Magnetic and magnetocaloric effect of Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass

Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass exhibited excellent magnetic refrigeration material with a wide temperature range and high refrigeration capacity(RC)was reported.Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass was observed with typical spin glass behavior around 15.5 K.In addition,we find that the magnetic entropy change(-△S_(M))originates from the sample undergoing a ferromagnetic(FM)to paramagnetic(PM)transition around 20 K.Under a field change from 0 T to 7 T,the value of maximum magnetic entropy change(-△S_(M)^(max))reaches 12.5 J/kg·K,and the corresponding value of RC reaches 487.7 J/kg in the temperature range from 6 K to 60 K.The large RC and wide temperature range make the Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass be a promising material for application in magnetic refrigerators.

Review of magnetic properties and magnetocaloric effect in the intermetallic compounds of rare earth with low boiling point metals

The magnetocaloric effect （MCE） in many rare earth （RE） based intermetallic compounds has been extensively in- vestigated during the last two decades, not only due to their potential applications for magnetic refrigeration but also for better understanding of the fundamental problems of the materials. This paper reviews our recent progress on studying the magnetic properties and MCE in some binary or ternary intermetallic compounds of RE with low boiling point metal（s） （Zn, Mg, and Cd）. Some of them exhibit promising MCE properties, which make them attractive for low temperature magnetic refrigeration. Characteristics of the magnetic transition, origin of large MCE, as well as the potential application of these compounds are thoroughly discussed. Additionally, a brief review of the magnetic and magnetocaloric properties in the quaternary rare earth nickel boroncarbides RENi2B2C superconductors is also presented.

Magnetocaloric effect of (Gd_(1-x)Nd_x)Co_2 alloys in low magnetic field

The phases and magnetocaloric effect in the alloys （Gd1-xNdx）Co2 with x = 0, 0.1, 0.2, 0.3, and 0.4 were investigated by X-ray diffraction analysis and magnetization measurement. The samples are single phase with a cubic MgCu2-type structure. The To decreases obviously with increasing Nd content from 404 K of the alloy with x = 0 to 272 K of the alloy with x = 0.4; forx = 0.3, the To is 296 K, which is near room temperature. In the samples （Gd1-xNdx）Co2 with x = 0.0, 0.1, 0.2, 0.3, and 0.4, the maximum magnetic entropy change is 1.471, 1.228, 1.280, 1.381 and 1.610 J·kg^-1·K^-1, respectively, in the applied field range of 0-2.0 T. The results of Arrott plots confirmed that the transition type were second order magnetic transition forx = 0, 0.3, and 0.4.

Magnetocaloric effect of (Gd_(1-x)Ce_x)Co_2 compounds in low magnetic fields

The phases in the compounds （Gd1-xCex）Co2 with x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 were investigated by X-ray diffraction, and the magnetocaloric effect for x = 0-0.4 was studied by magnetization measurements. The samples are almost single phase with a cubic MgCu2-type structure for x = 0-0.5. The magnetization decreases with an increase in Ce content. There is almost no magnetic transition for x = 0.5 at 100-350 K. The Curie temperature （To） of the （Gd1-xCex）Co2compounds with x from 0.1 to 0.4 are 350, 344, 340, and 338 K respectively. The maximum magnetic entropy change is 2.34 J·kg^-1·K^-1 when x = 0.3. The results of Arrott plots show that the magnetic phase transition is second-order magnetic phase transition in these compounds.

Research Advance on Magnetocaloric Effect of La-Fe-M(Al, Si) Compounds

Recent research progress on magnetocaloric effect of La-Fe-M (M = Al, Si) compounds was presented. La-Fe-M (M = Al, Si) compounds of high Fe content are excellent soft magnetic materials with NaZn13 structure. The Curie temperature of the compounds can be increased by substituting small amount of Co for Si, Al. The La(Fe1-xCoy)(x)Si13-x compounds with an appropriate ratio of Co and Si can produce giant magnetocaloric effect comparable to that for Gd5Si2Ge2 at room temperature. The La (FexSi1-x)(13) doped with H can also produce giant magnetocaloric effect at room temperature, which is much greater than that for Gd. For La (FexSi1-x)(13) compounds with low Si or high Si contents. The nature of phase transition near Curie temperature induced by temperature and magnetic field was described in detail.

Phase structure and magnetocaloric effect of (Tb_(1–x)Dy_x)Co_2 alloys

Phase structure and magnetocaloric effect of （Tb1-xDyx）Co2 alloys with x=0, 0.2, 0.4, 0.6, 0.8, and 1.0 were investigated using X-ray diffraction analysis, differential thermal analysis, and magnetization measurement. The samples were single phase with cubic MgCu2- type structure; with the increase of Dy content, Tc decreased from 240 K （TbCo2） to 130 K （DyCo2）, and the maximum magnetic entropy change ｜ △SM,max｜ increased from 3.133 to 8.176 J/kg-K under low magnetic field of 0-2 T. The Arrott plot and the change of ｜△SM,max｜ showed that magnetic phase transition from second order to first order occured with the increase of Dy content between x=-0.6 and 0.8.

