磁热效应材料的研究进展

磁制冷技术的发展取决于具有大磁热效应磁制冷材料的研发进展.经过长期的工作积累,特别是近20年来的努力,许多新型磁制冷材料的探索和研究极大地促进了磁制冷技术的进步.本文介绍了磁热效应的基本原理和磁制冷研究的发展历史,系统综述了低温区和室温区具有大磁热效应的磁制冷材料的研究进展,重点介绍了一些受到较为关注的磁热效应材料的最新研究成果.低温区磁制冷材料主要包括具有低温相变的二元稀土基金属间化合物(RGa,RNi,RZn,RSi,R_3Co以及R_(12)Co_7)、稀土-过渡金属-主族金属三元化合物(RTSi,RTAl,RT_2Si_2,RCo_2B_2,RCo_3B_2)以及四元化合物RT_2B_2C等,其中R代表稀土元素,T代表过渡金属.这些材料一般都具有二级相变,具有良好的热、磁可逆性,也因其合金属性具有良好的导热性.室温区磁制冷材料主要包括Gd-Si-Ge,La-Fe-Si,Mn As基,Mn基Husler合金,Mn基反钙钛矿,Mn-Co-Ge,Fe-Rh以及钙钛矿氧化物等系列.这些材料一般都具有一级相变,多数在室温具有巨大的磁热效应而受到国内外的极大关注.其中,La-Fe-Si系列是国际上普遍认为具有重要应用前景的磁制冷工质之一,也是我国具有自主知识产权的材料.本文还对磁制冷材料的发展方向进行了展望.     

MnFe(PGe) compounds: Preparation,structural evolution,and magnetocaloric effects

The interdependences of preparation conditions,magnetic and crystal structures,and magnetocaloric effects(MCE)of the Mn Fe PGe-based compounds are reviewed.Based upon those findings,a new method for the evaluation of the MCE in these compounds,based on differential scanning calorimetry(DSC),is proposed.The Mn Fe PGe-based compounds are a group of magnetic refrigerants with giant magnetocaloric effect(GMCE),and as such,have drawn tremendous attention,especially due to their many advantages for practical applications.Structural evolution and phase transformation in the compounds as functions of temperature,pressure,and magnetic field are reported.Influences of preparation conditions upon the homogeneity of the compounds’chemical composition and microstructure,both of which play a key role in the MCE and thermal hysteresis of the compounds,are introduced.Lastly,the origin of the"virgin effect"in the Mn Fe PGebased compounds is discussed.     

Effect of R substitution on magnetic properties and magnetocaloric effects of La1-xRxFe11.5Si1.5 compounds with R=Ce, Pr and Nd

<正>Magnetic properties and magnetocaloric effects of La_1-xR_xFe₁₁₀₅ Si₉105)（R=Pr,（0≤x≤0.5）;R = Ce and Nd, （0≤x≤0.3）） compounds are investigated.Partially replacing La with R = Ce,Pr and Nd in La_1-xR_xFe_11.5Si_1.5 leads to a reduction in Curie temperature due to the lattice contraction.The substitution of R for La causes an enhancement in field-induced itinerant electron metamagnetic transition,which leads to a remarkable increase in magnetic entropy change△S_m and also in hysteresis loss.However,a high effective refrigerant capacity RC_eff is still maintained in La_1-xR_xFe_11.5Si_1.5.In the present samples,a large△S_m and a high RC_eff have been achieved simultaneously.     

A review of a phenomenological model for magnetocaloric effect in ferromagnetic materials

The present work is devoted to a review of the phenomenological model proposed by Mahmoud Aly Hamad (M. Aly Hamad, Phase Transitions 85 (2012) 106–112) to predict the magnetocaloric effect in ferromagnetic material from the only measure of its magnetization as a function of temperature under an applied magnetic field. We questioned the reliability of that model. Based on some experimental data available in the literature, we have shown that, contrary to what is expected, the prediction of the magnetocaloric effect by this model is poor.     

Magnetic phase transition and magnetocaloric effect in Mn_(1-x)Zn_xCoGe alloys

The magnetic phase transition and magnetocaloric effect are studied in a series of Mn1-xZnxCoGe(x = 0.01, 0.02,0.04, and 0.08) alloys. By introducing a small quantity of Zn element, the structural transformation temperature of the MnCoGe alloy is greatly reduced and a first-order magnetostructural transition is observed. Further increasing the Zn concentration results in a second-order ferromagnetic transition. Large room-temperature magnetocaloric effects with small magnetic hysteresis are obtained in alloys with x = 0.01 and 0.02, which suggests their potential application in magnetic refrigeration.     

