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.     

Magnetocaloric and magnetoresistance properties of La2/3Sr1/3Mn1−xCoxO3 compounds

Structural, magnetic, magnetoresistance and magnetocaloric studies on La_2/3Sr_1/3Mn_1−xCo_xO₃ compounds were reported. The samples were prepared by the conventional ceramic method. X-ray analysis showed the presence of one phase only, in all studied samples. From electrical resistance measurements it was found that the samples show large negative magnetoresistance behavior. The magnetic measurements were performed in a large temperature range, 4.2–750 K and external magnetic fields up to 5 T. The adiabatic magnetic entropy changes, |ΔS|, were determined from magnetization data. Large magnetocaloric effect (MCE) has been obtained in all studied samples.     

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.     

Reduction of hysteresis loss and large magnetocaloric effects in substituted compounds of itinerant-electron metamagnets La(FexSi1−x)13

The maximum value of hysteresis loss E_h^MAX due to the itinerant-electron metamagnetic (IEM) transition of La(Fe_xSi_1−x)₁₃ and the partially substituted compounds La_1−zCe_z(Fe_0.86Si_0.14)₁₃ and La_1−z′Pr_z′(Fe_0.86Si_0.14)₁₃ increases when the magnetocaloric effects (MCEs) become large. It should be noted that the reduction of E_h^MAX without the decrease of large MCEs is achieved in La_1−zCe_z(Fe_0.86Si_0.14)₁₃ and La_1−z′Pr_z′(Fe_0.86Si_0.14)₁₃. For both the compound systems mentioned above, the critical temperature T₀ for the IEM transition decreases and the difference between T₀ and the Curie temperature T_C becomes larger with decreasing T_C. These results are consistent with the magnetic phase diagram of La(Fe_0.86Si_0.14)₁₃ under hydrostatic pressure. Consequently, the reduction of E_h^MAX in La_1−zCe_z(Fe_0.86Si_0.14)₁₃ and La_1−z′Pr_z′(Fe_0.86Si_0.14)₁₃ is closely related with the magnetovolume effects.     

Enhancement of magnetocaloric effects in La0.8R0.2(Fe0.919Co0.081)11.7 Al1.3 (R=Pr, Nd) compounds

The magnetic properties and magnetocaloric effects (MCEs) in La_0.8R_0.2(Fe_0.919Co_0.081)_11.7Al_1.3 (R=Pr, Nd) compounds have been investigated. When Pr and Nd substitute for La, the Curie temperature of compounds decreases. The values of the MCEs are enhanced significantly by a partial substitution of Nd for La. Under the field change of 2 and 5 T, the maximum magnetic entropy changes for La_0.8Nd_0.2(Fe_0.919Co_0.081)_11.7Al_1.3 compound are −4.56 and −9.46 J/Kg K, respectively. It can be exploited for room temperature magnetic refrigeration material.     

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 and optical properties of spinel FexCo3−xO4 thin films

Magnetic and optical properties of Fe_xCo_3−xO₄ thin films grown by sol–gel method have been investigated as the Fe composition (x  ) increases from 0 to 2. X-ray diffraction measurements revealed that the normal- and inverse-spinel phases coexist for 0.76?x?0.93$0.76?x?0.93$. The normal-spinel phase is dominant below x=0.76$x=0.76$ while the inverse-spinel phase above x=0.93$x=0.93$. The lattice constant of the inverse-spinel phase is found to be larger than that of the normal-spinel phase. For both phases the lattice constant increases with increasing x. The Fe_xCo_3−xO₄ films containing the inverse-spinel phase exhibit net magnetization that increases with increasing x  . Conversion electron Mössbauer spectrum measured on the x=0.93$x=0.93$ sample showed that Fe²⁺ ions prefer the octahedral sites, indicating the formation of the inverse-spinel phase. Analysis on the measured optical absorption spectra for the samples by spectroscopic ellipsometry indicates a dominance of the normal-spinel phase for low x in which Fe³⁺ ions mostly occupy the octahedral sites. Observation of a crystal-field transition at 1.6 eV originating from tetrahedral Fe³⁺ ion confirms the existence of the inverse-spinel phase for high x.     

