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.     

Large roomtemperature magnetocaloric effect with negligible magnetic hysteresis losses in Mn1−xVxCoGe alloys

The magnetic and magnetocaloric properties have been investigated in a series of Mn_1−xV_xCoGe (x=0.01, 0.02, 0.03, and 0.05) alloys. The substitution of V for Mn reduces the structural transformation temperature of MnCoGe alloy effectively and results in a second-order magnetic transition in Mn_0.95V_0.05CoGe alloys. Large room temperature magnetocaloric effect and almost zero magnetic hysteresis losses are simultaneously achieved in the alloys with x=0.01, 0.02, and 0.03. The reasons for the negligible magnetic hysteresis losses and the potential application for the roomtemperature magnetic refrigeration are discussed.     

Crystallography,magnetic properties and magnetocaloric effect in Gd4(BixSb1−x)3 alloys

A study of magnetic and thermal properties has been carried out on the alloys from the Gd₄(Bi_xSb_1−x)₃ series with x=0, 0.25, 0.5, 0.75, and 1. All of the alloys are ferromagnetic below their respective Curie temperatures which vary from 266 K for x=0 to 332 K for x=1.0. The magnetocaloric effect calculated from the temperature and magnetic field dependencies of the magnetization and heat capacity is moderate when compared to that of other materials, which order in the same temperature range. Both the magnetic ordering and the magnetocaloric effect peak temperatures increase nearly linearly with the increasing Bi content. Experimental magnetocaloric effect data obtained from two different measurement techniques are in excellent agreement.     

Magnetocaloric effect in Pr<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> manganites

The magnetocaloric effect in alternating magnetic fields has been investigated in Pr_{1 − x} Ag _x MnO₃ manganites with x = 0.05−0.25. The stepwise reversal of the sign of the magnetocaloric effect has been revealed in a weakly doped sample (x = 0.05) at low temperatures (∼80 K). This reversal is attributed to the coexistence of the ferromagnetic and canted antiferromagnetic phases with different critical temperatures.     

Magnetocaloric effect in sandwich structures of La<Subscript>1–<Emphasis Type="Italic">x</Emphasis> </Subscript>K<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>MnO<Subscript>3</Subscript> manganites

This paper reports on the results of the investigation into the magnetocaloric properties of sandwich structures of La_1–xK_xMnO₃ manganites with x = 0.11 (LKM11), 0.13 (LKM13), and 0.15 (LKM15) in magnetic fields of up to 18 kOe. The results of the analysis of the field and temperature dependences of the magnetocaloric effect in the structures LKM11 + LKM13 and LKM13 + LKM15 have demonstrated that the use of sandwich structures increases the efficiency of magnetic cooling in a magnetic field of 18 kOe by 45%.     

Magnetocaloric properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>K<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

A technology for obtaining single-phase ceramic samples of La_{1 − x} K _x MnO₃ manganites, as well as the dependence of their structure parameters on the potassium content, is described. The magnetocaloric effect in the samples has been measured by two direct methods, the classical method and the magnetic field modulation method, and has been calculated from the specific heat data. The values of the magnetocaloric effect obtained by these methods are significantly different. The observed discrepancies have been explained. Correlation between the doping level and the value of the effect has been found. It has been shown that the magnetic-field dependence of variation of the magnetic entropy near T _C in weak fields corresponds to theoretical calculations and that the value of the magnetocaloric effect in high magnetic fields can be predicted using this dependence.     

Magnetocaloric effect in La0.65−xEuxSr0.35MnO3

The magnetocaloric properties for the Eu-doped La_0.65?xEu_xSr_0.35MnO₃ samples with x = 0.05, 0.15, 0.20, and 0.30 upon 0.05T magnetic field have been investigated. It is found that the Eu doping in this system decreases the magnetocaloric properties lightly. Moreover, the results of Eu doping clearly indicate that the magnetocaloric effect in this system is tunable, which is beneficial for manipulating magnetocaloric refrigeration that occurs in various temperature ranges. This makes the La_0.65?xEu_xSr_0.35MnO₃ samples potential candidates for practical applications. A complete characterization of the magnetic properties of this material aids to the understanding required for the technological exploitation of such materials, and it suggests La_0.65?xEu_xSr_0.35MnO₃ perovskite as the promising magnetic refrigerant.     