Understanding the inverse magnetocaloric effect through a simple theoretical model

We investigated the inverse magnetocaloric effect using a theoretical magnetic model formed by two coupled magnetic lattices to describe a ferrimagnetic system. The influence of the compensation temperature, and the ferrimagnetic-paramagnetic phase transition on the magnetocaloric effect was analyzed. Also, a relation between the area under the magnetocaloric curve and the net magnetic moment of a ferrimagnetic system was established in this work.     

Magnetic phase transitions and magnetocaloric effect in the Fe-doped MnNiGe alloys

The magnetic phase transition and magnetocaloric effects in Fe-doped MnNiGe alloys are investigated. The substitution of Fe for Ni decreases the structural transition temperature remarkably, resulting in the magnetostructural transition occurring between antiferromagnetic and ferromagnetic states in MnNi_{1 - x}Fe_xGe alloy. Owing to the enhanced ferromagnetic coupling induced by the substitution of Fe, metamagnetic behaviour is also observed in TiNiSi-type phase of MnNi_{1 - x}Fe_xGe alloys at temperature below the structural transition temperature.     

Large reversible magnetocaloric effect in HoMn2O5

Magnetocaloric effect (MCE) in polycrystalline HoMn2O5 was investigated by isothermal magnetization curves from 2 K to 50 K. A relatively large magnetic entropy change, △SM = 7.8 J/(kg · K), was achieved with the magnetic field up to 70 kOe (1 Oe = 79.5775 A · m-1). The magnetic entropy change is reversible in the whole range of temperature. The contributions of elastic and magnetoelastic energy to the changing of the magnetic entropy are discussed in terms of the Landau theory. The reversibility of MCE with maximal refrigerant capacity RC = 216.7 J/kg makes polycrystalline HoMn2O5 promising as a magnetic refrigerant.     

Giant enhancement of magnetocaloric effect in metallic glass matrix composite

The magnetocaloric effect (MCE) has made great success in very low temperature refrigeration, which is highly desirable for application to the extended higher temperature range. Here we report the giant enhancement of MCE in the metallic glass composite. The large magnetic refrigerant capacity (RC) up to 103 J·kg⁻¹ is more than double the RC of the well-known crystalline magnetic refrigerant compound Gd₅Si₂Ge_1.9Fe_0.1 (357 J·kg⁻¹) and MnFeP_0.45As_0.55 (390 J·kg⁻¹)(containing either exorbitant-cost Ge or poisonous As). The full width at half maximum of the magnetic entropy change (ΔS _m) peak almost spreads over the whole low-temperature range (from 303 to 30 K), which is five times wider than that of the Gd₅Si₂Ge_1.9Fe_0.1 and pure Gd. The maximum ΔSm approaches a nearly constant value in a wide temperature span over 100 K, and however, such a broad table-like region near room temperature has seldom been found in alloys and compounds. In combination with the intrinsic amorphous nature, the metallic glass composite may be potential for the ideal Ericsson-cycle magnetic refrigeration over a broad temperature range near room temperature. Supported by the National Natural Science Foundation of China (grant Nos. 50621061 and 50731008) and the National Basic Research Program of China (973 Program) (Grant No. 2007CB613904)     

哈斯勒合金Ni-Co-Mn-Sn的马氏体相变及其磁热效应研究

通过结构和磁性测量,研究了四元哈斯勒合金Ni_50-xCo_xMn₃₈Sn₁₂（x=1, 2, 4, 6, 8）的晶体结构和相变特征.结果表明,Co原子的掺杂不但没有影响三元哈斯勒合金Ni-Mn-Sn的原有结构,而且还增强了样品在奥氏体相的铁磁交换作用.此外,通过Maxwell方程计算了其中三种成分样品（x= 2, 4, 6）的磁熵变ΔS_{M关键词： 哈斯勒合金 Ni-Co-Mn-Sn 马氏体相变 磁热效应}     

Magnetic properties and large magnetocaloric effects in amorphous Gd-Al-Fe alloys for magnetic refrigeration

A series of the amorphous Gd75-55Al25-5Fe0-40 alloy ribbons were prepared by melt spinning.The structure,magnetic properties and magnetocaloric effect(MCE) of these alloys were investigated.The prepared samples have shown the characteristics of a second-order phase transition with zero hysteresis loss and the Tc can be tuned by changing the Fe contents.For the different compositions,the magnetic entropy change(--Sm) for a field change of 0-5 T reached a maximum value of 7.14 J kg-1 K-1 in the Gd70Al20Fe10 a...     