Structure, magnetism and magnetocaloric effects in Er_(5)Si_(3)B_(x)(x=0.3,0.6) compounds

We investigate the structure, magnetic properties, magnetic phase transitions and magnetocaloric effects(MCEs) of Er5Si3Bx(x=0.3,0.6) compounds. The Er5Si3Bx(x = 0.3, 0.6) compounds crystalize in a Mn5Si3type hexagonal structure(space group: P63/cm) and exhibit a successive complicated magnetic phase transition. The extensive magnetic phase transitions contribute to the broad temperature range of MCEs exhibiting in Er_(5)Si_(3)B_(x)(x=0.3,0.6) compounds, with maximum magnetic entropy change(-ΔSM_(max)) and refrigeration capacity of 10.2 J·kg^(-1)·K^(-1), 356.3 J/kg and 11.5 J·kg^(-1)·K^(-1),393.3 J/kg under varying magnetic fields 0–5 T, respectively. Remarkably, the δTFWHMvalues(the temperature range corresponding to 1/2×|-ΔSM_(max)|) of Er5Si3Bx(x=0.3,0.6) compounds were up to 41.8 K and 39.6 K, respectively. Thus, the present work provides a potential magnetic refrigeration material with a broad temperature range MCEs for applications in cryogenic magnetic refrigerators.

Development of magnetocaloric materials in room temperature magnetic refrigeration application in recent six years

Some magnetocaloric materials were used successfully in magnetic refrigeration application and became one of the critical parts of magnetic refrigeration technology whose delightful progresses were made worldwide in the past 30 years. At the same time, the research on giant magnetocaloric materials will accelerate the development of room temperature magnetic refrigeration. In this paper, the new theoretical and experimental investigations on magnetic materials in room temperature application were described, including Gd and its binary and ternary intermetallic compounds, Mn-based compounds, La(Fe13-xMx)-based compounds and manganites. Based on the analysis of hysteresis, corrosion, cost and heat process, the comparison between different families of magnetic materials was discussed. Further research of room temperature magnetic refrigerant was suggested.

Effects of manganese doping on magnetocaloric effect in Ge-rich Gd_5Ge_(2.05)Si_(1.95) alloy

The structure, magnetic and magnetocaloric properties of the Ge-rich Gd5Ge2.05-xSi1.95-xMn2x （x=0.01 and 0.03） alloys were investigated by scanning electron microscopy, X-ray powder diffraction, differential scanning calorimeter （DSC） and magnetization measurements. The results of energy dispersive X-ray analysis （EDX） and X-ray diffraction analyses showed that the composition and crystal structure of the alloys were desired. DSC measurements were performed to determine the transformation temperatures for each alloy. Both alloys exhibited the first order phase transition around room temperature. The alloys showed an anti-ferromagnetic transition around 60 K. The isothermal magnetic entropy changes of the alloys were determined from the isothermal magnetization measurements by using the Maxwell relation. The maximum values of isothermal magnetic entropy change of the Gd5Ge2.05-xSi1.95-xMn2x alloy with x=0.01 was found to be -12.1 and -19.8 J/（kg·K） using Maxwell equation around 268 K in applied fields of 2 and 5 T, respectively.

Magnetocaloric effect in Gd5（Si,Ge）4 based alloys and composites

The research on magnetocaloric materials for applications concentrates,among other,on two parameters:the ordering temperature and the value of the magnetocaloric effect(MCE).The optimization consists in tuning the former without significant drop in the latter.These studies report on the magnetic susceptibility,magnetization curves,heat capacity and magnetocaloric effect measurements for compositionally and structurally modified Gd5Si4 compound.The modifications are based on the doping of the parent compound with an excess Gd atoms and substitution of Si with B as well as on the dimensional effect studied by mechanical milling.Moreover,composite samples of the type Gd:Gd5Si2Ge2 were investigated revealing the influence of the intergranular interactions on the magnetocaloric properties.It appears that these interventions enable a controllable steering of the ordering temperature shifting it towards the room temperature with,in some cases,minor reduction of the parameters characterizing MCE.

