Recent progresses in exploring the rare earth based intermetallic compounds for cryogenic magnetic refrigeration

Journal Pre-proof Recent progresses in exploring the rare earth based intermetallic compounds for cryogenic magnetic refrigeration Lingwei Li, Mi Yan PII:

S0925-8388(20)30173-0

DOI:

https://doi.org/10.1016/j.jallcom.2020.153810

Reference:

JALCOM 153810

To appear in:

Journal of Alloys and Compounds

Received Date: 11 September 2019 Revised Date:

7 January 2020

Accepted Date: 10 January 2020

Please cite this article as: L. Li, M. Yan, Recent progresses in exploring the rare earth based intermetallic compounds for cryogenic magnetic refrigeration, Journal of Alloys and Compounds (2020), doi: https://doi.org/10.1016/j.jallcom.2020.153810. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2020 Published by Elsevier B.V.

Recent progresses in exploring the rare earth based intermetallic compounds for cryogenic magnetic refrigeration ∗

Lingwei Li a, b and Mi Yan a, c a b

Institute of Advanced Magnetic Materials, Hangzhou Dianzi University, Hangzhou 310012, P. R. China

Key Laboratory of Electromagnetic Processing of Materials (Ministry of Education), Northeastern University, Shenyang 110819, P. R. China c

School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China

ABSTRACT: Nowadays, the magnetic materials with special functional characteristics are played very important roles in the development of our present modern society. The magnetic refrigeration (MR) technology which is based on the magnetocaloric effect (MCE) of magnetic solids has been considered as an energy-efficient alternative method to our present well used gas compression/expression refrigeration technology. The commercial products of magnetic refrigerators are still in the developing stage, searching and designing magnetic solids with outstanding MCE performances is one of the most important tasks at present. This paper briefly reviewed our recent progress in the investigation of the crystal structure, magnetic properties and magnetocaloric performances in several series of binary and ternary rare earth (RE) based intermetallic compounds. Some of them have been found to exhibit promising magnetocaloric performances at low temperatures which make them be considerable for cryogenic MR application.

Keywords: Rare earth based intermetallic compounds; Magnetic functional materials; Magnetocaloric effect; Magnetocaloric performances; Magnetic entropy change; Cryogenic magnetic refrigeration.

∗

Corresponding author. E-mail address: [email protected] (L. Li) 1 / 57

1. Introduction Nowadays, the magnetic functional materials, such as advanced permanent and soft magnets, magneto-impedance and microwave materials, magnetoresistance materials, magnetic shape memory alloys, etc. have played very important roles in the development of our modern society [1-8]. Recently, the magnetic refrigeration (MR) technology which is based on the magnetocaloric effect (MCE) of the magnetic solids has been considered as one of the most promising alternative methods to our present well used gas compression/expansion technology due to its high efficiency [6-12]. Moreover, the MR can be more compactly built since the main working materials are magnetic materials in solid states and therefore no harmful gases are involved. However, up to the present the commercial magnetic refrigerators are only in the laboratory developing stage. The MCE is a magneto-thermodynamic response for all magnetic solids and it is related to the coupling of the magnetic sub-lattice(s) with the magnetic field, which will change the entropy or the temperature of the system when the magnetic solids are subjected to a varying external magnetic field. The researchers in this field related to the MR and MCE are still focusing to search or design novel magnetic solids with outstanding magnetocaloric performance at present stage. Thus, the magnetic properties and magnetocaloric performances in plenty of magnetic solids, including oxides, alloys, amorphous, intermetallic, and composites have been systematically investigated experimentally and theoretically in the last thirty years [13-45], and a number of magnetic solids with outstanding room or near-room temperature magnetocaloric performances have been reported, such as, MnAs-based compounds [46-51], Gd5(SiGe)4-based compounds [51-55] Ni-Mn-X (X = Ga, In and Sn)-based Heusler alloys [56-63], La(Fe,Si)13Hx-based compounds [64-70], MnTMX (TM = Co, Ni and Fe; X = Si and Ge)-based compounds[71-76], etc. The rare earth (RE)-transition metal(s) (TM) based alloys and compounds have also been investigated extensively in recent years not only due to the existence of interesting physical properties but also for their potential applications in various industry fields [77-98]. Depending on 2 / 57

the constituent elements and crystal structures, various interesting physical properties, such as, magnetic ordering, spin/valence fluctuations, superconductivity, heavy-fermion behaviour, as well as the special magnetic functional characteristics, such as, magneto-resistance (MR) effect, magnetostrictive, microwave absorption, MCE, etc. have been observed [77-98]. Generally, the magnetism of RE or RE-based compounds mainly originated from the partially unfilled 4f shell electrons of RE3+ ions. The magnetic moments of RE ions could be quite large if the 4f electrons are well localized. Whereas, the electrons from the TM elements are itinerant, thus, a combination of both RE and TM ions often gives rise to exotic magnetic characters, despite the fact that TM elementals always show weak or even no magnetism. A huge number of RE-TM-based alloys and intermetallic compounds have been prepared and investigated with respect to the crystal structure, physical and chemical properties as well as the magnetic properties and magnetocaloric performances. And some of the selected RE-TM-based compounds are found to exhibit promising cryogenic magnetocaloric performance [99-112]. In this paper, we will briefly review our recent progress in the investigation of the crystal structure, magnetic properties and magnetocaloric performances in several series of binary or ternary RE-TM-based intermetallic compounds.

2. Experiment details 2.1. Sample preparation and characterization Most of the RE-TM-based intermetallic compounds mentioned in this review paper were prepared by the traditional arc-melting method together with several days annealing at high temperatures. First, the stoichiometric amounts of high purity (not worse than 99.9 wt.%) elements were melted on a water-cooled copper hearth. A small amount excess RE elementals (0.5-2 wt.%) were generally added to compensate the weight loss. Then, the sample was melted at least 4 times to ensure the homogeneity. The total weight losses obtained by this method were all less than 0.4%. Finally, the obtained ingots were subsequently annealed for more than 70 hours in the evacuated 3 / 57

quartz-tubes. Some of the samples with the consistent elementals of Zn, Mg, and Cd cannot be prepared by arc-melting method due to the fact of high vapour pressure (low boiling point) of these elements. These materials were prepared by the following processes. First, stoichiometric amounts of high-purity (not worse than 99.9 wt.%) elements were sealed in an arc-weld Nb- or Ta-crucible under the argon gas pressure of 80±5 kPa. Then, the crucible was fixed in a water-cooled holder of and heated up till all the elements were melted for 5-10 minutes by an induction melting method. Finally, the obtained products were grinded and pressed into pellets, then subsequently annealed for more than 70 hours in the evacuated quartz-tubes. The crystal structure and phase purity of all samples were characterized by means of X-ray powder diffraction (XRPD) at room temperature, Scanning Electron Microscope (SEM) and Energy Dispersive X-Ray Spectroscopy (EDX) technology. The temperature and magnetic field dependence of magnetization of all samples were measured by using the commercial vibrating sample magnetometer