Weak amplification of the magnetocaloric effect in manganites

The magnetocaloric effect (MCE) has been measured by direct method in La_0.8Ag_0.15MnO₃ and La_0.85Ag_0.15MnO₃ before and after coating of Fe–Co layer on the surfaces of manganites. An evaporated film thickness has been 500 nm. The measurements have shown the MCE to be increased by 7%–8% under 26 kOe after Fe–Co coating on the flat surfaces.     

Large inverse and normal magnetocaloric effects in HoBi compound with nonhysteretic first-order phase transition

HoBi single crystal and polycrystalline compounds with NaCl-type structure are successfully obtained, and their magnetic and magnetocaloric properties are studied in detail. With temperature increasing, HoBi compound undergoes two magnetic transitions at 3.7 K and 6 K, respectively. The transition temperature at 6 K is recognized as an antiferromagnetic-to-paramagnetic (AFM-PM) transition, which belongs to the first-order magnetic phase transition (FOMT). It is interesting that the HoBi compound with FOMT exhibits good thermal and magnetic reversibility. Furthermore, a large inverse and normal magnetocaloric effect (MCE) is found in HoBi single crystal in the $H|| [100]$ direction, and the positive $\Delta S_{\rm M}$ peak reaches 13.1 J/kg$\cdot$K under a low field change of 2 T and the negative $\Delta S_{\rm M}$ peak arrives at $-18 $ J/kg$\cdot$K under a field change of 5 T. These excellent properties are expected to be applied to some magnetic refrigerators with special designs and functions.     

Large magnetocaloric effect in van der Waals crystal CrBr3

We study the magnetocaloric effect (MCE) in van der Waals (vdW) crystal CrBr₃. Bulk CrBr₃ exhibits a second-order paramagnetic-ferromagnetic phase transition with T_C = 33 K. The maximum magnetic entropy change −ΔS_M near T_C is about 7.2 J·kg⁻¹·K⁻¹ with the maximum adiabatic temperature change ΔT^max_ad = 2.37 K and the relative cooling power RCP= 191.5 J·kg⁻¹ at μ₀H = 5 T, all of which are remarkably larger than those in CrI₃. These results suggest that the vdW crystal CrBr₃ is a promising candidate for the low-dimensional magnetic refrigeration in low temperature region.     

Order of magnetic magnetocaloric transition and large effect in Er3Co

We have studied the magnetic and magnetocaloric properties of the Er3Co compound, which undergoes ferromagnetic ordering below the Curie temperature Tc = 13 K. It is found by fitting the isothermal magnetization curves that the Landau model is appropriate to describe the Er3Co compound. The giant magnetocaloric effect （MCE） without hysteresis loss around Tc is found to result from the second-order ferromagnetic-to-paramagnetic transition. The max- imal value of magnetic entropy change is 24.5 J/kg.K with a refrigerant capacity （RC） value of 476 J/kg for a field change of 0-5 T. Large reversible MEC and RC indicate the potentiality of Er3Co as a candidate magnetic refrigerant at low temperatures.     

Review of magnetocaloric effect in perovskite-type oxides

We survey the magnetocaloric effect in perovskite-type oxides (including doped ABO 3-type manganese oxides, A3B2O7-type two-layered perovskite oxides, and A2B'B'O6-type ordered double-perovskite oxides). Magnetic entropy changes larger than those of gadolinium can be observed in polycrystalline La1-xCaxMnO3 and alkali-metal (Na or K) doped La0.8Ca0.2MnO3 perovskite-type manganese oxides. The large magnetic entropy change produced by an abrupt reduction of magnetization is attributed to the anomalous thermal expansion at the Curie temperature. Considerable magnetic entropy changes can also be observed in two-layered perovskites La1.6Ca1.4Mn2O7 and La2.5-xK0.5+xMn2O7+δ (0 x 0.5), and double-perovskite Ba2Fe1+xMo1-xO6 (0 ≤ x ≤ 0.3) near their respective Curie temperatures. Compared with rare earth metals and their alloys, the perovskite-type oxides are lower in cost, and they exhibit higher chemical stability and higher electrical resistivity, which together favor lower eddy-current heating. They are potential magnetic refrigerants at high temperatures, especially near room temperature.     