Influence of Sn substitution for Co in RCo_2 (R= Gd,Tb,Dy) alloys on the structure and magnetocaloric effect

The phases and the magnetocaloric effect in the alloys R（Co1-xSnx）2 with X = 0, 0.025, 0.050, 0.075, and 0.100 were investigated by X-ray diffraction analysis and magnetization measurement. The substitution of Sn in RCo2 is limited. The cubic MgCu2-type structure for the alloys of RCo2 was confirmed by X-ray powder diffraction and the remaining alloys mainly consisted of the RCo2 phase, along with some RCo3 and R5Sn3 impurity phases. The impurity phases increase with the increase of Sn content. The Tc of the alloys is not very sensitive to the Sn substitution for Dy（Co1-xSnx）2 and Tb（Co1-xSnx）2, whereas in Gd（Co1-xSnx）2, the Curie temperatures significantly increase. The maximum magnetic entropy changes in the alloys Dy（Co1-xSnx）2 （x = 0, 0.025, 0.050, 0.075） are 5.78, 5.43, 3.88, and 2.98 J·kg^-1·K^-1, respectively, and those in the Tb（Co1-xSnx）2 （x = 0, 0.025） are 3.44, and 2.29 J·kg^-1·K^-1 respectively in the applied field change of 0-2.0 T.

Effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La1-xPrxFe11.4Si1.6Hy hydrides

In this paper, we study the effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La（1-x）PrxFe11.4Si1.6Hy hydrides. The powder x-ray diffraction patterns of the La1-xPrxFe11.4Si1.6 and its hydrides show that each of the alloys is crystallized into the single phase of cubic Na Zn13-type structure. There are hydrogen-absorbing plateaus under 0.4938 MPa and 0.4882 MPa in the absorbing curves for the La0.8Pr0.2Fe11.4Si1.6 and La0.6Pr0.4Fe11.4Si1.6 compounds. The releasing processes lag behind the absorbing process, which is obviously different from the coincidence between absorbing and releasing curves of the La Fe11.4Si1.6 compound. The remnant hydrogen content for La0.6Pr0.4Fe11.4Si1.6 is significantly more than that for La0.8Pr0.2Fe11.4Si1.6 after hydrogen desorption, indicating that more substitutions of Pr for La are beneficial to retaining more hydrogen atoms in the alloys. The values of maximum magnetic entropy change are 14.91 J/kg·K and 17.995 J/kg·K for La0.8Pr0.2Fe11.4Si1.6H0.13 and La0.6Pr0.4Fe11.4Si1.6H0.87,respectively.

Large magnetocaloric effect and magnetoresistance in ErNi single crystal

The magnetic properties,magnetocaloric effect and magnetoresistance in Er Ni single crystal have been investigated in detail.With decreasing temperature,Er Ni single crystal undergoes two successive magnetic transitions:a paramagnetic to ferromagnetic transition at T_(C)=11 K and a spin-reorientation transition at TS_(R)=5 K.Meanwhile,a sharp field-induced metamagnetic transition is observed below the T_(C)along the a axis.Er Ni single crystal possesses a giant magnetocaloric effect around T_(C).The maximum magnetic entropy change is-36.1 J(kg K)^(-1)along the a axis under the field change of 0-50 k Oe.In particular,the rotating magnetocaloric effect in Er Ni single crystal reaches its maximum under a relatively low field,and the maximum rotating entropy change with a value of 9.3 J(kg K)^(-1)is obtained by rotating the applied field from the[011]to[100]directions under 13 k Oe.These results suggest that Er Ni could be a promising candidate for magnetic refrigeration working at liquid-helium temperature region.Moreover,a complicated transport behavior is uncovered in Er Ni single crystal,which is attributed to the complex magnetic states and magnetic polaronic effect.Both positive and negative magnetoresistance are observed.A considerable large magnetoresistance with the value of-34.5%is acquired at 8 K under50 k Oe when the field is along the[100]direction.

Magnetocaloric Properties of (Gd_(1-x)Tb_x)_3Al_2 Compounds Near Room Temperature

Magnetic and thermal properties of the (Gd 1- x Tb x ) 3Al 2 compounds were studied as potential magnetic refrigerant materials which are used in magnetic refrigeration near room temperature at low magnetic field. The compounds (Gd 1- x Tb x ) 3Al 2 with x =0, 0.1, 0.2 and 0 3 exhibit a second order magnetic transition. Curie temperature varies from 255 K for x =0.3 to 280 K for x =0. The maximum of the isothermal magnetic entropy change Δ S increases by substituting Tb element for Gd element. Δ S max =18.9 kJ·m -3 ·K -1 for x =0.1 by changing the magnetic field from 0 to 1 T.

