Magnetocaloric properties of La0.7Ca0.3MnO3 manganites with 16O → 18O isotopic substitution

This paper reports on a study of the effect of isotopic ¹⁶O → ¹⁸O oxygen substitution on the heat capacity and magnetocaloric properties of the La_0.7Ca_0.3MnO₃ manganite. Direct measurements of the magnetocaloric effect have demonstrated that, in La_0.7Ca_0.3MnO₃, the effect reaches a fairly large magnitude, but its temperature width is rather small. The ¹⁶O ar ¹⁸O isotopic substitution shifts the temperature of the maximum of the effect toward lower temperatures while leaving its magnitude practically unchanged. The magnetocaloric effect in the La_0.7Ca_0.3Mn¹⁶O₃ + La_0.7Ca_0.3Mn¹⁸O₃ sandwich structure has been measured by the direct method. It has been shown that fabrication of a sandwich from materials with close temperatures of the maxima of the magnetocaloric effect permits increasing the relative cooling power (RCP) compared with that of the starting materials.     

Improvement of refrigerant capacity of La0.7Ca0.3MnO3 material with a few percent Co doping

The influence of first and second order magnetic phase transitions on the magnetocaloric effect (MCE) and refrigerant capacity or relative cooling power (RCP) of La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃ materials has been investigated. Large low-field-induced magnetic entropy changes are observed in La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃ materials. The La_0.7Ca_0.3MnO₃ material experiences a large entropy change with a first-order magnetic phase transition at the Curie temperature, T_C. On the other hand, La_0.7Ca_0.3Mn_0.95Co_0.05O₃ displays a smaller entropy change with a second order phase transition. While a first-order magnetic transition material induces a larger MCE (7.528 J/kg K at 5 T) at T_C, this is limited to a narrow temperature range, resulting in a relatively small RCP (218 J/kg), while the Co-doped second-order magnetic transition material induces a smaller MCE (7.14 J/kg K for 5 T), but it is spread over a broader temperature range, resulting in a larger RCP (308 J/kg). The maximum magnetoresistance (MR, defined as ρ(0)/ρ(H)-1) under a field of 5 T is about 206% and 333% for La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃, respectively. The refrigeration capacity (RCP) is enhanced in La_0.7Ca_0.3Mn_0.95Co_0.05O₃ (by about 41%) due to small changes from Co doping. The magnetocaloric features of these materials at lower magnetic fields (MCE=3.163 for La_0.7Ca_0.3Mn_0.95Co_0.05O₃ and 4.63 J/kg K for La_0.7Ca_0.3MnO₃ at 1 T), and the high RCP and MR can provide some ideas for exploring novel magnetic refrigerants that can operate with permanent magnets rather than superconducting ones as the magnetic field source.     

Cation disorder and size effects on the magnetic transition in Ba-containing ferromagnetic manganites

The results of ⁵⁵Mn NMR, dc magnetization, and ac susceptibility studies are presented for La_0.7Ca_0.15Ba_0.15MnO₃, La_0.7Sr_0.15Ba_0.15MnO₃, and La_0.7Ba_0.3MnO₃ ferromagnetic manganites. While is a function of the mean radius of the La and alkaline-earth ions and the cation disorder, the form of the temperature dependence of the magnetic moment may be expressed as function of only. The phase transition is continuous for all three compounds. Received 5 March 1999     

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.     

Perovskite nanoparticles: Preparation by reactive milling and magnetic characteristics

La_0.7Sr_0.3MnO₃ and La_0.7Ca_0.3MnO₃ nanoparticles were synthesized by reactive milling method. Grain size determined from XRD, TEM, and magnetization measurements show an average diameter ?18 nm and decreasing with increasing milling time. DC and AC magnetic measurements evidenced an interacting superparamagnetism due to clustering of perovskite nanoferromagnets with spin dynamic time in range of 10⁻⁹–10⁻¹⁰ s.     

