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.     

Magnetic transitions in LaFe13−x−yCoySix compounds

The magnetic properties of a set of LaFe_13?x?yCo_ySi_x compounds (x = 1.6 ? 2.6; y = 0, y = 1.0) have been investigated using magnetic measurements, thermal expansion, ⁵⁷Fe Mössbauer spectroscopy and high resolution neutron powder diffraction methods over the temperature range 10–300 K. The natures of the magnetic transitions in these LaFe_13?x?yCo_ySi_x compounds have been determined. The Curie temperatures of LaFe_13?xSi_x were found to increase with Si content from T_C = 219(5) K for Si content x = 1.6 to T_C = 250(5) K for x = 2.6. Substitution of Co for Fe in LaFe_10.4Si_2.6 resulted in a further enhancement of the magnetic ordering temperature to T_C = 281(5) K for the LaFe_9.4CoSi_2.6 compound. The nature of the magnetic transition at the Curie temperature changes from first order for LaFe_11.4Si_1.6 to second order for LaFe_10.4Si_2.6 and LaFe_9.4CoSi_2.6. The temperature dependences of the mean magnetic hyperfine field values lead to T_C values in good agreement with analyses of the magnetic measurements. The magnetic entropy change, ?ΔS_M, has been determined from the magnetization curves as functions of temperature and magnetic field (ΔB = 0 ? 5 T) by applying the standard Maxwell relation. In the case of LaFe_12.4Si_1.6 for example, the magnetic entropy change around T_C is determined to be -ΔS_M ～ 14.5 J kg^?1 K^?1 for a magnetic field change Δ B = 0 ? 5 T.     

Microstructure and magnetocaloric effect in cast LaFe11.5Si1.5Bx (x=0.5, 1.0)

Phase formation, structure, and the magnetocaloric effect (MCE) in as-cast LaFe_11.5Si_1.5B_x (x=0.5, 1.0) compounds have been studied. The Curie temperatures, T_C, are ∼211 and 230 K for x=0.5 and 1.0, respectively, which are higher than that of annealed LaFe_11.5Si_1.5 (T_C=183 K), while the maximum magnetic entropy changes at the respective T_C under a magnetic field change of 0-5 T are 7.8 and 5.8 J/(kg K). Wavelength dispersive spectrometry (WDS) analysis shows that only a small fraction of boron atoms is dissolved in the NaZn₁₃-type structure phase, and that the compositions of the as-cast LaFe_11.5Si_1.5B_x (x=0.5, 1.0) alloys are much different from the intended nominal compositions. These as-cast alloys exhibit second-order magnetic phase transitions and low MCEs. However, based on the relative cooling power, the as-cast LaFe_11.5Si_1.5B_x alloys are promising candidates for magnetic refrigerants over a wide temperature range.     

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.     

Structure and magnetic properties of LaFe11.5−xCoxSi1.5C0.2 compounds for magnetic refrigeration near room temperature

The influence of cobalt on the microstructural, magnetic and magnetocaloric properties of LaFe_11.5−xCo_xSi_1.5C_0.2 (x=0.50–0.85) compounds was investigated. The ingots were prepared by using a vacuum induction melting furnace. Before annealing, a large amount of 1:13 phase was distinctly observed. Nearly single 1:13 phase was obtained after annealing at 1353 K for only 3 days. The easy formation of 1:13 phase in the annealing process could be attributed to carbon doping. The Curie temperature (T_C) increases linearly with increasing the cobalt content. Although the maximum magnetic entropy changes of the compounds decrease rapidly when T_C rises from 275 to 298 K, and it decreases mildly when T_C continues to rise. Two composite refrigerants based on the compounds are proposed. Their entropy changes remains approximately constant over the temperature range from 266 to 292 K and 289 to 309 K.     

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.     

Large magnetic entropy change near room temperature in the LaFe11.5Si1.5H1.3 interstitial compound

The LaFe_11.5Si_1.5H_1.3 interstitial compound has been prepared. Its Curie temperature T_C (288 K) has been adjusted to around room temperature, and the maximal magnetic entropy change (|ΔS|～17.0 J·kg^-1·K^-1 at T_C) is larger than that of Gd (|ΔS|～9.8 J·kg^-1·K^-1 at T_C=293 K) by ～73.5% under a magnetic change from 0 to 5 T. The origin of the large magnetic entropy change is attributed to the first-order field-induced itinerant-electron metamagnetic transition. Moreover, the magnetic hysteresis of LaFe_11.5Si_1.5H_1.3 under the increase and decrease of the field is very small, which is favourable to magnetic refrigeration application. The present study suggests that the LaFe_11.5Si_1.5H_1.3 compound is a promising candidate as a room-temperature magnetic refrigerant.     

