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.     

A magnetic, magnetostrictive and Mössbauer study of Tb0.3Dy0.7−xPrx(Fe0.9Al0.1)1.95 alloys

The effect of Pr substitution for Dy on the magnetization, magnetostriction, anisotropy and spin reorientation of a series of Tb_0.3Dy_0.7−xPr_x(Fe_0.9Al_0.1)_1.95 alloys (x=0, 0.1, 0.20, 0.25, 0.30, 0.35) at room temperature has been investigated. It was found that the magnetization and magnetostriction of the homogenized Tb_0.3Dy_0.7−xPr_x(Fe_0.9Al_0.1)_1.95 alloys decreases drastically with increasing x and the magnetostrictive effect disappears for x>0.2, but the spontaneous magnetostriction λ₁₁₁ increases approximately linearly with increasing x. Moreover, the magnetostriction exhibits slightly bigger value at x=0.1 than the free alloys and is saturated more easily with the magnetic field H, showing that a small amount of Pr substitution is beneficial to a decrease in the magnetocrystalline anisotropy. The analysis of the Mössbauer spectra indicated that the easy magnetization direction in the {1 1 0} plane deviates slightly from the main axis of symmetry with Pr concentration x, namely spin reorientation. Comparing with the Al substitution, the effect of Pr substitution for Dy on the spin reorientation is smaller.     

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.     

Magnetism, magnetocaloric effect and positive magnetoresistance in Fe-doped antipervoskite compounds SnCMn3−xFex (x=0.05-0.20)

The effects of Fe substitution on the structure, magnetic properties, magnetocaloric effect and positive magnetoresistance (MR) effect in antipervoskite compounds SnCMn_3−xFe_x (x=0.05-0.20) have been investigated systematically. Partial substitution of Fe for Mn leads to the monotonic reduction in both the Curie temperature T_C and saturated magnetization (M_S). It can be attributed to the reduction of electronic density of state at the Fermi energy by Fe-doping. The maximum values of magnetic entropy change (−ΔS_M) and positive MR gradually decrease as x increases, due to the broadening of magnetic phase transition. The refrigerant capacity increases initially with x≤0.05, then decreases gradually as x increases further, which is suggested to originate from the competition between the decreasing −ΔS_M and broadening temperature span. Our result indicates that the chemical doping on Mn site is an effective method for manipulating the properties of antiperovskite compounds AXMn₃.     

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.     

Magnetic entropy change in perovskite manganites La0.6Pr0.1Pb0.3MnO3 with double metal-insulator peaks

Following the double metal-insulator peaks found in series of perovskite manganites La_0.7−xPr_xPb_0.3MnO₃ (x=0, 0.05, 0.1), the magnetic entropy change of La_0.6Pr_0.1Pb_0.3MnO₃ was carefully investigated as a representative. The maximum magnetic entropy change (ΔS_H=−1.7 J/kg K at 300 K) and the expanded refrigerant capacity (about 123.8 J/kg) had been obtained under 10 kOe magnetic field variation, though the double peak of maximum magnetic entropy change had not occurred since the comparative faint magnetic signal from the Pr ions inhomogeneity existed in the octahedral frame submerged in the strong magnetic signal originated from the dominating octahedral frame both in the double exchange mechanism, but the width at half maximum in the magnetic entropy change comparatively broadened.     

Effect of Sn-doping on the structural,magnetic and magnetocaloric properties of La0.67Ba0.33Mn1−xSnxO3 compounds

Magnetocaloric effect (MCE) in fine-grained perovskite manganites of the type La_0.67Ba_0.33Mn_1−xSn_xO₃ (x=0.05, 0.1 and 0.15) were prepared by the solid-state method. The prepared samples remain single phase and exhibit paramagnetic to ferromagnetic phase transition (T_C) at 340, 325 and 288 K for x=0.05, 0.1 and 0.15, respectively. From the measured magnetization data of La_0.67Ba_0.33Mn_1−xSn_xO₃ compounds as a function of field (2 T), the associated magnetic entropy change close to their respective Curie temperatures and the relative cooling power (RCP) have been determined. Large MCE has been obtained in all samples and |ΔS_M|_max reached the highest value of 2.49 J/kg K at T_C (288 K) for the sample x=0.15, with H=2 T.     