(VSM)

as

well

as

superconducting-quantum-interference-device

(SQUID)

magnetometer with the DC magnetic fields up to 7 T which is generated by the superconducting magnet. 2.2. Determination of the magnetocalric performance To determine the magnetocaloric performance of the magnetic solids, figures of merit are necessary to be used for the comparison. Generally, the MCE can be directly characterized by the change of magnetic part ∆SM under the change of magnetic field (∆H). The temperature and ∆H dependence of -∆SM for all samples in this review work are all indirectly determined by using the equation of [6, 11], H  ∂M (H , T )  ∆S M (T , ∆H ) = ∫   dH , 0 ∂T  H

(1)

4 / 57

which is based on the Maxwell’s relation from the experimental data of the magnetization that was measured under discrete temperature and field-intervals. Additionally, two correlated parameters of refrigerant capacity (RC) and relative cooling power (RCP) have also been considered as the important parameters to determine the magnetocaloric performance of magnetic solids which are widely used to roughly determine the amount of the heat transfer during ideal MR cycles [6, 11]. The RCP can be evaluated by the product of the maximum magnetic entropy change -∆SMmax with full-width at half-maximum in ∆SM (T) curve, δTFWHM which is usually expressed as [107, 108],

RCP = −∆SMmax × δ T FWHM .

(2)

The RC can be evaluated by numerical integration of the -∆SM (T) curve at half-maximum of the peak in ∆SM (T) curve as the integration limits which is usually expressed as [107, 108]: RC = ∫

T2

T1

∆S M dT .

(3)

Here, T1 and T2 are the temperatures correspond to the half-maximum values at both sides in the -∆SM (T) curve, respectively. The values of -∆SMmax together with RCP and RC are applied to evaluate the magnetocaloric performances in the present review.

3. Crystal structure, magnetic properties and magnetocaloric performances in RE-TM-based intermetallic compounds 3.1. Binary RE-TM (RE = Nd, Ho, Er, and Tm; TM = Zn and Ga) compounds The equiatomic binary REZn compounds crystallize in a simple cubic CsCl-type structure (Pm3m space group), where RE atoms and Zn atoms occupy the equivalent positions and the coordination numbers are eight for all compounds. Previous investigations revealed that the REZn compounds undergo ferromagnetic (FM) to paramagnetic (PM) transition around 266, 205, 103, 72, 5 / 57

20, and 8.4 K for RE = Gd, Tb, Dy, Ho, Er, and Tm, respectively [81, 113-116]. Additionally, another low temperature spin reorientation (SR) transitions were also found around 64, 50, and 26 K for RE = Tb, Dy, and Ho, respectively [113-117]. The magnetic properties and magnetocaloric performances in REZn (RE = Gd-Tm) compounds have been investigated experimentally or/and theoretically [114-117]. The magnetic transition temperature(s) (TM) as well as the MCE parameters (−∆SMmax, RC and RCP) under ∆H of 0-5 T for REZn and REGa compounds (which will be shown below) together with some magnetic solids with promising cryogenic magnetocaloric performances are summarized in Table 1. The HoZn compound undergoes two successive magnetic transitions at 26 and 72 K, which correspond to SR transition and FM ordering, respectively. Accordingly, the -∆SM(T) curves exhibit one sharp peak (around TC) together with a shoulder (around TSR), and resulting in an appreciable MCE in a rather broad temperature range [115]. Moreover, the TmZn compound is FM ordering below TC of 8.4 K, which reveals a metamagnetic phase transition (field-induced) above and around TC. The value of -∆SMmax under ∆H of 0-7 T for TmZn can reach 29.7 J/kg K [117]. Furthermore, under the low ∆H of 0-1 and 0-2 T, the values of -∆SMmax are still as high as 11.8 and 19.6 J/kg K which are beneficial for active MR application. The values of maximum adiabatic temperature change (∆Tadmax) are as high as 3.3, 8.6, and 11.2K under ∆H of 0-2, 0-5, and 0-7 T, respectively. The giant MCE in TmZn compound is believed to due to its first-ordered metamagnetic (field-induced) phase transition [117]. Moreover, it is well known that the magnetic properties could be adjusted by external hydrostatic pressure. Thus, the pressure effect (up to 1.4 GPa) on magnetic properties for TmZn were also investigated [118]. The temperature dependence of M measured in ZFC and FC modes for TmZn with H of 0.1 T under various external pressures are illustrated in Fig. 1. All FC and ZFC M(T) curves reveal a typical PM to FM transition. The values of TC are 8.4, 9.1 and 11.2 K with the pressures of 0, 0.6 and 1.4 GPa, respectively. A set of M(H) curves for TmZn under the hydrostatic pressures are measured. Except some small differences in values, the M(H) curves show a similar 6 / 57

character under different external pressures. I. e., the metamagnetic transition (field-induced) appears in above and around TC, and the critical values of magnetic field increases gradually with increasing temperature. Fig. 2 illustrates the -∆SM(T) curves for TmZn under various external pressures which is estimated from the measured M (H, T) data by Eq. 1. The values of -∆SMmax for TmZn under ∆H of 0-5 T with the external hydrostatic pressures of 0, 0.6 and 1.4 GPa are 26.9, 24.7 and 22.4 J/kg K, respectively. The corresponding values of RC are 214, 203 and 141 J/kg. I. e., the MCE is supressed gradually with increasing hydrostatic pressure, which is probably due to the suppression of the first-ordered metamagnetic transition (field induced) by the external hydrostatic pressure [118]. Based on the Er-Zn phase diagram, the ErZn compound can co-exist with ErZn2 compound in a wide composition range [119], thus, the ErZn2/ErZn composite with the nominal composition of Er40Zn60 was fabricated and we systematically investigated its magnetic properties and magnetocalric performances. The Er40Zn60 alloy was confirmed to crystallize in ErZn and ErZn2 dual phases with the weight ratio of 46.2:53.8 based on the XRD and EDS results. Temperature dependence of M (left-scale) and dM/dT (right-scale) for Er40Zn60 alloy (H = 1 T) are illustrated in Fig. 3, the corresponding M(T) curves measured in the FC and ZFC modes (H = 0.1 T) are illustrated in the inset of Fig. 3. The Er40Zn60 alloy undergoes two magnetic transitions around 20 and 9 K, which are corresponding to the magnetic ordering temperatures of ErZn and ErZn2 compounds, respectively. A set of M(H) curves for Er40Zn60 alloy are measured to evaluate its MCE properties. Several typical M(H) curves are illustrated in Fig. 4 (a) for a clarify. The -∆SM(T) for Er40Zn60 alloy under ∆H of 0-2, 0-5, and 0-7 T are illustrated in Fig. 4 (b), which is calculated based on M (H, T) data by using Eq. 1. Two pronounced peaks have been observed in -∆SM(T) curves at ~20 and ~10 K which are corresponding to the ErZn and ErZn2 phases, respectively. Two peaks are overlapped and resulting in a table-like magnetocaloric performance in present dual-phase Er40Zn60 alloy, which is benefit for active MR application [120]. The values of -∆SMmax for Er40Zn60 alloy under ∆H of 0-5 and 0-7 T reach 19.5 and 25.4 J/kg K, respectively. The corresponding values of RCP(RC) reach 7 / 57

