Magnetocaloric effect in (La0.47Gd0.2)Sr0.33MnO3 polycrystalline nanoparticles

In this paper, nanosized particles of (La_0.47Gd_0.2)Sr_0.33MnO₃ perovskite-type oxides were successfully synthesized at a relatively low calcinated temperature at 800 °C for 10 h using amorphous molecular alloy as precursor. X-ray diffraction (XRD) and electron diffraction (ED) revealed that the resulting product is of pure single-phase rhombohedral structure. The Curie temperature T_C and magnetic entropy change (MCE) in (La_0.47Gd_0.2)Sr_0.33MnO₃ polycrystalline nanoparticles are determined and compared to those of similar systems prepared by the conventional solid-state reaction method. The Curie temperature T_C is shifted to 298 k, and a relatively large MCE with a broad peak around Curie temperature is observed in (La_0.47Gd_0.2)Sr_0.33MnO₃ polycrystalline particles. These results suggested that this material is a suitable candidate as working substance in magnetic refrigeration near room temperature.     

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.     

Magnetocaloric effect in La0.67Sr0.33MnO3 manganite above room temperature

The La_0.67Sr_0.33MnO₃ composition prepared by sol-gel synthesis was studied by dc magnetization measurements. A large magnetocaloric effect was inferred over a wide range of temperature around the second-order paramagnetic-ferromagnetic transition. The change of magnetic entropy increases monotonically with increasing magnetic field and reaches the value of 5.15 J/kg K at 370 K for Δμ0H=5 T. The corresponding adiabatic temperature change is 3.3 K. The changes in magnetic entropy and the adiabatic temperature are also significant at moderate magnetic fields. The magnetic field induced change of the specific heat varies with temperature and has maximum variation near the paramagnetic-ferromagnetic transition. The obtained results show that La_0.67Sr_0.33MnO₃ could be considered as a potential candidate for magnetic refrigeration applications above room temperature.     

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.     

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.     

Neutron-powder-diffraction study of structural and magnetic structure of La0.7Sr0.3Mn1−xTixO3 (x=0, 0.10, 0.20, and 0.30)

Neutron-diffraction and magnetic measurements have been used in order to study the structure and magnetic changes of La_0.7Sr_0.3Mn_1−xTi_xO₃ (x=0, 0.10, 0.20, and 0.30) perovskites. Magnetic measurements show that our samples exhibit a ferromagnetic–paramagnetic transition with decreasing temperature. Effects of Ti doping on the magnetic and nuclear structures are studied here by neutron-powder-diffraction for La_0.7Sr_0.3Mn_1−xTi_xO₃ (x=0.10, 0.20, and 0.30). Our analysis indicates that the three representative samples, with x=0.10, 0.20, and 0.30, have a hexagonal system of R3¯c space group, and that the magnetic moments order ferromagnetically into the (1 0 1) crystallographic planes, i.e. the magnetic moments of the Mn ion are in the ac plane, with no component along the b-axis. There is no crystalline structure changes when the Ti doping level increases.     

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.     

Structural, magnetic and magnetotransport behavior of La0.7SrxCa0.3−xMnO3 compounds

A systematic investigation of the structural, magnetic and electrical properties of a series of nanocrystalline La_0.7Sr_xCa_0.3−xMnO₃ materials, prepared by high energy ball milling method and then annealed at 900 °C has been undertaken. The analysis of the XRD data using the Win-metric software shows an increase in the unit cell volume with increasing Sr ion concentration. The La_0.7Sr_xCa_0.3−xMnO₃ compounds undergo a structural orthorhombic-to-monoclinic transition at x=0.15. Electric and magnetic measurements show that both the Curie temperature and the insulator-to-metal transition temperature increase from 259 K and 253 K correspondingly for La_0.7Ca_0.3MnO₃ (x=0) to 353 K and 282 K, respectively, for La_0.7Sr_0.3MnO₃ (x=0.3). It is argued that the larger radius of Sr²⁺ ion than that of Ca²⁺ is the reason to strengthen the double-exchange interaction and to give rise to the observed increase of transition temperatures. Using the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the resistivity versus temperature data measured in the range of 50-320 K and found that the activation barrier decreased with the raising Sr²⁺ ion concentration.     

