. The variation of the magnetization M vs. temperature T, under an applied magnetic field of 0.05 T, reveals a ferromagnetic–paramagnetic transition for all samples. The experimental results indicate that T_C decreases from 336 to 135 K with increasing Ga substitution. Magnetocaloric effect (MCE) was estimated, in terms of isothermal magnetic entropy change (−ΔS_M), using the M(T, μ₀H) data and employing the thermodynamic Maxwell equation. The maximum entropy change and Relative Cooling Power (RCP) show non-monotonic behaviors with increasing the concentration of Gallium. In fact, the maximum value of ΔS_Mmaxof AMn_1−xGa_xO₃ for x=0.00 and 0.2 samples is found to be, respectively, 2.87 and 1.17 J/kg/K under an applied magnetic field change of 2 T. For the same applied magnetic field (μ₀H=2 T), the RCP values are found to vary between 97.58 and 89 J/kg.     

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.     

Hydrothermal synthesis and Magnetocaloric effect of La0.5Ca0.3Sr0.2MnO3

The hydrothermal synthesis and magnetic entropy change for the perovskite manganite La_0.5Ca_0.3Sr_0.2MnO₃ have been studied. The La_0.5Ca_0.3Sr_0.2MnO₃ can be produced as phase-pure, crystalline powders in one step from solutions of metal salts in aqueous potassium hydroxide solution at a temperature of 513 K in 72 h. Scanning electron microscopy shows that the materials are made up of cuboid-shaped particles in typical dimension of 4.0×2.5×1.6 μm. Heat treatment can improve the magnetocaloric effect for the hydrothermal sample. The maximum magnetic entropy change ΔS_M for the as-prepared sample is 0.88 J kg⁻¹ K⁻¹ at 315 K for a magnetic field change of 2.0 T. It increases to 1.52 J kg⁻¹ K⁻¹, near its Curie temperature (317 K) by annealing the sample at 1473 K for 6 h. The hydrothermal synthesis method is a feasible route to prepare high-quality perovskite material for magnetic refrigeration application.     

Heat capacities of the electron acceptor 7,7,8,8-tetracyano- quinodimethane (TCNQ) and its radical-ion salt NH4(TCNQ) showing spin-Peierls transition

Heat capacities of the electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its radical-ion salt NH₄-TCNQ have been measured at temperatures in the 12-350 K range by adiabatic calorimetry. A λ-type heat capacity anomaly arising from a spin-Peierls (SP) transition was found at 301.3 K in NH₄-TCNQ. The enthalpy and entropy of transition are Δ_trsH=(667±7) J mol⁻¹ and Δ_trsS=(2.19±0.02) J K⁻¹ mol⁻¹, respectively. The SP transition is characterized by a cooperative coupling between the spin and the phonon systems. By assuming a uniform one-dimensional antiferromagnetic (AF) Heisenberg chains consisting of quantum spin (S=1/2) in the high-temperature phase and an alternating AF nonuniform chains in the low-temperature phase, we estimated the magnetic contribution to the entropy as Δ_trsS_mag=0.61 J K⁻¹ mol⁻¹ and the lattice contribution as Δ_trsS_lat=1.58 J K⁻¹ mol⁻¹. Although the total magnetic entropy expected for the present compound is R ln 2 (=5.76 J K⁻¹ mol⁻¹), a majority of the magnetic entropy (∼4.6 J K⁻¹ mol⁻¹) persists in the high-temperature phase as a short-range-order effect. The present thermodynamic investigation quantitatively revealed the roles played by the spin and the phonon at the SP transition. Standard thermodynamic functions of both compounds have also been determined.     

Magnetic hyperfine fields for Sn atoms in rare-earth intermetallides: huge deviation from proportionality between Bhf and Sz

The magnetic hyperfine fields for ¹¹⁹Sn impurity atoms, localized in Ga sites of ferromagnetic intermetallic compounds RGa (R=Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, and Tm), were measured by the Mössbauer spectroscopy technique. At T=5 K, the hyperfine field value (B_hf) varies from 3.3 T in TmGa to 28.0 T in GdGa. Huge deviation from the proportionality between B_hf and the projection of the R³⁺ ion spin (S_z=(g−1)J) was found. As the atomic number of the R element increases, the B_hf/S_z ratio drastically decreases from 12.6 T for PrGa to 3.3 T for TmGa. This unexpected result can be explained by the strong dependency of B_hf value on the relationship between the Sn-R atomic separation (R_nn) and the radius of the magnetic 4f shell (R_4f). In the framework of this concept, the available experimental data for Sn atom in the rare-earth compounds with non-magnetic sp elements were considered. The data may be described by the universal dependency on the single parameter, λ=R_nn/R_4f.     