Magnetocaloric effect at room temperature in manganese perovskite La0.65Nd0.05Pb0.3MnO3 with double resistivity peaks

Series of polycrystalline manganese perovskite oxides La_0.7−xNd_xPb_0.3MnO₃ (x=0, 0.05, and 0.1) are prepared by the sol-gel technique, La_0.65Nd_0.05Pb_0.3MnO₃ were representatively investigated because the peculiar double resistivity peaks were found; the maximum magnetic entropy change ΔS_H=−2.03 J/kg K and its good refrigerant capacity 71.05 J/kg around room temperature were obtained under 9 kOe magnetic field variation. The expected double peaks of magnetocaloric effect had not occurred since magnetic entropy change originated from the differential coefficient of magnetic moment to temperature; the relatively well refrigerant capacity possibly results from the faint magnetic inhomogeneity mixed in the double exchange strong magnetic signal.     

The influence of substitution of Co for Mn on magnetism of the HoMn6−xCoxSn6 compounds (0⩽x⩽0.25)

We have studied the effects of Co substitution for Mn on the structure and magnetic properties of the HoMn_6−xCo_xSn₆ compounds (0?x?0.25) with HfFe₆Ge₆-type structure (space group P6/mmm) by X-ray powder diffraction and magnetization measurements. A monotonic decrease of the lattice parameters a and c is observed with increasing Co content. While the compounds with x=0 and 0.05 exhibit ferrimagnetism in the whole temperature range, the compounds with 0.1?x?0.15 show ferrimagnetism, helimagnetism and re-entrant ferrimagnetism with decreasing temperature. For the compounds with x=0 and 0.05, the spin reorientation temperature is observed. A metamagnetic transition from helimagnetic magnetic ordering to ferrimagnetism is observed for the compounds with x=0.1 and 0.2. The results are summarized in the HoMn_6−xCo_xSn₆ magnetic phase diagram.     

Influence of boron on the giant magnetocaloric effect of La(Fe0.9Si0.1)13

The influences of boron addition on the phase formation, Curie temperature and magnetic entropy change of the NaZn₁₃-type La(Fe_0.9Si_0.1)₁₃ compound have been investigated. Eight boron containing La(Fe_0.9Si_0.1)₁₃B_x samples were prepared with x=0, 0.03, 0.06, 0.1, 0.2, 0.3, 0.5 and 0.6, respectively. Experimental results show that a small amount of B addition in La(Fe_0.9Si_0.1)₁₃ forms the solid solution NaZn₁₃-type structure phase by substituting B for Si or doping B into interstitial position of the lattice, preserves its giant magnetocaloric effects due to their first-order structural/magnetic transition, as well as increase its Curie temperature T_c slightly. The maximum magnetic entropy changes in the magnetic field change of 0–1.6 T are around 20 J kg^–1 K^–1 for the samples with Boron addition less than 0.3, while improving the Curie temperatures by 2 K.     

Metamagnetic transition and magnetocaloric effect in charge-ordered Pr0.68Ca0.32−xSrxMnO3 (x=0, 0.1, 0.18, 0.26 and 0.32) compounds

In this study, magnetic and magnetocaloric properties of Pr_0.68Ca_0.32−xSr_xMnO₃ (x=0, 0.1, 0.18, 0.26 and 0.32) compounds were investigated. X-ray results indicated that all the samples have a single phase of orthorhombic symmetry. The orthorhombic unit cell parameters increase with the increase in Sr content. Large negative magnetic entropy changes (−26.2 J/kg K at 38 K and 5 T for x=0 and −6.5 J/kg K at 83 K and 6 T for x=0.1) were attributed to ultrasharp metamagnetic transitions. The peak value of ΔS_m decreased from −4.1 J/kg K for x=0.18 sample to −2.4 J/kg K for x=0.32 at 1 T magnetic field.     