Magnetocaloric properties in the Cr-doped La0.7Sr0.3MnO3 manganites

Single-phase polycrystalline samples of La_0.7Sr_0.3Mn_1-xCr_xO₃ with nominal composition of x=0.00, 0.20, 0.40 and 0.50 were prepared by a conventional solid-state reaction method in air. Investigations of magnetization were carried out in the temperature range 5-400 K and magnetic field range 0-8 T. It was found that the Curie temperature T_C decreases with increasing x and the maximum magnetic entropy change (−ΔS_M) for x=0.20 is ∼1.203 and ∼2.653 J/kg K, respectively for 2 and 6 T magnetic field near the temperature of 280 K.     

Determination of Curie temperature by Arrott plot technique in Gd5(SixGe1−x)4 for x>0.575

Determination of Curie temperature by plotting magnetic moment vs. temperature curves requires a small applied field, which influences the measurement and temporarily disturbs the temperature of the sample especially for highly magnetocaloric materials. The Arrott plot technique was therefore used in order to determine the Curie temperature for a magnetocaloric Gd₅Si_2.7Ge_1.3 (x=0.675) single crystal sample. This technique was compared with other methods such as the inflection point technique and the line projection method. The results show how applied magnetic field influences the determination of Curie temperature. Using the Arrott plot the second-order transition Curie temperature for Gd₅Si_2.7Ge_1.3 was determined to be 304 K.     

Effects of nonmagnetic silver Ag doping on the structural, magnetic and electric properties in La0.67Pb0.33MnO3 manganese oxides

The influence of the silver Ag-substitution for Pb ions in the mixed valence perovskites La_0.67Pb_0.33−xAg_xMnO₃ (0≤x≤0.15) was investigated by X-ray magnetic and electric transport measurements. All compositions were synthesized using the sol-gel technique. X-ray diffraction and structure refinement show that they crystallize in the rhombohedral structure with the R3?c space group. Upon Ag doping on Pb sites, the lattice parameters, unit cell volume, and the Mn-O-Mn bond angle are reduced. All the samples exhibit a ferromagnetic-paramagnetic transition and metallic-semi-conductor one with increasing temperature. The substitution of Pb by Ag has great influence on the magnetic and electrical transport properties of this family of compounds, decreasing continuously both the Curie temperature (from 361 to 290 K) and the resistivity transition temperature T_p.     

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.     

Enhancement of magnetoresistances at room temperature in YSZ doping La0.67Sr0.33MnO3 system

The temperature dependence of the resistance of composite samples (1−x)La_0.67Sr_0.33MnO₃+xYSZ with different YSZ doping level x was investigated at magnetic fields 0-3 T, where YSZ represents yttria-stabilized zirconia. Results show that the YSZ dopant does not only adjust the metal-insulator transition temperature, but also increases the magnetoresistance effect. With increase of YSZ doping level for the range of x<2%, the metal-insulator transition temperature values T_P of the composites decrease, but T_P increases with increase of x further for the range of x>2%. Meanwhile, in the YSZ-doped composites, a broad metal-insulator transition temperature region was found at zero and low magnetic field, which results in an obvious enhanced magnetoresistance in the temperature range 10-350 K. Specially, a larger magnetoresistance value was observed at room temperature at 3 T, which is encouraging with regard to the potential application of magnetoresistance materials.     

Synthesis and enhanced low-field magnetoresistance in La0.67Ca0.33MnO3 /CuO composites

The (1−x)La_0.67Ca_0.33MnO₃+xCuO composites have been synthesized by a new liquid phase method. The XRD and SEM measurements reveal that little CuO is soluble in the structure of La_0.67Ca_0.33MnO₃ and is mainly distributed at the grain boundary of La_0.67Ca_0.33MnO₃. As CuO content x increases, the magnetization M values increase until x=0.05 and M values decrease when x further increases at low temperature. For x=0.10, 0.20 and 0.30 composites, double metal-insulator transitions accompanying a single ferromagnetic transition are observed. Large low-field magnetoresistance is achieved for the composites and the largest magnetoresistance appeared when x=0.20.     