447(362) and 645(503) J/kg, respectively [120]. From Table 1, we can find that the MCE parameters for present dual-phase Er40Zn60 alloy are comparable or even larger than some of the active cryogenic MR materials, indicating that the Er40Zn60 alloy could be a promising candidate for cryogenic MR [120]. The binary REGa compounds crystallize in orthorhombic CrB-type crystal structure with the space group of Cmcm. The basic unit of the structure is the triangular prism with RE atoms located at the corners and Ga atoms located nearly at the center, respectively. A second-ordered magnetic transition from PM to FM is found for REGa at 33, 44, 65, 32, and 15 K for RE = Pr, Nd, Ho, Er, and Tm, respectively. Additionally, the SR transition can also be found for RE = Nd, Ho, and Er [81, 121-125]. The magnetocaloric properties in REGa compounds have been well investigated [122-125] and the MCE parameters can also be found in Table 1. Moreover, rotating (or anisotropic) MCE (RMCE) is found in some selected crystals [132-138]. Instead by changing the external magnetic field, the refrigeration can be achieved as well by simply rotating the magnetic solids with RMCE under the fixed magnetic field. Therefore, the single crystal grains are selected from long time annealed NdGa arc-melted ingot, and we systematically studied the magnetic properties, MCE and RMCE [139]. Fig. 5 illustrates the temperature dependence of the reciprocal susceptibility 1/χ (right-scale) and susceptibility χ (left-scale) along the a-axis (intermediate direction), b-axis (hard direction) and c-axis (easy direction) for present NdGa crystal with H of 1 T. A clear PM to FM transition at TC of 42 K occurs along all axes [139]. The change in slope along a- and b- axes around 23 K is due to the transition of SR. The high temperature 1/χ-T (above 50 K) for present NdGa crystal obeys the Curie-Weiss law: 1/χ = (T-θp)/C (C represents Curie constant and θp represents paramagnetic Curie temperature). The evaluated effective magnetic moment (µeff) values are 3.49, 3.47, and 3.54

µB/Nd3+ for present NdGa crystal along a-, b-, and c-axes, respectively, which are all well consistent 8 / 57

with the values of free Nd3+ ion (3.62 µB) [139]. A set of Μ(H) curves are also determined with H along the a-, b-, and c-axes. Strong magneto-crystalline anisotropy can be observed in present NdGa crystal, thus, a large anisotropy in MCE would also happens. The -∆SM(T) for NdGa crystal along the a-, b-, and c-axes which is calculated based on the measured M (H, T) data by using Eq. (1) are illustrated in Fig. 6 (a-c), respectively. With the ∆H of 0-7 T, the peak values of -∆SM at TSR are 7.6 and 1.9 J/kg K for H along a- and b-axis, the corresponding peak values of -∆SM at TC reach 14.1, 4.7, and 21.1 J/kg K for H along a-, b-, and c-axis, respectively [139]. The -∆SMmax values for H along c-axis, especially under a low ∆H of 0-2 T (12.0 J/kg K) are comparable or larger than most of recently reported excellent cryogenic MCE materials (see table 1) make NdGa single crystal competive for cryogenic MR. The -∆SM(T) curves for NdGa crystal under ∆H of 0-7 T along a-, b-, and c-axes are illustrated in Fig. 7 (a) for a direct comparison. Large differences among different axes can be observed, indicating the magnetic entropy can change a lot by rotating the NdGa crystal under fixed H, i. e., a large RMCE. Therefore, the magnetic entropy change rotating from the hard-axis (b-axis) to the easy-axis (c-axis) (∆SR, cb) under fixed H is evaluated by: ∆SR, cb = ∆SM (H//c) − ∆SM (H//b),

(4)

where the ∆SM (H//c) and ∆SM (H//b) are the ∆SM with H along the a- and c- axes, respectively. The ∆SR, cb (T) curves for present NdGa crystal are illustrated in Fig. 7 (b). The maximun ∆SR values for NdGa crystal together with some recently reported large RMCE materials are illustrated in Table 2. The maximum ∆SR, cb value of NdGa crystal reaches 16.6 J/kg K at H of 7 T, which is obviously larger than that of reported large RMCE materials (from Table 2) [139]. Moreover, despite the higher magnetic field (changes) the larger MCE and RMCE can be obtained, it is difficult to design the MR cycles for H > 2 T by using permanent magnets, thus, low field RMCE materials are benefit for 9 / 57

