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.     

The interplay between the lattice and magnetism in La（Fe11.4Al1.6）C0.02 studied by powder neutron diffraction

The crystallographic structure and magnetic properties of La（Fell.4Alz.6）C0.02 are studied by magnetic measurernent and powder neutron diffraction with temperature and applied magnetic field. Rietveld refinement shows that La（Fe11.4Al1.6）C0.02 crystallizes into the cubic NaZn13-type with two different Fe sites： FeI （8b） and FeII （96i）, and that A1 atoms preferentially occupy the FeII site. A ferromagnetic state can he induced at a medial temperature of 39 K-139 K by an external magnetic field of 0.7 T, and a large lattice is correspondingly found at 100 K and 0.7 T. In all other conditions, La（Fe11.4Al1.6）C0.02 has no net magnetization in the paramagnetic （T 〉 TN = 182 K） or antifer- romagnetic states, and thus keeps its small lattice. Analysis of the Fe Fe bond length indicates that the ferromagnetic state prefers longer Fe-Fe distances.     

Magnetoresistances and magnetic entropy changes associated with negative lattice expansions in NaZn13-type compounds LaFeCoSi

Magnetoresistances and magnetic entropy changes in NaZn13-type compounds La（Fel-xCox）11.9Si1.1 （x=0.04, 0.06, and 0.08） with Curie temperatures of 243 K, 274 K, and 301 K, respectively, are studied. The ferromagnetic ordering is accompanied by a negative lattice expansion. Large magnetic entropy changes in a wide temperature range from ～230 K to ～320 K are achieved. Raising Co content increases the Curie temperature but weakens the magnetovolume effect, thereby causing a decrease in magnetic entropy change. These materials exhibit a metallic character below Tc, whereas the electrical resistance decreases abruptly and then recovers the metal-like behaviour above Tc. Application of a magnetic field retains the transitions via increasing the ferromagnetic ordering temperature. An isothermal increase in magnetic field leads to an increase in electrical resistance at temperatures near but above Tc, which is a consequence of the field-induced metamagnetic transition from a paramagnetic state to a ferromagnetic state.     

Magnetocaloric effects in Mn1.35Fe0.65P1-xSix compounds

The structural and magnetocaloric properties of Mn_1.35Fe_0.65P_1-xSi_x compounds are investigated. The Si-substituted compounds, Mn_1.35Fe_0.65P_1-xSi_x with x = 0.52, 0.54, 0.55, 0.56, and 0.57, are prepared by high-energy ball milling and the solid-state reaction. The X-ray diffraction shows that the compounds crystallize into the Fe₂P-type hexagonal structure with space group P62m. The magnetic measurements show that the Curie temperature of the compound increases from 253 K for x = 0.52 to 296 K for x = 0.56. The isothermal magnetic-entropy change of the Mn_1.35Fe_0.65P_1-xSi_x compound decreases with the Si content increasing. The maximal value of the magnetic-entropy change is about 7.0 J/kg稫 in the Mn_1.35Fe_0.65P_0.48Si_0.52 compound with a field change of 1.5 T. The compound quenched in water possesses a larger magnetic entropy change and a smaller thermal hysteresis than the non-quenched samples. The thermal hysteresis of the compound is less than 3.5 K. The maximum adiabatic temperature change is about 1.4 K in the Mn_1.35Fe_0.65P_0.45Si_0.55 compound with a field change of 1.48 T.     

Effect of hydrostatic pressure on the magnetic and lattice properties of the ferromagnet La(Fe0.86Si0.14)13

The temperature dependence of the lattice constant of the ferromagnet La(Fe_0.86Si_0.14)₁₃ has been measured at different pressures and temperatures. The numerical value of the bulk modulus at room temperature has been determined. The measurements of the temperature dependence of the lattice constant of the ferromagnet La(Fe_0.86Si_0.14)₁₃ at zero pressure and at 11.5 kbar have demonstrated that, at zero pressure, the lattice constant sharply decreases in the range from 160 to 210 K, whereas at a pressure of 11.5 kbar, the lattice constant decreases in the range from 110 to 180 K. This indicates that the Curie temperature T _C changes from 210 to ～170 K under pressure. The experimental results have been analyzed using the equations of states for the magnetic and elastic subsystems of the ferromagnet.     