Magnetic entropy-change in La0.67−xBixCa0.33MnO3 compound

Bi doped lanthanum manganites with the chemical composition of La_0.67−xBi_xCa_0.33MnO₃ (x=0$x=0$, 0.05, 0.1, 0.2) were prepared by the standard solid-state process. The Curie temperatures were measured to be 267 K for x=0$x=0$, 248 K for x=0.05$x=0.05$, 244 K for x=0.1$x=0.1$ and 229 K for x=0.2$x=0.2$ samples. It was found that the maximum value of the magnetic entropy change ∣ΔS_m∣ has reached the highest value of 6.08 J/kg K at 3 T for the composition with x=0.05$x=0.05$. Nearly the same maximum entropy change was observed for the x=0$x=0$ sample. A large decrease in the magnitude of the entropy change was observed for the x=0.2$x=0.2$ sample.     

Magnetic entropy change in GdCo13−xSix intermetallic compounds

The magnetic entropy change in GdCo_13−xSi_x (x=3.8, 4, 4.1, and 4.2) intermetallic compounds has been investigated by means of magnetic measurements in the vicinity of their Curie temperature. It was found that the magnetic ordering temperatures decrease from 60 K at x=3.8 to 28 K for x=4.2. The magnetic entropy change is calculated from isothermal magnetization versus magnetic field at various temperatures using the Maxwell relation. As a result, the maximum magnetic entropy changes of the investigated compounds, at their Curie temperatures, decrease from 11.5 J/kg K for x=4.2 to 6.86 J/kg K for x=3.8 in a field change of 0-3 T, whereas it decreases from 5.13 J/kg K for x=4.2 to 2.60 J/kg K for x=3.8 in a field change of 0-1 T. Moreover, the maximum value of the magnetic entropy change obtained at a higher field for GdCo_13−xSi_x with x=4 (23.75 J/kg K at 5 T) is comparable to that of various types of compounds with a cubic NaZn₁₃-type structure. Finally, the maximum of the magnetic entropy change is found to decrease with increasing Si content.     

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.     

Monodispersed nanocrystalline Co1–xZnxFe2O4 particles by forced hydrolysis: Synthesis and characterization

Zinc-substituted cobalt ferrites, Co_1–xZn_xFe₂O₄, were for the first time successfully prepared by forced hydrolysis method. The obtained materials are single phase, monodispersed nanocrystalline with an average grain size of about 3 nm. These materials are superparamagnetic at room temperature and ferrimagnetic at temperature lower than the blocking temperature. When the zinc substitution increases from x=0 to 0.4, at 4.2 K, the saturation magnetization increases from 72.1 to 99.7 emu/g. The high saturation magnetization of these samples suggests that this method is suitable for preparing high-quality nanocrystalline magnetic ferrites for practical applications.     

Magnetocaloric properties of the La0.7Pr0.3Fe13−xSix compounds

Magnetic entropy change ΔS_m, hysteresis loss and refrigerant capacity of NaZn₁₃-type La_0.7Pr_0.3Fe_13−xSi_x (1.5?x?2.0) compounds have been investigated. The Curie temperature T_C increases linearly with the increase of silicon concentration. Although the maximum value of ΔS_m under a field change of 0−5 T decreases from 30.5 to 11.4 J/kg K as x increases from 1.5 to 2.0, the hysteresis loss at T_C reduces remarkably from 89.2 J/kg for x=1.5 to zero for x=2.0 because the increase of Si content can weaken the itinerant electron metamagnetic transition. The effective refrigerant capacity RC_eff is maintained at high values of 362−439 J/kg for a field change of 0−5 T. This implies that a large ΔS_m and a high RC_eff can be achieved simultaneously in the La_0.7Pr_0.3Fe_13−xSi_x compounds.     