practical application. For the present NdGa crystal, the maximum ∆SR, cb reaches 10.1 J/kg K at the field of 2 T which is obvious largerly than that of reported large RMCE materials (from Table 2). The low-field large RMCE in NdGa crystal is probably due to its own low field strong magneto-crystalline anisotropy. The large RMCE and MCE, especially under low magnetic field (changes), make the NdGa crystal attractive for practical cryogenic MR application [139]. 3.2. Ternary RETMX (RE = Tb, Dy, Ho, and Er; TM = Fe, Co, and Pt; X = Al, Mg, and C) compounds In the past two decades, many ternary equi-atomic RETMX compounds were investigated in detail with respected to the magnetic and magnetocaloric properties [99-101, 140-147]. Generally, the magnetism of RETMX compounds is mainly from the RE ions and the TM ions show nonmagnetic. The crystallographic structure strongly depends on the variation of TM or/and X, thus affecting the magnetism and MCE of these compounds [99-101]. Some of the selected RETMX compounds were reported to process promising magnetocaloric performances [142-146]. In this section, our recent progresses of the new addition to this list are given as below. The magnetic transition temperature(s) (TM) as well as the MCE parameters (−∆SMmax, RC and RCP) under ∆H of 0-5 T for the REFeAl [143-146], RECo0.5Al1.5 [147], RECoC [148], RECoC2 [149, 150] and REPtMg [151] compounds are illustrated in Table 3. The REFeAl compounds crystallize in the hexagonal MgZn2-type crystal structure belonging to P63/mmc space group. The RE, Fe and Al occupy the 4f, 2a and 6h sites, respectively [143-146]. Kaštil et al. [144] reported that MCE in GdFeAl and TbFeAl, the corresponding -∆SMmax values are 3.3 and 2.6 J/kg K at 259 and 196 K under ∆H of 0-4 T, respectively. We have found that DyFeAl [145] undergoes a FM to PM transition at 129 K; whereas, two successive magnetic transitions have been observed at 55 and 28 K for HoFeAl [146], and at 80 and 38 K for ErFeAl [146], respectively. The values of -∆SMmax under ∆H of 0-5 T are 6.4, 6.1 and 7.5 J/kg K for DyFeAl, HoFeAl, and 10 / 57

ErFeAl, respectively [145, 146]. The corresponding RCP(RC) values are 595(446), 311(240), and 563(435) J/kg. Moreover, we have also studied the magnetocaloric performances in the RECo0.5Al1.5 (RE = Gd, Tb, Dy, and Ho) (also represented as R2CoAl3) compounds. All RECo0.5Al1.5 compounds are confirmed to crystallize in MgCu2-type crystal structure (Fd-3m space group), where the RE atoms form the diamond lattice and the remaining space is occupied by regular tetrahedra consisting of Al(Co) atoms [147]. All the compounds undergo a PM to FM transition with the TC of 70, 47, 33, and 20 K for RE = Gd, Tb, Dy and Ho, respectively [147]. Accordingly, the values of -∆SMmax under ∆H of 0-7 T are 16.2, 10.6, 9.4, and 16.5 J/kg K, respectively, and the corresponding of RCP(RC) values are 878(658), 541(423), 510(402), and 570(443) J/kg [147]. The equi-atomic RECoC compounds are found to crystallize in the tetragonal YCoC-type crystal structure (P4/mmm space group), which consists of alternating RE planes and Co-C planes. There are four neighboring C or Co atoms around the Co or C atom in the Co-C plane, respectively [148]. The temperature dependence of 1/χ (right-scale) and M (left-scale) with H of 1 T for TbCoC and ErCoC are given in Fig. 8 (a) and (b), respectively, the corresponding M(T) curves measured in FC and ZFC modes with H of 0.1 T are illustrated in the inset of Fig. 8. The high temperature 1/χ-T curve for both compounds obeys the Curie-Weiss law. The TbCoC reveals a FM to PM transition at TC of ~22 K, whereas, the ErCoC show a typical PM to antiferromagnetic (AFM) at TN (Néel temperature) around 10 K, and still AFM ordering at 1 T. A set of Μ(H) curves for RECoC (RE = Tb and Er) are determined, and a metamagnetic transition (field-induced) from AFM to FM or ferrimagnetic (FIM) state can be observed for ErCoC [148]. The -∆SM(T) for RECoC (RE = Tb and Er) which is calculated from the measured M (H, T) data by using Eq. (1) are given in Fig. 9 (a) and (b), respectively. The value of -∆SMmax for TbCoC is 18.9 J/kg K under ∆H of 0-7 T, the corresponding RCP(RC) values are 715(555) J/kg [148]. The -∆SM values for ErCoC are negative at low temperature region under low ∆H and change to positive with the increase of temperature and ∆H, which is related to the fact of the magnetic transition (field-induced) from AFM to FM or FIM 11 / 57

state. The -∆SMmax for ErCoC is 22.7 J/kg K under ∆H of 0-7 T, the corresponding RCP(RC) values are 618(488) J/kg [148]. Moreover, we also investigated the magnetocaloric performances in RECoC2 (RE = Gd, Ho, and Er) compounds, which crystallize in the orthorhombic CeNiC2-type crystal structure (Amm2 space group). There are two kinds of two-dimensional networks, one is composed of RE atoms and the other is composed of Co and C atoms [149, 150]. All RECoC2 compounds reveal a PM to FM transition with the TC values of 15, 14, and 11 K for RE = Gd, Ho and Er, respectively. Accordingly, the -∆SMmax values under ∆H of 0-5 T are determined to be 28.4, 15.6, and 17.2 J/kg K, respectively, and the corresponding RCP(RC) values are 566(369), 242(183), and 375(243) J/kg [149, 150]. The magnesium compounds REPtMg (RE = Tb, Dy, and Ho) crystallize in hexagonal ZrNiAl-type crystal structure (P 6 2m space group), in which RE atoms are combined with the three-dimensional [PtMg] networks through the shorter contact of RE-Pt. The RE atoms and Mg atoms occupy the 3f and 3g sites, while Pt atoms occupy the 1a and 2d sites, respectively [152]. Fig. 10 (a-c) illustrate the temperature dependence of 1/χ (right-scale) and Μ (left-scale) for REPtMg (RE = Tb, Dy, and Ho) with H of 1 T, respectively. The corresponding M(T) curves measured in the FC and ZFC modes with H of 0.2 T are presented in the insets of Fig. 10. The 1/χ-T curves for all the compounds obey the Curie-Weiss law at high temperatures. All the REPtMg compounds undergo a FM to PM transition around TC of ~58, ~29, and ~20 K for RE = Tb, Dy, and Ho, respectively [151, 152]. Moreover, an additional SR transition around 9 K is observed for HoPtMg. The -∆SM(T) for REPtMg compounds which was calculated based on the measured M (H, T) data by using Eq. (1) are illustrated in Fig. 11 (a-c), respectively. The values of -∆SMmax under ∆H of 0-7 T are 6.3, 8.9 and 12.2 J/kg K for TbPtMg, DyPtMg, and HoPtMg, respectively, the corresponding values of RCP(RC) are 278(210), 330(253) and 400(298) J/kg [151]. 3.3. Ternary RE2TM2Al (RE =Dy, Ho, Er, and Tm; TM = Co and Ni, Cu) and RE2Ni2In (RE = Pr, Nd, Dy, and Ho) compounds 12 / 57