Magnetic properties and specific heat of Dy1−xLaxNi2 compounds

Magnetic and specific heat measurements have been carried out on polycrystalline series of single-phase Dy_1−xLa_xNi₂ (0?x?1) solid solutions. The compounds have a Laves-phase superstructure (space group F4¯3m) with the lattice parameter gradually increasing with decreasing Dy content. The samples with x?0.8 are ferromagnetic with the Curie temperature below 22 K. At high temperatures, all solid solutions are Curie-Weiss paramagnets. The Debye temperature, phonon and conduction electron contributions as well as a magnetic contribution to the heat capacity have been determined from specific heat measurements. The magnetocaloric effect was estimated from specific heat measurements performed in a magnetic field of 0.42 and 4.2 T.     

Magnetic properties of the Pr1−xGdxCo4B compounds

In this work, we have investigated the effect of the substitution of Gd for Pr on the crystal structure and magnetic properties of the Pr_1−xGd_xCo₄B compounds for 0?x?1 using X-ray powder diffraction, magnetic measurements, and differential scanning calorimetry (DSC). These compounds have hexagonal CeCo₄B-type structure with the space group P6/mmm. The substitution of Gd for Pr leads to a decrease of the unit-cell parameters a and the unit-cell volume V, while the unit-cell parameter c increases slightly. Magnetic measurements indicate that all samples are ordered magnetically below room temperature. The Curie temperatures determined by DSC technique increase as Pr is substituted by Gd. The saturation magnetization at 5 K decreases upon Gd substitution up to x=0.6, and then increases again.     

Influence of Tb substitution for La on the structure,magnetic and magneto-transport properties of La1.2Sr1.8Mn2O7

The physical properties of Tb³⁺ ions substitution at A-site are investigated in the layered manganite La_1.2Sr_1.8Mn₂O₇. A series of La_1.2−xTb_xSr_1.8Mn₂O₇ (x=0, 0.05, 0.15, and 0.20) shows that doping with a Tb ion of smaller radius in La_1.2Sr_1.8Mn₂O₇ caused diffraction peaks to shift to high angle. Some samples have an impure diffraction at about 30°, but all samples form single-phase. Samples can be well indexed on a Sr₃Ti₂O7-type tetragonal structure with the space group I4/mmm. According to the M-T curves, when x≤0.05, the series of samples shows ferromagnetism at low temperatures. With increasing temperature, they have two magnetic transitions at different temperatures. When x≥0.15, the magnetizations dramatically decrease. The ρ–T curves of samples show the metal–insulator transition for x=0, 0.05, and the maximum MR values in magnetic field 5 T are 74% at about 73 K and 94% at about 86 K. When x≥0.15, the samples remain in the insulator state in the whole observed temperature range, and the maximum MR values of 86% and 69% appeared at 74 K and 42 K.     

The relation between magnetoresistance and magnetocaloric effect in La0.85Ag0.15MnO3 manganite

We present the temperature dependence of La_0.85Ag_0.15MnO₃ resistivity in the temperature interval between 77 and 340 K and magnetic fields up to 26 kOe. We offer a method of separating tunnel magnetoresistance from total magnetoresistance. A change in both the magnetic entropy, which is caused by the magnetocaloric effect (MCE), and the magnetoresistance are shown to be connected through a simple relationship to La_0.85Ag_0.15MnO₃.     

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.     

Large room temperature magnetoresistance in YSZ doped La0.67Ba0.33MnO3 composite

The temperature dependence of the resistivity for composite samples of (1−x)La_0.67Ba_0.33MnO₃+xYSZ(LBMO/YSZ) with different YSZ doping level of x has been investigated in a magnetic field range of 0-7000 Oe, where the YSZ represents yttria-stabilized zirconia (8 mol% Y₂O₃+92 mol% ZrO₂). With increasing YSZ doping level, the range of 0-10%, the metal-insulator transition temperature (T_P) decreases. However, the resistivity, specially the low temperature resistivity, increases. Results also show that the YSZ doping level has an important effect on a low field magnetoresistance (LFMR). In the magnetic field of 7000 Oe, a room temperature magnetoresistance value of 20% was observed for the composite with a YSZ doping level of 2%, which is encouraging for potential application of CMR materials at room temperature and low field.