Investigation of magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by magnetic,differential scanning calorimetry and thermal analysis

We investigated magnetocaloric effect in La_0.45Pr_0.25Ca_0.3MnO₃ by direct methods (changes in temperature and latent heat) and indirect method (magnetization isotherms). This compound undergoes a first-order paramagnetic to ferromagnetic transition with T_C=200 K upon cooling. The paramagnetic phase becomes unstable and it transforms into a ferromagnetic phase under the application of magnetic field, which results in a field-induced metamagnetic transition (FIMMT). The FIMMT is accompanied by release of latent heat and temperature of the sample as evidenced from differential scanning calorimetry and thermal analysis experiments. A large magnetic entropy change of ΔS_m=−7.2 J kg⁻¹ K⁻¹ at T=212.5 K and refrigeration capacity of 228 J kg⁻¹ are found for a field change of ΔH=5 T. It is suggested that destruction of magnetic polarons and growth of ferromagnetic phase accompanied by a lattice volume change with increasing magnetic field is responsible for the large magnetocaloric effect in this compound.     

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.     

Magnetic entropy change and magnetic phase transition of LaFe11.4Al1.6Cx （x=0-0.8） compounds

The unit cell volume and phase transition temperature of LaFe11.4Al1.6Cx compounds have been studied. The magnetic entropy change, refrigerant capacity and the type of magnetic phase transition are investigated in detail for LaFe11.4Al1.6Cx with x=0.1, All the LaFe11.4Al1.6Cx （x=0-0.8） compounds have the cubic NaZn13-type structure. The addition of carbon atoms brings about a considerable increase in the lattice parameter. The bulk expansion results in the change of phase transition temperature （Tc）, Tc increases from 187K to 269 K with x varying from 0.1 to 0.8, Meanwhile an increase in the lattice parameter can also cause a change of the magnetic ground state from antiferromagnetic to ferromagnetic. Large magnetic entropy change IASI is found over a large temperature range around Tc and the refrigerant capacity is about 322J/kg for LaFe11.4Al1.6C0.1. The magnetic phase transition belongs in weakly first-order one for x=0.1.     

Large magnetocaloric effect with a wide temperature range in Gd5Si4

Gd₅Si₄ magnets have attracted much attention due to their many appealing properties such as strong ferromagnetism, magnetovolume effect, and large reversal magnetocaloric effect (MCE). However, Gd₅Si₄ exhibits a relatively high Curie temperature (T_C ∼336 K) with a narrow refrigeration temperature span, which limits the refrigeration application at room temperature. Here we show that the T_C of Gd₅Si₄ can be reduced to 330 K and the phase transition temperature range can be effectively expanded by applying a high pressure of 6 GPa to the sample during heat treatment. In addition, the room-temperature magnetic entropy changes are improved and the refrigeration temperature span also becomes wider, which leads to an enhanced relative cooling power (RCP) of 748 Jkg^-1 under a magnetic field change of 5 T. These unique features indicate that the Gd₅Si₄ compound prepared under high pressure can serve as a magnetic refrigerant in a wide temperature range covering room temperature.     

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.     

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.     

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.     

Influence of Si and Co substitutions on magnetoelastic properties of R2Fe17 (R=Y, Er and Tm) intermetallic compounds

The magnetostriction of the off-stoichiometric R₂Fe₁₇-type intermetallic compounds based on R₂Fe_14−xCo_xSi₂ (R=Y, Er, Tm and x=0, 4) was measured, using the strain gauge method in the temperature range 77-460 K under applied magnetic fields up to 1.5 T. All compounds show sign change and reduction in magnetostriction values compared to the R₂Fe₁₇ compounds by Si substitution. For Y₂Fe₁₄Si₂ and Er₂Fe₁₄Si₂, saturation behaviour is observed near magnetic ordering temperature (T_C), whereas for Tm₂Fe₁₄Si₂, saturation starts from T>143 K. Also, Co substitution has different effects on the magnetostriction of R₂Fe₁₄Si₂ compounds. In Er₂Fe₁₀Co₄Si₂ and Tm₂Fe₁₀Co₄Si₂, saturation occurs below the spin reorientation temperature (T_SR). In addition, in Er₂Fe₁₄Si₂, a sign change occurs in the anisotropic magnetostriction (Δλ) as well as the volume magnetostriction (ΔV/V) at their T_SR values. The volume magnetostrictions of the Tm-containing compounds show an anomaly around their T_SR. In R₂Fe₁₄Si₂ compounds, parastrictive behaviour is also observed in ΔV/V near their T_C values. In addition, the magnetostriction of the sublattices is investigated. Results show that in R₂Fe₁₄Si₂ compounds, the rare-earth sublattice contribution to magnetostriction is negative and comparable to the iron sublattice, whereas, in R₂Fe₁₀Co₄Si₂ compounds, the rare-earth sublattice contribution is positive and larger than Fe sublattice. These results are discussed based on the effect of Si and Co substitutions on the anisotropy field of these compounds. Influence of the spin reorientation transition on the magnetostriction of these compounds is discussed in terms of the anisotropic sublattice interactions.     