Magnetic, magnetocaloric, and magnetotransport properties of RCo1.8Mn0.2 (R=Er, Ho, Dy, and Tb) compounds

The magnetic, magnetocaloric, and magnetotransport properties of RCo_1.8Mn_0.2 (R=Er, Ho, Dy, and Tb) were studied by room temperature X-ray diffraction, magnetization, and resistivity measurements at a temperature interval of 5-400 K and magnetic fields up to 5 T. The Curie temperature of RCo₂ was found to increase significantly when 10% Mn was substituted for Co. The effective paramagnetic moments were found to be in reasonable agreement with their theoretical values. A large magnetoresistance (MR) of Δρ/ρ_o≈−13.5% for R=Ho at T≈153 K for ΔH=5 T has been observed. The maximum relative cooling capacities vary from 467 J/kg at low temperature for R=Er to 202 J/kg at the near room temperature for R=Tb.     

Effect of Mn-site vacancies on the magnetic entropy change and the Curie temperature of La0.67Ca0.33Mn1−xO3 perovskite

Single-phase polycrystalline samples of La_0.67Ca_0.33Mn_1−xO₃ (x=0.00, 0.02, 0.04, 0.06) have been prepared using the sol-gel method. The structure, magnetocaloric properties and the Curie temperature of the samples with different Mn vacancy concentrations have been investigated. The experimental results show that vacancy doping at the Mn-sites has a significant influence on the magnetic properties of La_0.67Ca_0.33Mn_1−xO₃. The Curie temperature decreases monotonically with increasing the Mn-site vacancy concentration x. A remarkable enhancement of the magnetic entropy change has been obtained in the La_0.67Ca_0.33Mn_0.98O₃ sample. The entropy change reaches |ΔS_M|=3.10 J kg⁻¹ K⁻¹ at its Curie temperature (264 K) under an applied magnetic field H=10 kOe, which is almost the same value as that of pure Gd.     

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.     

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.     

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.     

Carbon-doping effects on the metamagnetic transition and magnetocaloric effect in MnAsCx

Carbon doping effects in MnAs alloys have been investigated. More carbon doping in MnAs alloys leads to lower Curie temperature, larger thermal hysteresis and sharper slope of the dependence of critical field on reduced temperature due to severe lattice distortion. The obtained maximum of magnetic entropy change for a field change of 5 T is about 12.8 J kg⁻¹ K⁻¹ near room temperature, and increases with more doping carbon content to about 22.4 J kg⁻¹ K⁻¹ in MnAsC_0.03 and 13.2 J kg⁻¹K⁻¹ in MnAsC_0.05.     

Structural, magnetic and magnetocaloric properties of La0.7−xEuxBa0.3MnO3 perovskites

Polycrystalline perovskite manganites La_0.7−xEu_xBa_0.3MnO₃(x=0.05, 0.1 and 0.15) were prepared by sol-gel method. The prepared samples remain single phase with a perovskite structure, revealed by X-ray diffraction. The structure refinement of La_0.7−xEu_xBa_0.3MnO₃(x=0.05, 0.1 and 0.15) samples was performed in the hexagonal setting of the R3¯c space group. The dependence of magnetization M on applied magnetic field H and temperature T was measured carefully near the Curie temperature T_C for all the samples. With the increasing Eu content, both the unit cell volume and Curie temperature T_C of 298 K has been detected with a maximum of magnetic entropy |ΔS_M^max| for the La_0.7−xEu_xBa_0.3MnO₃ with x=0.15, reaching a value of 2.3 J/kg K when a magnetic field of 10 kOe was applied and the relative cooling power (RCP) is 46 J/kg. These results suggest that the material may be a suitable candidate as working substance in magnetic refrigeration near room temperature.