Magnetic Entropy Change of (Gd_(1-x)RE_x)_5Si_4(RE=Dy, Ho) Alloys

The magnetic properties, including Curie points, magnetic phases transition and magnetic entropy changes, of （Gd1-xREx）5Sin（RE = Dy, Ho） alloys were systematically studied. The results show that the alloys keep the Sm5Ge4 orthorhombic structures as Gd5Si4, and the Curie points of the alloys almost linearly decrease with increasing content of x, so that the Curie points can be adjusted by adding different concentrations of Dv or Ho in the alloys. The magnetic properties of these alloys obey second order transition. The costs of these alloys are cheaper than that of Gd- Si-Ge alloys because there is not expensive element such as Ge. The large magnetic entropy change at low fields （ 〈 2 T） and wide temperature ranges of these alloys suggest that they are suitable to be the gradient function materials and candidates of magnetic refrigerants at room temperature with low fields.

Preparation and magnetic properties of nanosized (La_(0.47)Gd_(0.2))Sr_(0.33)MnO_3

Nanosized (La0.47 Gd0.2)Sr0.33MnO3 perovskite oxides were prepared at relatively low calcinating temperature of 600℃ and 800℃ for 10h using amorphous complex precursor. Curie temperatureTc and magnetocaloric effects（MCE） were investigated. X-ray diffraction（XRD） and electron diffraction（ED） reveal that the resulting products are of pure single-phase rhombohedral perovskite structure. Transmission electron microscopy（TEM） observation finds that the particle sizes are about 40-50nm and 80-100nm, and the Tc are 285.1K and 285.9K, MCE are about 2.02J/（kg·K-1 ） and 3.90J/（kg·K-1 ） at 5T magnetic field. A relatively large MCE with a broad peak around Curie temperature is observed in sample sintered at 800℃ for 10h. This suggests that nanosized (La0.47 Gd0.2)Sr0.33MnO3 is a suitable material as working substance in magnetic refrigeration in room temperature.

Magnetic properties and large magnetocaloric effects of GdPd intermetallic compound

With the intention to explore excellent magnetocaloric materials, the intermetallic compound GdPd was synthesized by arc melting and heat treatment. The microstructure, magnetic and magnetocaloric properties of the intermetallic compound of GdPd were investigated by X-ray diffraction（XRD）, scanning electron microscopy（SEM） and the physical property measurement system（PPMS）. A large reversible magnetocaloric effect is observed in GdPd accompanied by a second order magnetic phase transition from paramagnetism to ferromagnetism at ～39 K. The paramagnetic Curie temperature（θp） and the effective magnetic moment（μ（eff））are determined to be 34.7 K and 8.12 μB/Gd,respectively. The maximum entropy change（｜△SM（Max）｜） and the relative cooling power（RCP） under a field change of 5 T are estimated to be 20.14 J/（kg·K） and 433 J/kg, respectively. The giant reversible magnetocaloric effects（both the large△SM and the high RCP） together with the absence of thermal and field hysteresis make the GdPd compound an attractive candidate for low-temperature magnetic refrigeration.

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.

室温磁致冷材料的研究进展

对室温磁致冷材料的最新进展作了综合报道,主要包括Gd、Gd-Si-Ge、La-Fe-(Si、Al)、Mn-As-Sb、Mn-Fe-P-As几个化合物系列。Gd,居里温度294K,其磁热性能在所有纯金属中最好;Gd5Si2Ge2,居里温度274K,在此温度处具有巨磁热效应;在La-Fe-Co-Si、La-Fe-Co-Al化合物中,改变Co的含量可以使化合物的居里温度得到调整,其磁热性能可以与Gd比拟甚至超过Gd;MnFeP0.45As0.55,居里温度308K,具有巨磁热效应,磁热性能远远超过Gd。在MnAs1-xSbx化合物中,随Sb(0<x<0.1)含量的变化,材料的居里温度在318K～230K连续调整,但仍保持大的磁热效应。最后指出将居里温度不同的材料进行合理组合而得到复合材料,以拓宽材料的磁热效应曲线是室温磁致材料研究发展的一个重要途径。

磁致冷材料研究进展

介绍了磁致冷材料磁热效应的表征方法,概述了国内外各温度区间磁致冷材料的研究进展。在20K以下温区,磁致冷材料研究主要集中在具有高导热率、低点阵热容和极低有序化温度的石榴石,如Gd3Ga5O12(GGG),Dy3Al5O12(DAG),Gd3Ga5-xFexO12(GGIG)及Er基磁致冷材料;20K^77K温度区间,磁致冷材料研究主要集中在重稀土金属间化合物中,如(Dy1-xErx)Al2复合材料等;在室温附近,具有大磁热效应的磁致冷材料以稀土Gd,Gd5(SixGe1-x)4(0≤x≤0.5)和MnFeP1-xAsx(0.15≤x≤0.66)合金为代表,特别是Gd5Si2Ge2(TC=274K)和MnFeP0.45As0.55(TC=300K)合金,在磁场5T下具有巨磁热效应,是Gd的2倍以上。总结了各温度区间磁致冷材料的选择依据。重点评述了室温磁致冷材料的最新研究成果,展望了室温磁致冷材料的发展前景。