The magnetic phase transitions and magnetocaloric effect in MnNi1−xCoxGe alloys

The magnetic phase transitions and the magnetocaloric effects in MnNi_1−xCo_xGe (x=0.38 and 0.40) alloys were investigated. The substitution of Co for Ni in the MnNiGe antiferromagnet results in the metamagnetic transitions from antiferromagnetic to ferromagnetic state, which associates with very small thermal and magnetic hystereses. Positive and negative values of magnetic entropy changes are exhibited around the metamagnetic transition temperature and Curie temperature, respectively. The relatively large refrigerant capacity in low magnetic field along with the good reversibility suggest that MnNi_1−xCo_xGe (x=0.38 and 0.40) alloys are potential candidates for magnetic refrigeration.     

Model of the magnetorefractive effect in manganites within the effective medium theory

The magnetorefractive effect (MRE) in manganites has been studied within the effective medium theory. The MRE has been calculated in manganites La_1–xK_xMnO₃ (x = 0.1 and 0.15) for light transmission and reflection. Good agreement with experimental results demonstrates direct relation of the MRE to the magnetoresistance and optical properties of manganites with various substitution levels. It has been shown that the MRE can exceed 10% in the near- and mid-IR region near the magnetic phase transition and can change sign during light transmission and reflection in the region of phonon modes. The results make it possible to recommend the MRE as a contactless method for studying magnetoresistive materials and for developing sensors and microelectronic elements.     

Properties of magnetocaloric La(Fe,Co,Si)13 produced by powder metallurgy

We present a comprehensive study of the magnetocaloric materials series La(Fe_1−xCo_x)_11.9Si_1.1 with 0.055<x<0.122. The ferromagnetic samples were manufactured using a novel powder metallurgy process by which industrial scale production is feasible. This new production method makes the materials more attractive as magnetic refrigerants for room temperature magnetic refrigeration. The Curie temperature of the compounds can be easily tuned by altering the Co content and all samples have little magnetic anisotropy and present a second-order magnetic transition so that thermal and magnetic hysteresis is absent. For all seven samples, we have calculated the magnetic entropy change, ΔS_M, from initial curve measurements and measured the adiabatic temperature change, ΔT_ad, directly. In addition, for two of the samples, we determined the heat capacity as a function of applied magnetic field and the thermal conductivity. Where relevant, the results are compared with those of Gd, the benchmark material for room temperature magnetic refrigeration.     

Magnetocaloric properties of manganites La<Subscript>1−x</Subscript>(Ag,K)<Subscript>x</Subscript>MnO<Subscript>3</Subscript>

The temperature and magnetic-field dependences of the magnetocaloric effect in manganites La_1−x Ag _x MnO₃ (x = 0.1; 0.15; 0.2) and La_1−x K _x MnO₃ (x = 0.1; 0.11; 0.13; 0.15; 0.175) were studied by a direct method. Large changes in the sample temperature were detected as a magnetic field changed by ΔH = 10 kOe. Temperatures of the magnetocaloric effect maxima are near room temperatures. Field dependences of the magnetocaloric effect show no signs of saturation in fields to 30 kOe.     

Structural, magnetic, magnetocaloric and magnetotransport properties in Ge doped Ni-Mn-Sb Heusler alloys

The effect of Ge substitution on the magnetic, magnetocaloric and transport properties of Ni₄₅Co₅Mn₃₈Sb_12−xGe_x (x=0-3) has been investigated. The decrease in the exchange interaction brought by Ge substitution can be seen from the reduction in the magnetization of austenite phase and the increase in the martensitic transition temperature. The magnetocaloric effect and the magnetoresistance values are found to be quite sensitive to small changes in Sb/Ge ratio. Taking into account various properties, the present series seems to be a promising multifunctional system.     

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.     

Phase transitions induced by a strong magnetic field in electron-doped manganites

The magnetic and magnetoelastic properties of single crystals of electron-doped rare-earth manganites La_1?x Sr _x MnO₃ are studied. Phase transitions from the A-type antiferromagnetic phase to the C-type anti-ferromagnetic phase in a strong magnetic field are revealed in La_1?x Sr _x MnO₃ manganites with a strontium content x = 0.65. A similar phase transition is observed in manganites with a strontium content x = 0.8, at which the La_0.2Sr_0.8MnO₃ manganite is assumed to transform from the C-type antiferromagnetic phase to the G-type antiferromagnetic phase.     