Large reversible magnetocaloric effect induced by metamagnetic transition in antiferromagnetic HoNiGa compound

The magnetic properties and magnetocaloric effects(MCE) of Ho Ni Ga compound are investigated systematically.The Ho Ni Ga exhibits a weak antiferromagnetic(AFM) ground state below the Neel temperature TNof 10 K, and the AFM ordering could be converted into ferromagnetic(FM) ordering by external magnetic field. Moreover, the field-induced FM phase exhibits a high saturation magnetic moment and a large change of magnetization around the transition temperature,which then result in a large MCE. A large-?S_M of 22.0 J/kg K and a high RC value of 279 J/kg without magnetic hysteresis are obtained for a magnetic field change of 5 T, which are comparable to or even larger than those of some other magnetic refrigerant materials in the same temperature range. Besides, the μ_0H~(2/3)dependence of |?S_M~(pk)| well follows the linear fitting according to the mean-field approximation, suggesting the nature of second-order FM–PM magnetic transition under high magnetic fields. The large reversible MCE induced by metamagnetic transition suggests that Ho Ni Ga compound could be a promising material for magnetic refrigeration in low temperature range.     

Magnetism and giant magnetocaloric effect in rare-earth-based compounds R_3BWO_9(R = Gd,Dy, Ho)

The magnetism and magnetocaloric effect(MCE) of rare-earth-based tungstate compounds R_3 BWO_9(R=Gd,Dy,Ho) have been studied by magnetic susceptibility,isothermal magnetization,and specific heat measurements.No obvious long-range magnetic ordering can be found down to 2 K.The Curie-Weiss fitting and magnetic susceptibilities under different applied fields reveal the existence of weak short-range antiferromagnetic couplings at low temperature in these systems.The calculations of isothermal magnetization exhibit a giant MCE with the maximum changes of magnetic entropy being 54.80 J/kg-K at 2 K for Gd_3 BWO_9,28.5 J/kg-K at 6 K for Dy_3 BWO_9,and 29.76 J/kg-K at 4 K for Ho_3 BWO_9,respectively,under a field change of 0-7 T.Especially for Gd_3 BWO_9,the maximum value of magnetic entropy change(-ΔS_M~(max)) and adiabatic temperature change(-ΔT_(ad)~(max)) are 36.75 J/kg·K and 5.56 K for a low field change of 0-3 T,indicating a promising application for low temperature magnetic refrigeration.     

Magnetic properties and magnetocaloric effect in TbCo2-xFex compounds

Magnetic properties and magnetocaloric effect in TbCo2-xFex compounds are studied by DC magnetic measurement. With increasing content of Fe, the entropy changes decrease slightly, though the Curie temperature is tuned from 231 K （x = 0） to 303 K （x = 0.1）. Magnetic entropies of TbCo2 compound are calculated by using mean field approximation （MFA）. Results estimated by using Maxwell relation are consistent with that of MFA calculation. It is shown that the entropy changes are mainly derived from the magnetic entropy changes. The lattice has almost no contribution to the entropy change in the vicinity of phase transition.     

Large reversible magnetocaloric effect in spinel MnV2O4 with minimal Al substitution

Magnetocaloric effect of MnV_1.95Al_0.05O₄ was studied by the magnetization and heat capacity measurements. MnV_1.95Al_0.05O₄ is a cubic spinel structure with ferromagnetism of second order in nature and performs reversible magnetic entropy around the magnetic transition temperature. The large magnetic entropy changes −ΔS_M∼5.2 and 8.2 J/kg K and the adiabatic temperature changes ΔT_ad∼1.5 and 2.6 K are revealed for the magnetic field changes of 2 and 4 T near the Curie temperature (T_C) of 59.6 K, respectively. The relative cooling power (RCP) are about 82.2 and 177.2 J/kg K for magnetic field changes 2 and 4 T, respectively. Compared with the parent compound, although the −ΔS_M and ΔT_ad become smaller, the refrigeration working temperature span and the RCP have been improved.