On the determination of the magnetic entropy change in materials with first-order transitions

An accurate method to determine the magnetic entropy change in materials with hysteretic first-order transitions is presented, which is needed to estimate their potential for applications. We have investigated the effect of the maximal entropy change derived from magnetization measurements performed in different measurement processes. The results show that the isothermal entropy change can be derived from the Maxwell relations even for samples with large thermal hysteresis. In the temperature region with hysteresis, overestimating the entropy change can be avoided by measuring the isothermal magnetization of the sample after it is cooled from the paramagnetic state to the measurement temperature. In this way the so-called peak effect is not observed as shown here for a few 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.     

Possible influence of two-band superconductivity on the behaviour of the second magnetization peak in La2−xSrxCuO4 single crystals

An anomalous temperature T dependence of the field H_on for the onset of the second magnetization peak (SMP) in La_1.81Sr_0.19CuO₄ single crystals (with the external magnetic field H oriented parallel to the c axis) is discussed. While the peak field H_p and the magnetization at H_p have a continuous variation with T, H_on exhibits a sudden decrease with increasing T for T  11 K–15 K. The analysis of the nature of the SMP in La_2−xSr_xCuO₄ single crystals in terms of a simple dynamic energy balance relation suggests that the observed behaviour could be related to the particular T dependence of the superfluid density in the case of two-band superconductivity, affecting the T variation of the elastic energy of the vortex system at low H.     

Magnetocaloric effect in La0.75Sr0.25MnO3 manganite

The polycrystalline manganite La_0.75Sr_0.25MnO₃ prepared by an alternative carbonate precipitation route reveals the rhombohedral perovskite structure. Magnetization isotherms measured up to 2 T are used to determine Curie temperature of 332 K by means of Arrott plot. Maximum of magnetic entropy change is found at Curie temperature. The relative cooling power equal to 64 J/kg for 1.5 T magnetic field, is superior as compared to the manganite with the same chemical composition from the sol-gel method.     

Multi-magnetic phases in Fe1−xNixTa2O6

X-ray, neutron diffraction and magnetic susceptibility are reported for Fe_xNi_1−xTa₂O₆ mixed oxides. X-ray refinement indicates homogeneous samples for all the reported concentrations. The neutron-diffraction measurements reveal magnetic structures with double propagation vectors. This system exhibits at least two bicritical points at about x=0.15 and 0.60. For these concentrations, at low temperatures, the system shows the coexistence of two magnetic structures. This bicritical behaviour is interpreted as induced by competition between the different magnetic structures.     

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.     

The order of magnetic phase transition in La(Fe1−xCox)11.4Si1.6 compounds

Magnetic transitions in La(Fe_1−xCo_x)_11.4Si_1.6 compounds with x=0–0.08, have been studied by DC magnetic measurements and Mössbauer spectroscopy. The temperature dependence of the Landau coefficients has been derived by fitting the magnetization, M(μ₀H), using the Landau expansion of the magnetic free energy. For x0.02 there is a strongly first-order magnetic phase transition between ferromagnetic and paramagnetic (F–P) states in zero external field and a metamagnetic transition from paramagnetic to ferromagnetic (P–F) above T_c. Increasing the cobalt content drives the F–P transition towards second order and eliminates the metamagnetic transition.     

Magnetic properties of Nd1−xKxMnO3 compounds

Polycrystalline Nd_1−xK_xMnO₃ (x=0.10–0.20) compounds have been prepared in single phase form with Pbnm space group. The magnetic properties were studied by measuring dc magnetization and ac susceptibility. They exhibit paramagnetic to ferromagnetic transition with transition temperature ranging from 116 to 128 K. The magnetization data have been analyzed by using Brillouin function model and by taking into account the ferromagnetic interaction. The effective spin contribution towards ferromagnetic interaction and spin canting angle have been estimated. The spin canting angle is found to decrease with increase in doping. Magneto-caloric effect (MCE) has been studied and the maximum change in entropy was found to be 1.76 J/kg K for 1 T field. Metal–insulator transition and colossal magnetoresistance of the order of 60% for 1 T field have been observed for x=0.20 sample.     