Magnetocaloric effect in La(Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>13</Subscript> ferromagnets

The isothermal changes in the magnetic entropy and the lattice entropy and the adiabatic temperature change in La(Fe_0.88Si_0.12)₁₃ and La(Fe_0.86Si_0.14)₁₃ ferromagnets in a magnetic field are calculated. The calculations are performed with a generalized magnetostriction model of a ferromagnet; the calculation results are compared to experimental data. It is shown that the change in the lattice entropy decreases the magnetocaloric effect and makes it possible to explain the experimental data obtained for La(Fe _x Si_{1 − x} )₁₃ (x = 0.86, 0.88) ferromagnets. The temperature dependences of the bulk compression moduli of these ferromagnets are calculated, and these dependences indicate a strong lattice softening in the vicinity of the magnetic phase transition in them. The thermal expansion coefficient and some magnetic properties of the ferromagnet with x = 0.86 are measured to determine the numerical values of the parameters entering into calculation formulas.     

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.     

Influence of hydrogenation on the electronic structure and the itinerant-electron metamagnetic transition in strong magnetocaloric compound La(Fe0.88Si0.12)13

The influence of interstitial hydrogen on the electronic structure and the itinerant-electron metamagnetic (IEM) transition in strong magnetocaloric compound La(Fe_0.88Si_0.12)₁₃H_1.6 has been investigated by Mössbauer spectroscopy. A slight change in the average hyperfine field at 4.2 K was observed after hydrogen absorption. In contrast, the thermally induced first-order transition related to the IEM transition for y=1.6 appears at the Curie temperature T_C=330 K, much higher than T_C=195 K for y=0.0. The increase of isomer shift δ_IS at 4.2 K indicates that the valence electron transfer from hydrogen to Fe is negligibly small, hence the change in the magnetic state is closely associated with a volume expansion after hydrogen absorption. No change in shape by hydrogenation for the Mössbauer spectra in the paramagnetic state has been observed except for a difference in only δ_IS, indicating the volume expansion by hydrogenation is isotropic. Accordingly, the significant increase of T_C by hydrogen absorption is attributed to the magnetovolume effect associated with characteristic feature in IEM compounds. A discontinuous change of ferromagnetic moment, ΔM, around T_C has been observed by Mössbauer spectra, as expected from the magnetization measurement. The value of ΔM is slightly decreased by increase of T_C after hydrogenation but its magnitude is almost the same due to the stabilization of ferromagnetic moment. As a result, strong magnetocaloric effect is maintained up to room temperature after hydrogenation.     

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 (La-Gd)Fe11.4Si1.6 metamagnetic compound

The effect of the partial substitution of La by Gd atoms on the magnetic entropy change of the LaFe_11.4Si_1.6 metamagnetic compound was studied using Mössbauer spectroscopy and DC magnetization measurements. A considerable enhancement of the magnetic entropy change was observed in Gd-substituted compounds, while the Curie temperature slightly decreased with the increase of the Gd content. For the 20% Gd-substituted compound, a giant magnetic entropy change value of −16 J/kg K at 190 K was attained under a field varying from 0 to 2 T.     

Crystal structure and magnetic properties of Nd（Mn1-xFex）2Si2 compounds

X-ray powder diffraction,resistivity and magnetization studies have been performed on polycrystalline Nd(FexMn1-x)2Si2 (0 ≤ x ≤ 1) compounds which crystallize in a ThCr2Si2-type structure with the space group I4/mmm.The field-cooled temperature dependence of the magnetization curves shows that,at low temperatures,NdFe2Si2 is antiferromagnetic,while the other compounds show ferromagnetic behaviour.The substitution of Fe for Mn leads to a decrease in lattice parameters a,c and unit-cell volume V .The Curie temperature of the compounds first increases,reaches a maximum around x = 0.7,then decreases with Fe content.However,the saturation magnetization decreases monotonically with increasing Fe content.This Fe concentration dependent magnetization of Nd(FexMn1-x)2Si2 compounds can be well explained by taking into account the complex effect on magnetic properties due to the substitution of Mn by Fe.The temperature’s square dependence on electrical resistivity indicates that the curve of Nd(Fe0.6Mn0.4)2Si2 has a quasi-linear character above its Curie temperature,which is typical of simple metals.     

R13Fe74Si13三元合金的结构与磁性

本文对R₁₃Fe₇₄Si₁₃(R=Ce,Pr,Nd,Gd,Tb,Dy,Ho,Er,Y)三元合金的结构和磁性进行了研究。结果表明,R₁₃Fe₇₄Si₁₃的主相为R₂(Fe_0.85Si_0.1517赝二元金属间化合物,而不出现类似于R₂Fe₁₄B的三元 关键词：     

Effect of interstitial nitrogen on magnetism and entropy change of LaFe11.7Si1.3 compound

Crystal structure, magnetism and magnetocaloric properties of LaFe_11.7Si_1.3N_y (y=0, 1.3) compounds have been studied by X-ray diffraction and magnetic measurements. The LaFe_11.7Si_1.3N_y compounds present a cubic NaZn₁₃-type structure. Insertion of 1.3 nitrogen atoms per LaFe_11.7Si_1.3 formula increases the lattice parameter and Curie temperature from 11.467 to 11.733 Å and from 190 to ∼230 K, respectively. Besides, the absorption of nitrogen drives drastically the magnetic transition from first to second order and accordingly strongly decreases the magnetocaloric effect compared to the parent alloy. Under an external field change of 5 T, the value of isothermal entropy change −ΔS is about 28 and 3.5 J/kg K for LaFe_11.7Si_1.3 and LaFe_11.7Si_1.3N_1.3, respectively, close to their Curie temperature. However, the relative cooling power RCP(S) of the nitride is about half that of the parent alloy.     