Magnetic properties of Ho1−xMmxCo2 (x=0, 0.1, 0.2, 0.3 and 0.4) alloys and their hydrides

The influence of Mm (Mm=mischmetal) substitution and hydrogen absorption on the magnetic properties of Ho_1−xMm_xCo₂ (x=0, 0.1, 0.2, 0.3 and 0.4) alloys have been determined through the temperature dependence of ac susceptibility and thermopower measurements. The changes in magnetic-ordering temperature of Ho_1−xMm_xCo₂ alloys have been explained based on the dilution of the magnetic ions and weakening of 4f–3d exchange interactions. The gradual disappearance of the magnetic transition temperature upon increasing hydrogen concentration (y) has been interpreted by the lattice expansion and charge transfer between absorbed hydrogen and 3d-band of Ho_1−xMm_xCo₂.     

Magnetic properties of the Ce2Fe17−xMnx helical magnets up to high magnetic fields

Magnetic properties of the Ce₂Fe_17−xMn_x, x=0–2, alloys in magnetic fields up to 40 T are reported. The compounds with x=0.5–1 are helical antiferromagnets and those with 1<x?2 are helical ferromagnets or helical antiferromagnets at low and high T, respectively. Mn ions in the system carry average magnetic moment of 3.0±0.2 μ_B that couple antiparallelly to the Fe moments. Easy-plane magnetic anisotropy in the Ce₂Fe_17−xMn_x compounds weakens upon substitution of Mn for Fe. The absolute value of the first anisotropy constant in the Ce₂Fe_17−xMn_x helical ferromagnets decreases slower with increasing temperature than that calculated from the third power of the spontaneous magnetization. Noticeable magnetic hysteresis in the Ce₂Fe_17−xMn_x, x=0.5–2, helical magnets over the whole range of magnetic fields reflects mainly irreversible deformation of the helical magnetic structure during the magnetization of the compounds. A contribution from short-range order (SRO) magnetic clusters to the magnetic hysteresis of the helical magnets has been also estimated.     

Magnetic and magneto-transport properties of double perovskite Ba2−xSrxFeMoO6 system

The structural magnetic and magneto-transport properties of double perovskite system Ba_2−xSr_xFeMoO₆ (0?x?1.0) prepared in bulk polycrystalline form are reported in this paper. X-ray diffraction analysis showed that samples are single phase and the lattice constants decreases with increase in the Sr content. The degree of Fe-Mo ordering has been found decreasing in the series with an increase in the Sr content. Parent compound Ba₂FeMoO₆ exhibits saturation magnetic moment value of 3.54 μ_B/f.u. at 85 K in a magnetic field of 6000 Oe. Temperature dependence of resistivity shows metallic behavior for all the samples. The magneto-resistance (MR) of the compound with x=0.4 is higher than that of the other samples. At room temperature this system shows a saturation magnetization value of 1.73 μ_B/f.u. and MR value of 7.08% (1 T). The observed variations in the structural and magnetic properties are attributed to the change of chemical pressure due to the substitution of Sr in place of Ba. The effect of antisite disorder (ASD) defects on magneto-transport properties is studied in more detail.     

Magnetocaloric properties of DyCo2−xGax alloys

The influence of the substitution of Ga atoms for Co atoms in DyCo₂ compounds on magnetocaloric properties has been investigated. A series of DyCo_2−xGa_x alloys with x=0, 0.03, 0.06, 0.1, 0.15, and 0.2 was prepared by the arc-melting method for this investigation. Experimental results revealed that the Ga substitution for Co in DyCo₂ can form a single phase with the cubic Laves phase structure up to x=0.2. As the Ga content x increases, the lattice parameter and the Curie temperature T_c increases from 143 to 196 K linearly. The maximum magnetic entropy changes in a low field change of 0-1.5 T, increasing from 8.24 to 10.61 J/K kg when the Ga content x increases from 0 to 0.03, but decreasing gradually to 3.51 J/K kg as the Ga content further increases to x=0.2. All the samples show a relatively large magnetic entropy change with very small hysteresis loss.