Estimation of the magnetic entropy change by means of Landau theory and phenomenological model in La0.6Ca0.2 Sr0.2MnO3/Sb2O3 ceramic composites

In this paper, magnetocaloric properties of La_0.6Ca_0.2Sr_0.2MnO₃/Sb₂O₃ oxides have been investigated. The composite samples were prepared using the conventional solid-state reaction method. The second-order phase transition can be testified with the positive slope in Arrott plots. An excellent agreement has been found between the ?ΔS_M values estimated by Landau theory and those obtained using the classical Maxwell relation. The field dependence of the magnetic entropy change analysis shows a power law dependence,|ΔS_M|≈Hⁿ , with n(T_C) = 0.65. Moreover, the scaling analysis of magnetic entropy change exhibits that ΔS_M(T) curves collapse into a single universal curve, indicating that the observed paramagnetic to ferromagnetic phase transition is an authentic second-order phase transition. The maximum value of magnetic entropy change of composites is found to decrease slightly with the further increasing of Sb₂O₃ concentration. A phenomenological model was used to predict magnetocaloric properties of La_0.6Ca_0.2Sr_0.2MnO₃/Sb₂O₃ composites. The theoretical calculations are compared with the available experimental data.     

Conductivity of La1−x CaxMnO3 under magnetic resonance of Mn ions

A change in the electrical conductivity, σ, is observed in the manganese perovskite La_1?x Ca_xMnO₃, with x=0 and 0.3 under saturation of the magnetic resonance transitions of Mn ions. This effect has a maximum in the temperature range of the magnetic phase transition of the compounds. Two contributions to the change in σ are found. The first, dominating in LaMnO₃, is an increase in σ caused by heating of the sample under magnetic resonance. The second is a σ decrease due to reorientation of the Mn spins, observed in La_0.7Ca_0.3MnO₃.     

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.     

Tuning the magnetocaloric properties of La0.7Ca0.3MnO3 manganites through Ni-doping

The effect of Ni²⁺ doping on the magnetic and magnetocaloric properties of La_0.7Ca_0.3MnO₃ manganites synthesized via the auto-combustion method is reported. The aim of studying Ni²⁺-substituted La_0.7Ca_0.3Mn_1 ? xNi_xO₃ ($x=0,0.02,0.07$, and 0.1) manganites was to explore the possibility of increasing the operating temperature range for the magnetocaloric effect through tuning of the magnetic transition temperature. X-ray diffraction analysis confirmed the phase purity of the synthesized samples. The substitution of Mn³⁺ ions by Ni²⁺ ions in the La_0.7Ca_0.3MnO₃ lattice was also corroborated through this technique. The dependence of the magnetization on the temperature reveals that all the compositions exhibit a well-defined ferromagnetic to paramagnetic transition near the Curie temperature. A systematic decrease in the values of the Curie temperature is clearly observed upon Ni²⁺ doping. Probably the replacement of Mn³⁺ by Ni²⁺ ions in the La_0.7Ca_0.3MnO₃ lattice weakens the Mn³⁺–O–Mn⁴⁺ double exchange interaction, which leads to a decrease in the transition temperature and the magnetic moment in the samples. By using Arrott plots, it was found that the phase transition from ferromagnetic to paramagnetic is second order. The maximum magnetic entropy changes observed for the $x=0,0.02,0.07$, and 0.1 composites was 0.85, 0.77, 0.63, and 0.59 J/kg?K, respectively, under a magnetic field of 1.5 T. In general, it was verified that the magnetic entropy change achieved for La_0.7Ca_0.3Mn_1 ? xNi_xO₃ manganites synthesized via the auto-combustion method is higher than those reported for other manganites with comparable Ni²⁺-doping levels synthesized via standard solid state reaction. The addition of Ni²⁺ increases the value of the relative cooling power as compared to that of the parent compound. The highest value of this parameter (～60 J/kg) is found for a Ni-doping level of 2% around 230 K in a field of 1.5 T.     

Particle size effects on La0.7Ca0.3MnO3: size-induced changes of magnetic phase transition order and magnetocaloric study

The structure, magnetic properties, and magnetocaloric effect of La_0.7Ca_0.3MnO₃ ceramics with different particle sizes have been investigated. It is found that the Curie temperature increases first, and then decreases as particle size decreases and the type of magnetic phase transition changes from first-order to second-order, which may be attributed to surface pressure effects. The maximum magnetic entropy change and relative cooling power (RCP) show non-monotonic behaviors with decreasing the particle size. However, for the 3400 nm sample, the magnetic entropy change −ΔS_M reaches the maximum values of 6.41 and 8.63 J/kg K for the field changes of 2.0 and 4.5 T, respectively. Furthermore, the estimated large RCP values under lower magnetic fields in La_0.7Ca_0.3MnO₃ are comparable with those of typical magnetic refrigerant materials in the corresponding temperature range, suggesting those compounds might be promising candidates for magnetic refrigeration.     