There are four different types of crystal structure for ternary RE2TM2X compounds, i.e. the orthorhombic W2CoB2-type (Immm space group), the orthorhombic Mn2AlB2-type (Cmmm space group), the tetragonal Er2SnAu2-type (space group of P42/mnm), and the tetragonal Mo2FeB2-type (P4/mbm space group) [108, 153-156]. Most of RE2TM2X compounds are ordering magnetically, some of them are reported to process promising magnetocaloric performances which make them attractive for cryogenic MR [157-162]. Zhang [108] have reviewed the structural, magnetic and MCE properties in the RE2TM2X with RE of Gd-Tm, TM of Ni, Cu, Co, and X of In, Cd, Ga, Al. Thus, only our recent progresses of RE2Ni2In (RE = Pr, Nd, Dy, and Ho) [163] and RE2TM2Al (RE =Dy-Tm; TM = Co, Ni, and Cu) [164] compounds are given in this section. The magnetic transition temperature(s) (TM) as well as the MCE parameters (-∆SMmax, RC and RCP) under ∆H of 0-5 T for RE2Ni2In and RE2TM2Al compounds together with some other selected RE2TM2X compounds are illustrated in Table 4. The crystal structure of RE2Ni2In compounds are different for the light-RE and heavy-RE, i. e., tetragonal Mo2FeB2-type crystal structure (P4/mbm space group) for RE = Pr and Nd, whereas, orthorhombic Mn2AlB2-type crystal structure (Cmmm space group) for RE = Dy and Ho. The layer of RE atoms is separated by layers of Ni and In atoms, and its interlayer spacing is consistent with the lattice constant c in the light-RE-based RE2Ni2In. For the heavy-RE-based RE2Ni2In, the local symmetry of the rare earth atoms with magnetic moments is m2m, and the non-magnetic Ni and In atoms exist around each rare earth atom [163]. The Pr2Ni2In and Nd2Ni2In compounds undergo a FM to PM transition at TC of 7.5 and 10.5 K, respectively. The Dy2Ni2In and Ho2Ni2In compounds undergo a PM to AFM transition at TN of 19 and 10.5 K, respectively. Moreover, an additional SR transition at ~5.5 K for Ho2Ni2In compound can be detected [163]. Moreover, the M of the RE2Ni2In (RE = Dy and Ho) compounds increase linearly with increasing H, and show an abrupt increment at ~2 T, indicating the existence of AFM ground state, and a field-induced AFM to FM or FIM transition [163]. The values of -∆SMmax under ∆H of 0-5 T are 9.3, 11.5, 6.4 and 11.5 J/kg K for 13 / 57

Pr2Ni2In, Nd2Ni2In, Dy2Ni2In, and Ho2Ni2In, respectively, and the corresponding RCP(RC) values are 60(47), 101(74), 130(95) and 210(152) J/kg [163]. The RE2TM2Al (RE = Dy-Tm; TM = Co and Ni) compounds crystallize in orthorhombic W2B2Co-type (Immm space group) crystal structure. The lattice parameters and unit cell volumes increase as the radius of RE atom increases in RE2TM2Al compounds. Additionally, the bond lengths and angles of RE2Co2Al are significantly larger than those of RE2Ni2Al for the same RE elements [164]. Fig. 12 (a-h) illustrate the M(T) curves for RE2TM2Al (RE = Dy-Tm; TM = Co and Ni) under H of 0.2 T, respectively. The corresponding M(T) curves measured under H of 1 T are illustrated in the insets of Fig. 12. Two successive magnetic transitions are found for all the RE2TM2Al compounds, which can be usually observed in the similar systems [108, 163-166]. The lower temperature one is due to the SR of the moments, and the higher temperature one is related to the magnetic transition from PM to FM or AFM [164]. The FM transition for RE2Co2Al and the AFM transition for RE2Ni2Al can still be seen, but the transition temperatures shift to higher temperature than that of under 0.2 T. The values of TC for RE2Co2Al are 62, 32, 27, and 11.5 K for RE = Dy, Er, Ho, and Tm, respectively, and the corresponding values of TSR are of 41, 21, 9, and 7 K [164]. The values of TN for RE2Ni2Al compounds are 19, 6, 12, and 6 K for RE = Dy, Er, Ho, and Tm, respectively, the corresponding TSR for RE2Ni2Al are 4, 3, 6, and 3 K, respectively. Large hysteresis can be found in Dy2Co2Al. The M(H) curves for Dy2Ni2Al and Tm2Ni2Al show linearly above and below TN, indicating a weak MCE. Fig. 13 (a-f) illustrate the -∆SM(T) curves of RE2TM2Al compounds, which are evaluated based on Eq. (1). We can see that the -∆SMmax for all RE2TM2Al occur near TC or TN. Two peaks (or one peak with a pronounced shoulder) in the -∆SM(T) curves near TC and TSR can be found for Ho2Co2Al. Moreover, negative -∆SM values can be observed for Er2Ni2Al and Ho2Ni2Al, which is the typical feature for materials with AFM ordering. The values of -∆SMmax under ∆H of 0-5 T are 10.4, 11.5, 6.0, 5.9, 6.2 and 7.7 J/kg K for Dy2Co2Al, Ho2Co2Al, Ho2Ni2Al, Er2Co2Al, Er2Ni2Al and Tm2Co2Al, respectively, and the corresponding RCP(RC) values are 279(194), 14 / 57

580(410), 151(122), 152(120), 362(280) and 127(100) J/kg [164]. 3.4. Ternary RE4TMX (RE = Ho, Er and Tm; TM = Co, Pd, and Pt; X = Mg and Cd) compounds The ternary RE-rich RE4TMX compounds crystallize in the cubic Gd4RhIn-type crystal structure. Up to the present, plenty of the RE4TMX type compounds have been successfully synthesized [169-179]. The striking structural motifs of the RE4TMX structure are TM-centered trigonal prisms formed by the RE atoms. These prisms are condensed with the hierarchical motif of the adamantane structure and voids are filled by X4 tetrahedra. The RE atoms occupy three different sites of 24g, 24f and 16e, and TM and X atoms locate in the same sites of 16e. The magnetocaloric performances in RE4PtMg (RE = Er and Ho) and RE4PdMg (RE = Er and Eu) have been investigated, and considerable reversible MCEs together with large RCP(RC) values were found [173-175]. The compounds undergo a PM to FM transition at TC of 21.5, 28, 150, and 16 K for Er4PtMg, Ho4PtMg, Eu4PdMg, and Er4PdMg, respectively. The corresponding values of -∆SMmax under ∆H of 0-7 T are 20.6, 16.9, 7.2, and 22.5 J/kg K [173-175]. Moreover, the MCE for Eu4PdMg shows a table-like performance over a quite wide temperature range which is quite benefit for active MR applications [173]. The MCE parameters (−∆SMmax, RC and RCP) under ∆H of 0-5 T together with the magnetic transition temperature (TM) for the RE4TMX compounds are illustrated in Table 5. Fig. 14 (a) and (b) illustrate the temperature dependence of 1/χ (right-scale) and Μ (left-scale) (H = 1 T) for RE4CoCd (RE = Tm and Ho) compounds, respectively, the corresponding M(T) curves measured in the ZFC and FC modes (H = 0.1 T) are illustrated in the inset of Fig. 14. The 1/χ-T curves for both compounds obey the Curie-Weiss law at high temperatures. Both compounds undergo a PM to FM transition at TC of ~22 and ~4.5 K for Ho4CoCd and Tm4CoCd, respectively [128]. The -∆SM(T) curves for Ho4CoCd and Tm4CoCd compounds which was calculated based on the measured M (H, T) data by using Eq. (1) are illustrated in Fig. 15 (a) and (b), respectively. The