Giant magnetocaloric effect in the Gd5Ge2.025Si1.925In0.05 compound

The magnetocaloric properties of the Gd 5 Ge 2.025 Si 1.925 In 0.05 compound have been studied by x-ray diffraction,magnetic and heat capacity measurements.Powder x-ray diffraction measurement shows that the compound has a dominant phase of monoclinic Gd5Ge2Si2-type structure and a small quantity of Gd 5(Ge,Si) 3-type phase at room temperature.At about 270 K,this compound shows a first order phase transition.The isothermal magnetic entropy change(△SM) is calculated from the temperature and magnetic field dependences of the magnetization and the temperature dependence of MCE in terms of adiabatic temperature change(△Tad) is calculated from the isothermal magnetic entropy change and the temperature variation in zero-field heat-capacity data.The maximum S M is 13.6 J·kg-1·K-1 and maximum △Tad is 13 K for the magnetic field change of 0-5 T.The Debye temperature(θD) of this compound is 149 K and the value of DOS at the Fermi level is 1.6 states/eV·atom from the low temperature zero-field heat-capacity data.A considerable isothermal magnetic entropy change and adiabatic temperature change under a field change of 0-5 T jointly make the Gd5Ge2.025Si1.925 In 0.05 compound an attractive candidate for a magnetic refrigerant.     

Effects of interstitial H and/or C atoms on the magnetic and magnetocaloric properties of La(Fe, Si)13-based compounds

La(Fe, Si)₁₃-based compounds have been considered as promising candidates for magnetic refrigerants particularly near room temperature. Herein we review recent progress particularly in the study of the effects of interstitial H and/or C atoms on the magnetic and magnetocaloric properties of La(Fe, Si)₁₃ compounds. By introducing H and/or C atoms, the Curie temperature T _C increases notably with the increase of lattice expansion which makes the Fe 3d band narrow and reduces the overlap of the Fe 3d wave functions. The first-order itinerant-electron metamagnetic transition is conserved and the MCE still remains high after hydrogen absorption. In contrast, the characteristic of magnetic transition varies from first-order to second-order with the increase of C concentration, which leads to remarkable reduction of thermal and magnetic hysteresis. In addition, the introduction of interstitial C atoms promotes the formation of NaZn₁₃-type (1:13) phase in La(Fe, Si)₁₃ compounds, and thus reducing the annealing time significantly from 40 days for LaFe_11.7Si_1.3 to a week for LaFe_11.7Si_1.3C_0.2. The pre-occupied interstitial C atoms may depress the rate of hydrogen absorption and release, which is favorable to the accurate control of hydrogen content. It is found that the reduction of particle size would greatly depress the hysteresis loss and improve the hydrogenation process. By the incorporation of both H and C atoms, large MCE without hysteresis loss can be obtained in La(Fe, Si)₁₃ compounds around room temperature, for instance, La_0.7Pr_0.3Fe_11.5Si_1.5C_0.2H_1.2 exhibits a large |ΔS _M| of 22.1 J/(kg·K) at T _C = 321 K without hysteresis loss for a field change of 0–5 T.     

The effect of different temperature annealing on phase relation of LaFe11.5Si1.5 and the magnetocaloric effects of La0.8Ce0.2Fe11.5−xCoxSi1.5 alloys