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 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.     

Percolative transport in the vicinity of charge-order ferromagnetic transition in a hole-doped manganite

We report measurements of non-linear charge transport in epitaxial (La_1−x Pr _x )_0.7Ca_0.3MnO₃ thin films fabricated on (100) oriented SrTiO₃ single crystals by pulsed laser deposition. The end members of this series, namely Pr_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3MnO₃ are canonical charge-ordered (CO) and ferromagnetic manganites, respectively. The onset of the CO state in Pr_0.7Ca_0.3MnO₃ is manifested by a pronounced insulating behavior below ∼ 200 K. The CO state remains stable even when a large (∼ 2×10⁵ V/cm) electric field is applied across the thin film samples. However, on substitution of Pr with La, a crossover from the highly resistive CO state to a state of metallic character is observed at relatively low electric fields. The current-voltage characteristics of the samples at low temperatures show hysteretic and history dependent effects. The electric field driven charge transport in the system is modelled on the basis of an inhomogeneous medium consisting of ferromagnetic metallic clusters dispersed in a CO background.     

Maximum magnetic entropy change modulated toward room temperature in perovskite manganites La0.7−xNdx(Ca,Sr)0.3MnO3

With Nd³⁺ doping and Ca²⁺, Sr²⁺ modulating in the sol–gel technique, a series of polycrystalline perovskite samples La_0.7?xNd_x(Ca,Sr)_0.3MnO₃ (x = 0, 0.05, 0.1, 0.15, 0.20, 0.25) was prepared, their maximum magnetic entropy changes were tuned to room temperature (ΔS_H = ?1.47 J/kg K at 298 k for La_0.45Nd_0.25(Ca,Sr)_0.3MnO₃), an enhancement of the maximum magnetic entropy change (ΔS_H = ?1.89 J/kg K at 315 k) and its refrigerant capacity (about 45.3 J/kg) had also been obtained under 9 kOe magnetic field variation for La_0.55Nd_0.15(Ca,Sr)_0.3MnO₃ contrast to La_0.7(Ca,Sr)_0.3MnO₃.     

Room temperature magnetocaloric effect of La-deficient bulk perovskite manganite La0.7MnO3−δ

Room temperature magnetocaloric effect in La-deficient bulk perovskite manganite La_0.7MnO_3−δ prepared by conventional solid-state reaction has been reported. The maximum value of the magnetic entropy change (about−1.32 J/kg K) and the refrigerant capacity (approximately close to 37 J/kg) had been obtained at 290 K corresponding to a magnetic field variation of 1 T for La_0.7MnO_3−δ. It is the strong Jahn-Teller coupling that changes Mn-O bond length and Mn-O-Mn bond angles and then the canted spin arrangement and induces the strong double-exchange coupling to a comparatively high magnetic transition temperature. This Curie temperature near room temperature with easy fabrication and higher chemical stability makes La_0.7MnO_3−δ a potential candidate as a working substance in magnetic refrigeration technology.     