15 / 57

values of -∆SMmax under ∆H of 0-7 T are 18.1 and 19.2 J/kg K for Ho4CoCd and Tm4CoCd, respectively, the corresponding RCP(RC) values are 278(211) and 400(298) J/kg [128]. The considerable ∆SM together with the large values of RCP(RC) make Tm4CoCd and Ho4CoCd are considerable for cryogenic MR. Moreover, the large MCE for Tm4CoCd is found around the boiling point of Helium point (4.2 K), which would find some application for Helium liquefaction. Thus, we have also synthesized the Tm4PtMg and Tm4PdMg compounds and studied their magnetic properties and magnetocaloric performance [176]. The M(T) curves (H = 0.05 and 0.2 T) measured in the FC and ZFC modes under for Tm4PdMg and Tm4PtMg are illustrated in Fig. 16 (a) and (b), respectively. As expected, both compounds undergo a FM to PM transition with a quite low TC of 6 and 4.5 K for Tm4PdMg and Tm4PtMg, respectively [176]. The -∆SM(T) for Tm4PdMg and Tm4PtMg compounds which was calculated from the measured M (H, T) data by using Eq. (1) are illustrated in Fig. 17 (a) and (b), respectively. The values of -∆SMmax under ∆H of 0-7 T are 18.0 and 16.5 J/kg K for Tm4PdMg and Tm4PtMg, respectively, the corresponding RCP(RC) values are 414(319) and 353(275) J/kg [176]. 3.5. Quaternary RENi2B2C (RE = Dy, Ho, and Er) superconductors and RENiBC (RE = Tb, Dy, and Ho) compounds The quaternary RENi2B2C compounds crystallize in the tetragonal filled-LuNi2B2C-type crystal structure which is displayed with the alternating Ni2B2 and RE-C layers along the c-axis. The shape of NiB4 tetrahedrons is closely related to the radii of rare earth atoms. There are a large number of covalent bonds between Ni and B atoms or B and C atoms [179-188]. The RENi2B2C compounds are of great interest since the superconductivity (SC) coexists with the magnetic ordering (AFM) for RE = Dy, Ho, Er, and Tm [179-187]. We have investigated the magnetocaloric performance of the pure and doped RENi2B2C superconductors experimentally, some of them are found to exhibit considerable cryogenic MCEs which are related to a metamagnetic transition (field-induced) from

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AFM to FM or FIM state [183-187]. The RENi2B2C compounds are superconducting below critical temperature (Tc) of 6.4, 8.2, and 10.5 K, together with an AFM transition at TN around 10.5, 6.5 and 6 K for RE = Dy, Ho, and Er, respectively [185]. The values of -∆SMmax under ∆H of 0-5 T reach 17.6, 17.7 and 9.8 J/kg K for RE = Dy, Ho, and Er, and the corresponding values of ∆Tadmax are 9.7, 11, and 4.6 K, respectively. Moreover, a giant reversible MCE has been obtained in Dy site Tm substitution Dy0.9Tm0.1Ni2B2C superconductor [186]. The values of TN and the -∆SM peak temperatures of Dy1-xHoxNi2B2C superconductors shift to lower temperature gradually with increasing x, and the -∆SMmax keeps at a large value, which are benefit for active application [187]. Very recently, Zhang et al have investigated the magnetic properties and MCE in RECo2B2C compounds. The values of -∆SMmax are determined to be 10.3, 18.1 and 17.8 J/kg K under ∆H of 0-5 T around their TC of 17.2, 5.3 and 7.7 K for RE = Gd, Tb and Dy, respectively [189]. The crystal structure of RENiBC compounds with the tetragonal LuNiBC-type (P4/nmm space group) is very close to the RENi2B2C compounds except for an additional RE-C plane between Ni2B2 layers [181]. No superconductivity can be found for the RENiBC compounds down to 2 K except for RE = Lu, and FM ordering can be observed below 20 K for all the heavy RE elementals [190-193]. The magnetism and magnetocaloric performances in GdNiBC and ErNiBC compounds were investigated. Both RENiBC undergo a FM to PM transition around TC of 15 and 5 K for RE = Gd and Er, respectively. Moreover, a table-like MCE from 4 to 20 K together with an enhanced RC are achieved in GdNiBC-ErNiBC composites [192]. The MCE parameters (-∆SMmax, RC and RCP) under ∆H of 0-5 T together with the magnetic transition temperature (TM) for RENi2B2C and RENiBC compounds are summarized in Table 6. Fig. 18 (a-c) illustrate the M(T) curves measured in the FC and ZFC modes under various H for TbNiBC, DyNiBC, and HoNiBC, respectively. A typical PM to FM transition occurs at TC ~ 14 and 16 K for TbNiBC and DyNiBC, respectively. Whereas, for HoNiBC, a PM to AFM transition occurs at TN ~ 10 K for H ≤ 0.3 T, whereas, a PM to FM or FIM

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transition happens for H > 0.3 T [193]. Fig. 19 (a-c) illustrate the -∆SM(T) which was calculated based on the measured M (H, T) data by using Eq. (1) for TbNiBC, DyNiBC, and HoNiBC compounds, respectively. The values of -∆SMmax under ∆H of 0-7 T are 24.1, 20.3, and 24.9 J/kg K and the values of ∆Tadmax are 13.2, 10.5, and 13.9 K for TbNiBC, DyNiBC, and HoNiBC, respectively, the corresponding RCP(RC) values are 730(568), 668(508), and 632(486) J/kg [193].

