Magnetic transition and large reversible magnetocaloric effect in EuCu1.75P2 compound

The magnetocaloric effect(MCE) in EuCu1.75P2 compound is studied by the magnetization and heat capacity measurements.Magnetization and modified Arrott plots indicate that the compound undergoes a second-order phase transition at TC ～ 51 K.A large reversible MCE is observed around TC.The values of maximum magnetic entropy change(-△SxMma) reach 5.6 J·kg-1·K-1 and 13.3 J·kg-1·K-1 for the field change of 2 T and 7 T,respectively,with no obvious hysteresis loss in the vicinity of Curie temperature.The corresponding maximum adiabatic temperature changes(△Tadmax) are evaluated to be 2.1 K and 5.0 K.The magnetic transition and the origin of large MCE in EuCu1.75P2 are also discussed.     

GREAT MAGNETIC ENTROPY CHANGE IN La(Fe, M)13 (M=Si, Al) WITH Co DOPING

Very large magnetic entropy change Δ S_M, which originates from a fully reversible second-order transition at Curie temperature T_C, has been discovered in compounds La(Fe, Si)₁₃, La(Fe, Al)₁₃ and those with Co doping. The maximum change ΔS_M\approx19 J·kg^-1·K^-1, achieved in LaFe_11.4Si_1.6 at 209K upon a 5T magnetic field change, exceeds that of Gd by more than a factor of 2. The T_C of the Co-doped compounds shifts to higher temperatures. ΔS_M still has a considerable large magnitude near room temperature. The phenomena of very large ΔS_M, convenience of adjustment of T_C, and also thesuperiority of low cost, strongly suggest that the compounds La(Fe, M)₁₃ (M=Si, Al) with Co doping are suitable candidates for magnetic refrigerants at high temperatures.     

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.     

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.     

The studies of high-temperature and short-time annealing,phase transition process,and magnetic property for LaFe11.7Si1.3 compound

The high-temperature phase transition is analyzed according to the DSC of as-cast LaFe_11.7 Si_1.3 compound and the X-ray patterns of LaFe_11.7Si_1.3 compounds prepared by high-temperature and short-time annealing. Large amount of 1:13 phase begins to appear in LaFe_11.7Si_1.3 compound annealed near the melting point of LaFeSi phase (about 1422?K). When the annealing temperature is close to the temperature of peritectic reaction (about 1497?K), the speed of 1:13 phase formation is the fastest. The phase relation and microstructure of the LaFe_11.7Si_1.3 compounds annealed at 1523?K (5?h), 1373?K (2?h)?+?1523?K (5?h), and 1523?K (7?h) +1373?K (2?h) show that longer time annealing near peritectic reaction is helpful to decrease the impurity phases. For studying the influence of different high-temperature and short-time annealing on magnetic property, the Curie temperature, thermal, and magnetic hystereses, and the magnetocaloric effect of LaFe_11.7Si_1.3 compound annealed at three different temperatures are also investigated. Three compounds all keep the first order of magnetic transition behavior. The maximal magnetic entropy change ΔS_M (T, H) of the samples is 12.9, 16.04, and 23.8?J?kg^?1?K^?1 under a magnetic field of 0–2?T, respectively.     

Mn5Ge2.7M0.3 (M=Ga，Al，Sn) 化合物的磁性和磁熵变

研究了Mn₅Ge_2.7M_0.3(M=Ga，Al，Sn)化合物的磁性和磁熵变. x射线衍射实验表明，研究的化合物均呈六角Mn₅Si₃型结构. 三种原子对Ge原子的替代，使得平均Mn原子磁矩下降，但居里温度没有明显的变化. 由于磁矩的降低，导致磁熵变值的下降，在磁场变化为4.0×10⁶A·m^-1时，对应于M=Ga，Al和Sn的样品，最大磁熵变值ΔS^max_Ｍ分别为6.1，6.3和5.3J·kg^-1K^-1，但磁熵变峰值的半高宽ΔＴ_ＦＷＨＭ有所增加. 另外，Mn₅Ge_2.7M_0.3(M=Ga，Al，Sn)化合物在高于居里温度的Arrott曲线上出现了一个不连续点，即样品在一定温度下的顺磁磁化率在某一临界磁场下发生了突变，临界磁场与温度几乎呈正比关系.这可能是由于样品在加一定磁场时3d带的费米能级发生了变化，使得有效电子数的减少所致. 关键词： 居里温度 平均Mn原子磁矩 磁熵变 Arrott图     

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.     