Preparation and magnetic properties of LaMnO3 + δ (0 ≤ δ ≤ 0.154)

The structural, electrical, and magnetic properties of ceramic perovskite manganites LaMnO_{3 + δ} (δ = 0–0.154) are investigated. It is found that, in a weak magnetic field (B = 2 G), the LaMnO_{3 + δ} manganite with δ = 0.065 at temperatures below the Curie temperature T _C of the paramagnet-ferromagnet phase transition has a mixed (spin glass + ferromagnet) phase. In LaMnO_{3 + δ} manganites with the parameter δ = 0.100–0.154, this phase transforms into a frustrated ferromagnetic phase. A similar transformation was observed previously in La_1?x Ca_xMnO₃ compounds at calcium contents in the range 0 ≤ x ≤ 0.3. This similarity is explained by the fact that, in both materials, the Mn⁴⁺ concentration and, accordingly, the hole concentration c change equally in the concentration range from ～0.13 to 0.34 with an increase in x or δ. However, the magnetic irreversibility, the concentration dependences of the Curie temperature T _C(c) and the magnetic susceptibility X(c), and the critical behavior of the temperature dependence of the susceptibility X(T) in the vicinity of the Curie temperature T _C differ substantially for these two materials. The observed differences are associated with the distortion of the cubic perovskite structure, the decrease in the degree of lattice disorder, and a more uniform distribution of holes in the LaMnO_{3 + δ} manganites as compared to the La_{1 ? x} Ca_xMnO₃ compounds.     

The magnetic entropy change in La0.8Ce0.2Fe11.4Si1.6Bx compounds prepared by copper-mold casting

The magnetocaloric effect (MCE) of La_0.8Ce_0.2Fe_11.4Si_1.6B_x (x=0.0-0.5) compounds, prepared by a copper-mold casting (CMC) method, has been investigated. Comparing with the conventional arc-melting (CAM) method, the relatively homogenous composition and microstructure were achieved in the precursor alloys prepared by the CMC method. As a result, the annealing time is dramatically shortened from several weeks for CAM alloys to 2 h for CMC alloys, suggesting that CMC method is a time-saving and energy-saving method for fabrication of MCE alloys. On the other hand, it is revealed that B addition gives rise to an enhancement of Curie temperature (T_C), a reduction of thermal lag and magnetic hysteresis and a broadening of working temperature span as well. Although the peak value of magnetic entropy change decreases with B content, various B-contained compounds hold close refrigerant capacities. Comprehensively considering magnetocaloric properties of the B-contained La_0.8Ce_0.2Fe_11.4Si_1.6B_x compounds, it can be concluded that the B-contained compounds prepared by CMC method are promising candidates of magnetocaloric materials in practical application.     

Effect of trivalent cation substitution for manganese upon ferromagnetism in Ln0.57Ca0.43MnO3 (Ln=Pr, Nd)

The substitution of small contents of trivalent cations for manganese in the oxides Ln_0.57Ca_0.43Mn_1−xM_xO₃ (Ln=Pr, Na) has been explored for M=Al, Ga, Fe, Cr, Sc, In. It is shown that similarly to Ba-doping, the M-doped Pr-manganites exhibit a great predisposition to ferromagnetism in a low magnetic field of 0.25 T, reaching ferromagnetic (FM) fractions of 85% for M=Ga and 100% for m=Cr, whereas in contrast only small FM fractions (∼8%) can be reached for the M-doped Nd-manganites. The great ability of both Pr and Nd manganites to exhibit ultrasharp steps at 2.5 K, at increasing magnetic field is also demonstrated. The different behaviors of the so-doped manganites are interpreted in terms of geometric effects (size of the A-sites cations and of the doping elements) and of electronic configurations and magnetic properties of the dopants.     

Powder metallurgy influences on the magnetic properties of Gd5.09Ge2.03Si1.88 alloy

Magnetic refrigeration is an innovative technology owing to its high-efficiency, low-energy consumption, and environmental friendliness. However, the manufacturing process of the magnetocaloric materials is an obstacle to the effective application of those materials on refrigeration systems. In this work, we present a magnetic characterization of the Gd_5.09Ge_2.03Si_1.88.alloy, analyzing the as-cast bulk and the sintered tablets after some heat treatments. The study of powder metallurgy parameters such as grain size, compacting pressure and sintering process has showed results comparable to the as-cast alloy, which presents ΔS_T=−18 /kg K.     

Large low-field inverse magnetocaloric effect near room temperature in Ni50−x Mn37+x In13 Heusler alloys

Low field inverse magnetocaloric effect (IMCE) associated with first-order martensitic transition in Ni_50−x Mn_37+x In₁₃ (x=3,4,5) alloys was investigated. By tuning the composition of Ni/Mn, large change in the magnetization occurring between martensite and austenite phases in a narrow temperature interval was achieved, which results in large IMCE. Under low magnetic field change of 2 T, a large positive magnetic entropy change (ΔS _M ) of 23.5 J/kg K with a net refrigeration capacity of 53 J/kg was obtained near room temperature (308 K) in the x=3 alloy. The results show that a small variation in Ni/Mn ratio significantly influences the martensitic transition temperature and the associated magnetic and magnetocaloric properties.     

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.