4. Summary In short, our recent progress of the investigation of the crystal structure, magnetic properties and magnetocaloric performances as well as their potential application for active cryogenic MR in binary RE-TM (RE = Nd, Ho, Er, and Tm; TM = Zn and Ga) compounds, ternary RETMX (RE = Tb, Dy, Ho, and Er; TM = Fe, Co, and Pt; X = Al, Mg, and C) compounds, ternary RE2TM2Al (RE =Dy, Ho, Er, and Tm; TM = Co and Ni, Cu) and RE2Ni2In (RE = Pr, Nd, Dy, and Ho) compounds, ternary RE4TMX (RE = Ho, Er and Tm; TM = Co, Pd, and Pt; X = Mg and Cd) compounds, as well as quaternary RENi2B2C (RE = Dy, Ho, and Er) superconductors and RENiBC (RE = Gd, Tb, Dy, Ho, and Er) compounds have been reviewed. Among of them, NdGa crystal displays promising low field MCE and RMCE, and TmZn compound shows a metamagnetic phase transition (field-induced) and a giant MCE is observed under low magnetic fields. Moreover, suitable hydrostatic pressure applied in TmZn compound can effectively regulate the phase transition temperature and magnetic entropy change value. The dual-phase Er40Zn60 alloy have large MCE parameters could be a promising candidate for cryogenic MR. The RE-rich RE4TMX compounds process large MCEs over a quite wide temperature span which is benefit for active MR applications. Table-like MCE from 4 to 20 K together with an enhanced RC are achieved in GdNiBC-ErNiBC composites. In addition, promising and comparable magnetocaloric parameters are also obtained in some of RE-TM-based intermetallic compounds. The present review could provide some valuable information for better understanding 18 / 57

the fundamental properties of RE-TM-based intermetallic compounds as well as for searching proper magnetic solids for active cryogenic MR application. Acknowledgments This work was supported by the Ten Thousand Talents Plan of Zhejiang Province (No. 2018R52003), the Fundamental Research Funds for the Provincial University of Zhejiang (No. GK199900X022), and the National Natural Science Foundation of China (Nos. 91963123, 51671048, 11374081, and 11004044).

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Table 1. The magnetic transition temperature(s) (TM) as well as the MCE parameters (−∆SMmax, RCP and RC) under ∆H of 0-5 T for REZn and REGa compounds (which will be shown below) together with some magnetic solids with promising cryogenic magnetocaloric performances. Materials

TM (K)

-∆SMmax (J/kg K)

RCP (J/kg)

RC (J/kg)

Ref.

HoZn

72/26

12.1

792

596

[115]

ErZn

20

19.1

397

302

[116]

TmZn

8.4

26.9

269

214

[117]

Er40Zn60

20/9

19.5

447

362

[120]

PrGa

37/27

10.7

187

~140

[122]

NdGa

42/20

15.5

563

~422

[123]

ErGa

30/15

21.3

682

~512

[124]

TmGa

15/12

34.2

530

~398

[125]

ErMn2Si2

~4.5

25.2

365

~274

[126]

HoAgGa

7.2

8.6

352

~264

[127]

Er4CoCd

12.5

20.4

503

392

[177]

Er3Ni2

17/12

19.5

448

~336

[129]

HoPdIn

23/6

14.6

496

~374

[130]

GdCo2B2

25

17.1

462

~347

[131]

31 / 57

Table 2. The maximum ∆SR (∆SRmax) values for NdGa crystal together with some large RMCE materials under various TM and ∆H. Materials

TM (K)

∆H (T)

∆SRmax (J/kg K)

Ref.

TmMnO3

16

5

5

[132]

TbMnO3

9

2

~2.4

[133]

TbMnO3

9

7

~8.2

[133]

DyMnO3

8

3

8.4

[134]

DyMnO3

8

7

16.3

[134]

HoMn2O5

43.5/39

7

12.43

[135]

TbMn2O5

36/5

7

13.14

[136]

TmFeO3

17

5

9.01

[137]

TbFeO3

9

5

17.4

[137]

KEr(MoO4)2

10

2

10

[138]

KEr(MoO4)2

10

5

13

[138]

NdGa

42/23

2

10.1

[139]

NdGa

42/23

7

16.6

[139]

32 / 57

Table 3. The magnetic transition temperature(s) (TM) as well as the MCE parameters (−∆SMmax, RCP and RC) under ∆H of 0-5 T for present REFeAl, RECo0.5Al1.5, RECoC, RECoC2 and REPtMg compounds. Materials

TM (K)

-∆SMmax (J/kg K)

RCP (J/kg)

RC (J/kg)

Ref.

GdFeAl

259

3.3*

348*

~261*

[144]

TbFeAl

196

2.6 *

350*

~263*

[144]

DyFeAl

129

6.4

595

~446

[145]

HoFeAl

55/28

6.1

311

240

[146]

ErFeAl

80/38

7.5

563

435

[146]

GdCo0.5Al1.5

70

13.2

602

~452

[147]

TbCo0.5Al1.5

47

8.6

368

~276

[147]

DyCo0.5Al1.5

33

7.7

340

~255

[147]

HoCo0.5Al1.5

20

14.1

382

~287

[147]

TbCoC

22

16.5

470

363

[148]

ErCoC

10

18.7

371

289

[148]

GdCoC2

15

28.4

566

~425

[149]

HoCoC2

11

15.6

242

183

[150]

ErCoC2

14

17.2

375

~281

[150]

TbPtMg

58

5.1

192

~142

[151]

DyPtMg

29

7.2

220

~174

[151]

HoPtMg

20

10.2

283

~212

[151]

“*” means the values with the magnetic field change of 0-4 T.

33 / 57

Table 4. The magnetic transition temperature(s) (TM) as well as the MCE parameters (−∆SMmax, RCP and RC) under ∆H of 0-5 T for RE2TM2Al and RE2Ni2In compounds together with some other selected RE2TM2X compounds. Materials

TM (K)

-∆SMmax (J/kg K)

RCP (J/kg)

RC (J/kg)

Ref.