NaZn13型结构LaFe13－xAlxCy化合物的磁熵变与磁相变的研究

研究了NaZn₁₃型结构LaFe_13-xAl_xC_0.1(x=1.6，1.8)间隙化合物的磁制冷能力和磁相变.利用麦克斯韦关系式计算得到，高Al含量LaFe_13-xAl_x碳化物的最大磁熵变值|ΔS|_m低于低Al含量碳化物的最大磁熵变值.随Al含量的增加，化合物的磁熵变峰展宽，但由于磁熵变大幅降低，衡量磁制冷能力的q值随之降低.基于朗道相变原理，考虑到自旋涨落的影响，磁自由能可以展开到磁化强度的6次方项，材料的相变类型由磁化强度的4次方项系数a₃(T)的符号来进行判断.随着Al含量的增加，研究的碳化物相变由弱的一级相变转为二级相变. 关键词： 13-xAl_x碳化物')" href="#">LaFe_13-xAl_x碳化物 磁制冷能力 磁相变     

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.     

Hydrogen absorption of LaFe11.5Si1.5 compound under low hydrogen gas pressure

Hydrogen absorptions of LaFe11.5Si1.5 compound in 1-atm hydrogen gas at different temperatures are investigated. The hydrogen content in the hydrogenated sample does not increase with the increase of temperature of hydrogen absorption but changes complicatedly. The characteristic of first-order transition in LaFe11.5Si1.5 compound is weakened after hydrogen absorption. It leads the peaks of magnetic entropy to become wider and the hysteresis loss to reduce significantly, but relative cooling power (RCP) is not changed considerably.     

Magnetic properties and magnetocaloric effects in NaZn13-type La（Fe, Al）13-based compounds

In this article,our recent progress concerning the effects of atomic substitution,magnetic field,and temperature on the magnetic and magnetocaloric properties of the LaFe13-xAlx compounds are reviewed.With an increase of the aluminum content,the compounds exhibit successively an antiferromagnetic(AFM) state,a ferromagnetic(FM) state,and a mictomagnetic state.Furthermore,the AFM coupling of LaFe 13-xAlx can be converted to an FM one by substituting Si for Al,Co for Fe,and magnetic rare-earth R for La,or introducing interstitial C or H atoms.However,low doping levels lead to FM clusters embedded in an AFM matrix,and the resultant compounds can undergo,under appropriate applied fields,first an AFM-FM and then an FM-AFM phase transition while heated,with significant magnetic relaxation in the vicinity of the transition temperature.The Curie temperature of LaFe13-xAlx can be shifted to room temperature by choosing appropriate contents of Co,C,or H,and a strong magnetocaloric effect can be obtained around the transition temperature.For example,for the LaFe 11.5Al1.5C0.2H1.0 compound,the maximal entropy change reaches 13.8 J·kg-1 ·K-1 for a field change of 0-5 T,occurring around room temperature.It is 42% higher than that of Gd,and therefore,this compound is a promising room-temperature magnetic refrigerant.     

Magnetocaloric effect in Gd6Co1.67Si3 compound with a second-order phase transition

The magnetic properties and the magnetic entropy change AS have been investigated for Gd6Co1.67Si3 compounds with a second-order phase transition. The saturation moment at 5 K and the Curie temperature TC are 38.1μB and 298 K, respectively. The AS originates from a reversible second-order magnetic transition around TC and its value reaches 5.2 J/kg.K for a magnetic field change from 0 to 5T. The refrigerant capacity （RC） of Gd6Co1.67Si3 are calculated by using the methods given in Refs.[12] and [21], respectively, for a field change of 0 5T and its values are 310 and 440 J/kg, which is larger than those of some magnetocaloric materials with a first-order phase transition.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.