The phase relation of LaFe_11.5Si_1.5 alloys annealed at different high-temperature from 1223 K (5 h) to 1673 K (0.5 h) has been studied. The powder X-ray diffraction (XRD) patterns show that large amount of 1:13 phase begins to form in the matrix alloy consisting of α-Fe and LaFeSi phases when the annealing temperature is 1423 K. In the temperature range from 1423  to 1523 K, α-Fe and LaFeSi phases rapidly decrease to form 1:13 phase, and LaFeSi phase is rarely observed in the XRD pattern of LaFe_11.5Si_1.5 alloy annealed at 1523 K. With annealing temperature increasing from 1573  to 1673 K, the LaFeSi phase is detected again in the LaFe_11.5Si_1.5 alloy, and there is La₅Si₃ phase when the annealing temperature reaches 1673 K. There almost is no change in the XRD patterns of LaFe_11.5Si_1.5 alloys annealed at 1523 K for 3-5 h. According to this result, the La_0.8Ce_0.2Fe_11.5−xCo_xSi_1.5 (0≤×≤0.7) alloys are annealed at 1523 K (3 h). The analysis of XRD patterns shows that La_0.8Ce_0.2Fe_11.5xCo_xSi_1.5 alloys consist of the NaZn₁₃-type main phase and α-Fe impurity phase. With the increase of Co content from x=0 to 0.7, the Curie temperature T_C increases from 180 to 266 K. Because the increase of Co content can weaken the itinerant electron metamagnetic transition, the order of the magnetic transition at T_C changes from first to second-order between x=0.3 and 0.5. Although the magnetic entropy change decreases from 34.9 to 6.8 J/kg K with increasing Co concentration at a low magnetic field of 0-2 T, the thermal and magnetic hysteresis loss reduces remarkably, which is very important for the magnetic refrigerant near room temperature.     

Magnetocaloric effect in the La0.8Ce0.2Fe11.4−xCoxSi1.6 compounds

The effects of substitution of Co for Fe on the magnetic and magnetocaloric properties of La_0.8Ce_0.2Fe_11.4−xCo_xSi_1.6 (0, 0.2, 0.4, 0.6, 0.8 and 1.0) compounds have been investigated. X-ray diffraction shows that all compounds crystallize in the NaZn₁₃-type structure. Magnetic measurements show that the Curie temperature (T_C) can be tuned between 184 and 294 K by changing the Co content from 0 to 1. A field-induced methamagnetic transition occurs in samples with x=0, 0.2 and 0.4. The magnetic entropy changes of the compounds have been determined from the isothermal magnetization measurements by using the Maxwell relation.     

Simultaneous enhancements of Curie temperature and magnetocaloric effects in the La1−xCexFe11.5Si1.5Cy compounds

The effects of introducing Ce and C atoms on the Curie temperature (T_C), the magnetic entropy change (ΔS_M) and the hysteresis loss have been investigated in the NaZn₁₃-type LaFe_11.5Si_1.5 compound. Partial replacement of La with Ce leads to a decrease in T_C and an increase in ΔS_M; however, the introduction of interstitial C atoms can adjust T_C to high temperature. The itinerant-electron metamagnetic transition is weakened after carbonization, which results in a reduction of both the hysteresis loss and magnetocaloric effect (MCE). The maximum value of ΔS_M for La_0.8Ce_0.2Fe_11.5Si_1.5C_0.2 is found to be −28 J/kg K at T_C=207 K with an effective refrigeration capacity of 420 J/kg for a field change from 0 to 5 T. Our study reveals that the enhancements of both T_C and MCEs can be achieved simultaneously in the La_1−xCe_xFe_11.5Si_1.5C_y compounds by adjusting the concentrations of Ce and C atoms appropriately.     

La0.8-xCa0.2MnO3纳米颗粒的居里温度与磁热效应

采用溶胶凝胶法制备了系列La_0.8-xCa_0.2MnO₃多晶样品,用X射线衍射分析确定了样品的钙钛矿结构,用透射电子显微镜观察了样品的形貌及粒径分布情况,用PAR155型振动样品磁强计测量了样品的磁性随外场和温度的变化,确定样品的居里温度并计算了各样品的磁熵变.磁测量及计算结果表明制备的各样品的居里温度在180—260K的范围内且随焙烧温度和La³⁺离子空位浓度的不同而变化,不同温度焙烧的样品均有较大的磁熵变值,其中1100℃焙烧的La_0.77Ca_0.2MnO₃,多晶样品在240.5K,H=1.0T的外场下的磁熵变达3.76J/kg·K,对实验结果做了定性的分析.该材料具有较高的居里温度和较大的磁熵变,所需外场强度适中,电阻率高,性能稳定,适合做高温磁制冷材料. 关键词： 钙钛矿 居里温度 磁热效应     

Magnetocaloric effect in R2Fe17 (R=Sm,Gd, Tb,Dy, Er)

A series of R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) have been synthesized. The magnetocaloric effect (MCE) of these compounds has been investigated by means of magnetic measurements in the vicinity of their Curie temperature. The Curie temperature of Er₂Fe₁₇ is 294 K. The maximum magnetic entropy change of Er₂Fe₁₇ under 5 T magnetic field is ∼3.68 J/kg K. In the R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) system, the maximum magnetic entropy change under 1.5 T magnetic field is 1.72, 0.89, 1.32, 1.59, 1.68 J/kg K corresponding to their Curie temperature (400, 472, 415, 364, 294 K), respectively.