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.     

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.     

Properties of magnetocaloric La(Fe,Co,Si)13 produced by powder metallurgy

We present a comprehensive study of the magnetocaloric materials series La(Fe_1−xCo_x)_11.9Si_1.1 with 0.055<x<0.122. The ferromagnetic samples were manufactured using a novel powder metallurgy process by which industrial scale production is feasible. This new production method makes the materials more attractive as magnetic refrigerants for room temperature magnetic refrigeration. The Curie temperature of the compounds can be easily tuned by altering the Co content and all samples have little magnetic anisotropy and present a second-order magnetic transition so that thermal and magnetic hysteresis is absent. For all seven samples, we have calculated the magnetic entropy change, ΔS_M, from initial curve measurements and measured the adiabatic temperature change, ΔT_ad, directly. In addition, for two of the samples, we determined the heat capacity as a function of applied magnetic field and the thermal conductivity. Where relevant, the results are compared with those of Gd, the benchmark material for room temperature magnetic refrigeration.     

Asymmetric first‐order transition and interlocked particle state in magnetocaloric La(Fe,Si)13

In‐situ synchrotron XRD measurements of the magnetocaloric material LaFe_11.8Si_1.2 are used to understand virgin effects and asymmetry of the underlying first order magnetovolume transition. A remarkable change of the transition kinetics occurs after the first cycle, which we attribute to the formation of cracks originating from the volume change. Tomographic imaging revealed that the bulk material disintegrates via an interlocked state where fragments are loosely connected. Though cracks have opened between the fragments, the transition is sharp, which we attribute to magnetostatic interactions. In the cycled sample we find a strong asymmetry between the transition interval upon heating and cooling, which we explain by isostatic pressure acting on parts of the sample during the cooling transition. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Magnetic behaviour of the cubic La(Fe,Al)13 compounds

The magnetic properties of the cubic NaZn₁₃ type pseudobinary compounds LaFe_XAl_13–x were studied in the temperature range T=4.2–300 K by means of⁵⁷Fe-Mössbauer spectroscopy, magnetization and zero-field susceptibility measurements. The compounds LaFe_xAl_13–x show a rather peculiar concentration dependence of the type of magnetic ordering as well as of the ordering temperature.     

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.     

Multiple metamagnetic transitions in the magnetic refrigerant La(Fe,Si)13Hx

The effect of hydrostatic pressure on thermally and field-induced first-order magnetic phase transitions is studied in the La(Fe,Si)_(13)-type compounds. A peculiar series of consecutive field-induced transitions is realized using a distinct combination of hydrostatic pressure and negative pressure created by the interstitial insertion of hydrogen. The pressure-induced discontinuous magnetization jumps result in an enhanced cooling power, thus opening up the possibility to exploit in full the magnetocaloric potential of this compound class.     

Comprehensive performance of a ball-milled La0.5Pr0.5Fe11.4Si1.6B0.2Hy/Al magnetocaloric composite

Due to the hydrogen embrittlement effect, La(Fe,Si)₁₃-based hydrides can only exist in powder form, which limits their practical application. In this work, ductile and thermally conductive Al metal was homogeneously mixed with La_0.5Pr_0.5Fe_11.4Si_1.6B_0.2 using the ball milling method. Then hydrogenation and compactness shaping of the magnetocaloric composites were performed in one step via a sintering process under high hydrogen pressure. As the Al content reached 9 wt.%, the La_0.5Pr_0.5Fe_11.4Si_1.6B_0.2H_y/Al composite showed the mechanical behavior of a ductile material with a yield strength of ~44 MPa and an ultimate strength of 269 MPa accompanied by a pronounced improvement in thermal conductivity. Due to the ease of formation of Fe-Al-Si phases and the several micron and submicron sizes of the composite particles caused by ball milling process, the magnetic entropy change of the composites was substantially reduced to ~1.2 J/kg· K-1.5 J/kg· K at 0 T-1.5 T.     

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.     

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.     

Simulation of the magnetic and magnetocaloric properties of hydrides of the La(Fe0.88Si0.12)13 compound by applying a negative pressure

Based on the model calculation, it has been shown that the effect of hydration of the ferromagnetic compounds La(Fe_0.88Si_0.12)₁₃H _y is quantitatively adequately described by the introduction of a negative pressure. The calculations have been performed for compounds with hydrogen concentrations y = 0, 0.5, 1.0, and 1.5. It has been found that these concentrations correspond to the pressures P = 0, ?0.95, ?1.85, and ?2.80 GPa, respectively. The calculated Curie temperature, magnetization, characteristics of the magnetocaloric effect, and other properties are in satisfactory agreement with experiment.     

Itinerant electron metamagnetism and magnetocaloric effect in Dy(Co,Si)2

Itinerant electron metamagnetism in Dy(Co_1-xSi_x)₂ compounds was studied in the light of a recent theoretical model based on magnetovolume effect and spin fluctuations. The nature of the magnetic transition in these compounds was analyzed within the framework of this model. The magnetocaloric effect in these compounds has been calculated and correlated with the strength of itinerant electron metamagnetism. The domain wall pinning effect was found to be dominant at low temperatures.     