Magnetic properties of the intermetallic compound Ce5Ge4

Magnetic and magnetocaloric properties of the compound Ce₅Ge₄ have been studied. This compound has orthorhombic Sm₅Ge₄-type structure (space group Pnma, no. 62) and orders ferromagnetically at ~12 K (T_C). The paramagnetic Curie temperature is ~−20 K suggesting the presence of competing ferromagnetic and antiferromagnetic interactions in this compound. The magnetization does not seem to saturate even in fields of 90 kOe at 3 K consistent with the presence of competing interactions. Saturation magnetization value (extrapolated to 1/H→0) of only 0.8μ_B/Ce³⁺ is obtained compared to the free ion value of 2.14μ_B/Ce³⁺. This moment reduction in the ordered state of Ce₅Ge₄ could be due to partial antiferromagnetic/paramagnetic ordering of the Ce moments and may also be due to crystalline electric field effects. Magnetic entropy change near T_C, calculated from the magnetization vs. field data, is found to be moderate with a maximum value of ~9 J/kg/K at ~11 K for a field change of 90 kOe.     

La(Fe,Si)13-based magnetic refrigerants obtained by novel processing routes

The structure and magnetic properties of LaFe_13−xSi_x and Co-substituted LaFe_11.8−xCo_xSi_1.2 alloys prepared by melt spinning, as well as of LaFe_11.57Si_1.43H_x hydrides prepared by reactive milling are investigated. The hysteresis in the temperature- and field-induced phase transitions is significantly reduced as compared with conventional bulk alloys, which makes these materials very attractive for magnetic refrigerant applications. The unusual combination of features characteristic of first- and second-order phase transitions in the La(Fe,Si)₁₃-based compounds is discussed on the basis of density-functional electronic structure calculations.     

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.     

Reduction of hysteresis loss in LaFe11.7Si1.3Hx hydrides with significant magnetocaloric effects

Magnetic properties and magnetocaloric effects (MCEs) have been investigated in hydrogenated LaFe_11.7 Si_1.3H _x (x=0,1.37, and 2.07) compounds. It is found that the Curie temperature, T _C, can be tuned from 192 to 338 K by adjusting the hydrogen content from 0 to 2.07. It is attractive that both thermal and magnetic hysteresis are remarkably reduced because of the weakness of the itinerant-electron metamagnetic transition after hydrogenation. The maximal hysteresis loss at T _C decreases from 33.4 to 8.8 J/kg as x increases from 0 to 2.07. For the samples with x=0,1.37, and 2.07, the maximal values of the isothermal magnetic entropy change, ΔS _M, are 20.9, 15.1, and 15.83 J/kg K for the increasing field and 20.76 J/kg K, 14.53 J/kg K and 15.61 J/kg K for the decreasing field at T _C, with efficient refrigeration capacities of 439, 330, and 304 J/kg for a field change of 0–5 T, respectively. Large reversible MCE and small hysteresis with considerable refrigeration capacity indicate the potential of LaFe_11.7Si_1.3H _x hydride as a candidate magnetic refrigerant around room temperature.     

LaFe11.5Si1.5中的磁不稳定性

通过对LaFe_11.5Si_1.5化合物进行自旋极化和固定磁矩(FSM)的能带 计算，发现LaFe_11.5Si_1.5化合物具有磁不稳定性的特征，无磁态和铁磁 态的能量 差别很小，FSM计算表明LaFe_11.5Si_1.5化合物具有低自旋态和高 自旋态的双 磁性态特征，在一定条件下能够在两磁性态之间发生变磁转变.通过计算的结果，定性地分 析了实验上所观察的一些现象. 关键词： 磁不稳定性 变磁转变