Evidence of reduction in spin disorder by Ho3+ doping in La0.7Ca0.3MnO

We have shown in a recent study that substitution of Ho³⁺ ions (4f¹⁰; magnetic momen _μB) in La_0.7Ca_0.3MnO₃ causes significant reduction in electrical resistivity compared with Y³⁺ (4d⁰; non-magnetic) ion substitution. This reduction in resistivity was attributed to the reduced spin disorder scattering in La_0.7Ca_0.3MnO₃ samples containing magnetic Ho³⁺. We have estimated the Mn-spin canting angles in Ho³⁺ - and Y³⁺-doped La_0.7Ca_0.3MnO₃ compounds from the resistivity data using the magnetic localization model. We find that the canting angles of the Mn spins in the Ho³⁺ doped compounds are smaller than those obtained for the Y³⁺-doped compounds for all compositions and at all applied magnetic fields, showing clearly a reduction in the spin disorder in the former. The difference between the T _C values for Ho³⁺ - and Y³⁺-doped compounds for all compositions may be attributed to the presence of an internal field due to Ho³⁺ doping. This internal field may be responsible for the decrease in spin disorder in the Ho³⁺-doped compounds. The increase in the canting angles with increase in Ho³⁺ and Y³⁺ content could be attributed to the decrease in the strength of the ferromagnetic exchange interactions. A strong ferromagnetic coupling (as discussed recently by the present authors and co-workers) of Ho³⁺ moments with the Mn moments is responsible for the observed behaviour.     

Mn位W掺杂对La0.3Ca0.7MnO3体系磁结构的影响

通过对La_0.3Ca_0.7Mn_1-xW_xO₃(x=0.00，0.04，0.08，0.12，0.15)多晶样品M-T曲线、M-H曲线及ESR谱的测量，研究了Mn位W掺杂对电荷有序体系La_0.3Ca_0.7MnO₃磁结构的影响.结果表明，当掺杂量为0.00≤x≤0.08时，体系存在电荷有序(CO)相，AFM/CO态共存于相变温度以下，电荷有序温度T_CO随着W掺杂量的增加而增加；x＝0.04时，样品在低温下为FM相与AFM/CO相共存，在CO相建立前、后均有FM从PM中分离出来；当x≥0.12时，CO态融化，在极低温度下存在顺磁-铁磁(PM-FM)相变. 关键词： 磁结构 电荷有序 融化 Mn位掺杂     

Improvement of refrigerant capacity of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> single crystal with a few percent Fe doping

Large low-field-induced magnetic entropy changes, ΔS _M, are observed in La_0.67Ca_0.33MnO₃ and La_0.67Ca_0.33Mn_0.96Fe_0.04O₃ single crystals. The peaks of ΔS _M broadened asymmetrically to high temperatures under higher magnetic fields for two materials should be attributed to the first-order magnetic phase transition at T _c. A small amount of iron doping results in an increase in the refrigerant capacity of the material though the magnetic entropy change decreases. The discovery of excellent magnetocaloric features of these single crystals in the low magnetic field can provide some ideas for exploring novel magnetic refrigerants operating under permanent magnet rather than superconducting one as magnetic field source. Supported by the State Key Project of Fundamental Research (Grant No. 2005CB724402), and the National Natural Science Foundation of China (Grant No. 50672126) Contributed by CHENG ZhaoHua     

Magnetocaloric effect in nano- and polycrystalline manganite La0.7Ca0.3MnO3

La_0.7Ca_0.3MnO₃ samples were prepared in nano- and polycrystalline forms by the sol–gel and solid state reaction methods, respectively, and structurally characterized by synchrotron X-ray diffraction. The magnetic properties determined by ac susceptibility and dc magnetization measurements are discussed. The magnetocaloric effect in this nanocrystalline manganite is spread over a broader temperature interval than in the polycrystalline case. The relative cooling power of the poly- and nanocrystalline manganites is used to evaluate a possible application for magnetic cooling below room temperature. PACS 75.30.Sg; 75.47.Lx; 77.80.Bh     

Co-existence of giant magnetoresistance and large magnetocaloric effect near room temperature in nanocrystalline La0.7Te0.3MnO3

Sol-gel prepared nanocrystalline La_0.7Te_0.3MnO₃ has rhombohedral crystal structure (space group R3¯C) at room temperature and orders ferromagnetically at ∼280 K (T_C). A large magnetic entropy change of ∼12.5 J kg⁻¹ K⁻¹ is obtained near T_C for a field change of 50 kOe. This magnetocaloric effect could be explained in terms of Landau theory. The temperature dependence of electrical resistivity shows metal-insulator transition at T_C and a giant magnetoresistance of ∼52% in 50 kOe. The co-existence of giant magnetoresistance and large magnetocaloric effect near room temperature makes nanocrystalline La_0.7Te_0.3MnO₃ a promising material for magnetic refrigeration and spintronic device applications.