The stability of the ferromagnetic state in La(Fe0.86Al0.14)13 under high pressure

The ferromagnetic (FM) La(Fe_0.86Al_0.14)₁₃ Invar alloy displays a pressure-induced FM to antiferromagnetic (AF) phase transition at a pressure as low as p⪅0.1 GPa. A quantitative analysis of the results shows that the FM → AF magnetic phase transition recently observed in La(Fe_xAl_1−x)₁₃ at ambient pressure is governed by the decrease of the unit cell volume rather than the increase of the number of Fe nearest neighbor atoms.     

Magnetic phase diagram of La(Fe0.873Co0.007Al0.12)13 cluster intermetallic compound

The magnetic properties of the La(Fe_0.873Co_0.007Al_0.12)₁₃ intermetallic compound have been studied. The compound is a cluster antiferromagnet showing the metamagnetic transition. The magnetic phase diagram of the compound has been constructed. The temperature dependence of the inverse paramagnetic susceptibility of La(Fe_0.873Co_0.007Al_0.12)₁₃ obeys the Curie–Weiss law. The large positive paramagnetic Curie point indicates the presence of predominantly ferromagnetic exchange interactions. The Neel temperature can be considered as the temperature of the ferromagnetic ordering of the Fe magnetic moments in clusters coupled antiferromagnetically.     

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.     

与Al发生扩散反应的非晶(Fe0.99Mo0.01)78Si9B13晶化

高压下与Ａｌ发生扩散反应的非晶（Ｆｅ０．９９Ｍｏ０．０１）７８Ｓｉ９Ｂ１３（ＦＭＳＢ）的不同。与Ａｌ反应的ＦＭＳＢ非晶在３．０￣５．０ＧＰａ,７８０￣９００Ｋ热处理时,晶化为α－Ｆｅ（Ａｌ）和次亚稳非晶合金;在这一压力范围以外,７２０￣９００Ｋ热处理时,晶化为α－Ｆｅ（Ｓｉ）,Ｆｅ３Ｂ或Ｆｅ２Ｂ。与Ａｌ发生反应的ＦＭＳＢ非晶可能通过与Ａｌ的扩散反应在Ａｌ／ＦＭＳＢ界面开始晶化。压力和温度对晶化过程     

Scaling analysis of the magnetocaloric effect in Gd5Si2Ge1.9X0.1 (X=Al, Cu, Ga, Mn, Fe, Co)

The field dependence of the magnetic entropy change has been studied for a series of doped Gd₅Si₂Ge₂ alloys, which possess a magnetic phase transition that is either entirely second order or a combination of primarily second-order mixed to a very minor degree with a first-order transition arising from a magneto-structural phase change. By analyzing the field scaling of the refrigerant capacity as well as of the reference temperatures used for constructing a universal scaling curve, a procedure for estimating the values of the critical exponents for the alloys was developed. For the cases where the transition is entirely second order, the results obtained from this procedure are comparable to the values obtained from the Kouvel–Fisher method. For the case of Fe-doped alloys which partially possess a first-order phase change, the Kouvel–Fisher method is inapplicable. However, their critical exponents determined by our developed procedure can be used to estimate the Curie temperature of the orthorhombic majority phase.     

Magnetic properties and magnetocaloric effect in RE55Co30Al10Si5 (RE = Er and Tm) amorphous ribbons

The magnetic and magnetocaloric effects (MCE) of the amorphous $RE_{55}$Co$_{30}$Al$_{10}$Si$_{5}$ ($RE={\rm Er}$ and Tm) ribbons were systematically investigated in this paper. Compounds with $R ={\rm Er}$ and Tm undergo a second-order magnetic phase transition from ferromagnetic (FM) to paramagnetic (PM) around Curie temperature $T_{\rm C} \sim 9.3$ K and 3 K, respectively. For Er$_{55}$Co$_{30}$Al$_{10}$Si$_{5}$ compound, an obvious magnetic hysteresis and thermal hysteresis were observed at low field below 6 K, possibly due to spin-glass behavior. Under the field change of 0 T-5 T, the maximum values of magnetic entropy change ($-\Delta S_{\rm M}^{\rm max}$) reach as high as 15.6 J/kg$\cdot$K and 15.7 J/kg$\cdot$K for Er$_{55}$Co$_{30}$Al$_{10}$Si$_{5}$ and Tm$_{55}$Co$_{30}$Al$_{10}$Si$_{5}$ compounds, corresponding refrigerant capacity (RC) values are estimated as 303 J/kg and 189 J/kg, respectively. The large MCE makes amorphous $RE_{55}$Co$_{30}$Al$_{10}$Si$_{5 }$ ($RE={\rm Er}$ and Tm) alloys become very attractive magnetic refrigeration materials in the low-temperature region.