High-temperature ferromagnetism in Zn1−xMnxO semiconductor thin films

Clear evidence of ferromagnetic behavior at temperatures >400 K as well as spin polarization of the charge carriers have been observed in Zn_1−xMn_xO thin films grown on Al₂O₃ and MgO substrates. The magnetic properties depended on the exact Mn concentration and the growth parameters. In well-characterized single-phase films, the magnetic moment is 4.8 μ_B/Mn at 350 K, the highest moment yet reported for any Mn doped magnetic semiconductor. Anomalous Hall effect shows that the charge carriers (electrons) are spin-polarized and participate in the observed ferromagnetic behavior.     

Magnetic properties of Mn-substituted GdCoxMn1−xO3 and LaCoxMn1−xO3

Partial substitution of manganese by cobalt in rare-earth perovskites REMnO₃ leads to unusual magnetic phenomena because of the simultaneous presence of Mn³⁺, Mn⁴⁺, Co²⁺ and Co³⁺ species. The magnetic nature of the RE cation plays a fundamental role in the magnetic properties. We present herein two specific families: for RE=La the magnetic behavior of the |Co+Mn| network is observed, while for Gd its strong magnetic moment interacts with the transition metals, leading to a spin reversal state. Magnetic interactions are maximized at x=0.50, as if two regimes exist: for x<0.5 Co substitutes Mn in the REMnO₃ manganite, and for x>0.5 Mn substitutes Co in the RECoO₃ cobaltite.     

Rotational magnetization processes in exchange biased Ni81Fe19/Fe50Mn50 bilayers

The rotational magnetization process of an exchange coupled Ni₈₁Fe₁₉(10 nm)/Fe₅₀Mn₅₀(10 nm) bilayer was studied by Kerr microscopy. The domain processes in rotating magnetic fields near the exchange bias field H_eb are very sensitive to local variations of coupling strength and direction. A characteristic domain splitting was found that shows a remarkably different behavior for weaker and stronger coupled areas. While the magnetization in weaker coupled areas follows the rotating field for H≈H_eb, the stronger coupled areas switch back spring-like. As a result high-angle walls are formed between both areas causing rotational hysteresis.     

Structure, magnetic and transport properties of La1−xBixMnO3

We have investigated the structural, magnetic and transport properties of La_1−xBi_xMnO₃ samples. As the Bi content increases, a structural transition from rhombohedral to pseudocubic and a magnetic phase transition from ferromagnetic ordering to cluster glass are identified. Metal–insulator (MI) transitions and large magnetoresistance (MR) effects are observed at low Bi doping levels, while insulating behavior of resistivity is found in the whole measured temperature range at high-doping levels. Two distinct ferromagnetic insulating (FI) states are found at low temperatures in this system. One can be suppressed and the other can be enhanced by applying magnetic fields. Possible reasons for the observed structural, magnetic phase transitions and changes of resistivity behavior with Bi doping are discussed.     

Electronic structure studies of Mg0.95Mn0.05Fe2−2xTi2xO4 (0x0.8)

The electronic structure of Mg_0.95Mn_0.05Fe_2−2xTi_2xO₄ (0x0.8) compound is investigated using near edge X-ray absorption fine structure, (NEXAFS) spectroscopy measurements, carried out at O K, Fe and Ti L_3,2-edges at room temperature. The O K-edge spectra indicate that the Fe 3d orbitals have been considerably modified and a new spectral feature start dominating in the pre-edge region at higher Ti doping. The Fe 2p NEXAFS spectra exhibit a mixed valent Fe²⁺/Fe³⁺ states apart from the conversion of Fe³⁺ to Fe²⁺ with the substitution of Ti ions. The Ti L_3,2-edge spectra indicate that Ti ions remain unchanged at 4+ state. These variations in the host electronic structure due to Ti substitution are consistent with the dielectric and transport properties of the material.