Pr2Ni2In

7.5

9.3

60

47

[163]

Nd2Ni2In

10.5

11.5

101

74

[163]

Dy2Ni2In

19

6.4

130

95

[163]

Ho2Ni2In

10.5/5.5

11.5

210

152

[163]

Dy2Co2Al

62/41

10.4

279

194

[164]

Ho2Co2Al

27/9

11.5

580

410

[164]

Er2Co2Al

32/21

5.9

152

120

[164]

Tm2Co2Al

11.5/7

7.7

127

100

[164]

Ho2Ni2Al

12/4

6.0

151

122

[164]

Er2Ni2Al

12.5/3

16.2

362

280

[164]

Dy2Cu2In

49.5/19.5

13.3

409

318

[165]

Ho2Cu2In

30

17.4

416

320

[166]

Ho2Cu2Cd

30/15

20.3

481

346

[167]

Ho2Co2Ga

38.5

11.7

271

202

[168]

Er2Co2Ga

25.5

9.6

223

162

[168]

34 / 57

Table 5. The MCE parameters (−∆SMmax, RCP and RC) under ∆H of 0-5 T together with the magnetic transition temperature(s) (TM) for RE4TMX compounds. Materials

TM (K)

-∆SMmax (J/kg K)

RCP (J/kg)

RC (J/kg)

Ref.

Eu4PdMg

150

5.5

977

832

[173]

Er4PdMg

21.5

15.5

457

~343

[174]

Ho4PtMg

28

13.4

527

411

[175]

Er4PtMg

16

17.9

483

389

[175]

Tm4PdMg

6

14.9

287

229

[176]

Tm4PtMg

4.5

13.7

225

174

[176]

Ho4CoCd

22

14.3

541

427

[128]

Er4CoCd

12.5

20.4

503

392

[177]

Tm4CoCd

4.5

15.8

345

251

[128]

Er4NiCd

5.9

18.3

595

476

[178]

35 / 57

Table 6. The MCE parameters (−∆SMmax, RCP and RC) under ∆H of 0-5 T together with the magnetic transition temperature(s) (TM) and superconductivity transition temperature (Ts) for RENi2B2C and RENiBC compounds. Materials

Ts (K)

TM

-∆SMmax (J/kg

RCP

RC

(K)

K)

(J/kg)

(J/kg)

Ref.

DyNi2B2C

6.4

10.5

17.6

290

~218

[185]

Dy0.9Tm0.1Ni2B2C

4.5

9.2

14.7

306

~230

[186]

Dy0.5Ho0.5Ni2B2C

6.2

8

18.5

275

~207

[187]

HoNi2B2C

8.2

6.5

17.7

283

~212

[185]

ErNi2B2C

10.5

6

9.8

129

~97

[185]

TbNi2B2C

-

15/6

7.3

171

128

[188]

GdCo2B2C

-

17.2

10.3

238

191

[189]

TbCo2B2C

-

5.3

18.1

438

342

[189]

HoCo2B2C

-

7.7

17.8

480

365

[189]

GdNiBC

-

15

19.8

474

~356

[192]

TbNiBC

-

14

20.8

499

~374

[193]

DyNiBC

-

16

17.4

465

~349

[193]

HoNiBC

-

10

21.5

424

~318

[193]

ErNiBC

-

5

24.8

416

312

[192]

“-” means no superconductivity transition can be found.

36 / 57

Figure captions Fig. 1. Temperature dependence of M measured in both ZFC and FC modes with H of 0.1 T for TmZn compound under various hydrostatic pressures. The figure/data is taken from Ref. [117, 118]. Fig. 2. Temperature dependence of -∆SM for TmZn compound under various pressures of (a) 0 GPa, (b) 0.60 GPa and (c) 1.40 GPa, respectively. The figure/data is taken from Ref. [117]. Fig. 3. Temperature dependence of M (left-scale) and dMFC/dT (right-scale) for Er40Zn60 alloy under H of 1 T. Inset: The M(T) curves measured in the ZFC and FC modes under H of 0.1 T. The figure/data is taken from Ref. [120]. Fig. 4. (a): The M(H) curves for Er40Zn60 alloy at some selected temperatures. (b): The -∆SM(T) for Er40Zn60 alloy under ∆H of 0-2, 0-5, and 0-7 T. The figure/data is taken from Ref. [120]. Fig. 5. Temperature dependence of susceptibility χ (left-scale) and the reciprocal susceptibility 1/χ (right-scale) for NdGa single crystal under H of 1 T along the easy direction (c-axis), intermediate direction (a-axis) and hard direction (b-axis). The figure/data is taken from Ref. [139]. Fig. 6. (a), (b) and (c) for the -∆SM(T) of NdGa single crystal along the a, b, and c axes, respectively. The figure/data is taken from Ref. [139]. Fig. 7. (a): The -∆SM(T) curves under ∆H of 0-7 T for NdGa single crystal along a , b, and c axes. (b): Temperature dependence of ∆SR, cb for NdGa single crystal). The figure/data is taken from Ref. [139]. Fig. 8. Temperature dependence of Μ (left-scale) and 1/χ (right-scale) under H of 1 T for (a) TbCoC and (b) ErCoC compounds. Insets: The M(T) curves measured in the ZFC and FC modes under H of 0.1 T for TbCoC and ErCoC compounds. The figure/data is taken from Ref. [148]. Fig. 9. The -∆SM(T) for (a) TbCoC and (b) ErCoC compounds. The figure/data is taken from Ref. [148]. Fig. 10. Temperature dependence of Μ (left-scale) and 1/χ (right-scale) under H of 1 T for (a) TbPtMg, (b) DyPtMg, and (c) HoPtMg compounds. Insets: The M(T) curves for (a) TbPtMg, (b) DyPtMg, and (c) HoPtMg compounds measured in the ZFC and FC modes under H of 0.2 T. The figure/data is taken from Ref. [151]. 37 / 57

Fig. 11. The -∆SM(T) for (a) TbPtMg, (b) DyPtMg, and (c) HoPtMg compounds. The figure/data is taken from Ref. [151]. Fig. 12. The M(T) curves under H of 0.2 T for (a) Dy2Co2Al, (b) Ho2Co2Al, (c) Er2Co2Al, (d) Tm2Co2Al, (e) Dy2Ni2Al, (f) Ho2Ni2Al, (g) Er2Ni2Al and (h) Tm2Ni2Al compounds, respectively. Insets: The M(T) curves measured under H of 1 T for Dy2Co2Al, Ho2Co2Al, Er2Co2Al, Tm2Co2Al, Dy2Ni2Al, Ho2Ni2Al, Er2Ni2Al and Tm2Ni2Al compounds. The figure/data is taken from Ref. [164]. Fig. 13. The -∆SM(T) curves for (a) Dy2Co2Al, (b) Ho2Co2Al, (c) Er2Co2Al, (d) Tm2Co2Al, (e) Ho2Ni2Al, and (f) Er2Ni2Al compounds, respectively. The figure/data is taken from Ref. [164]. Fig. 14. Temperature dependence of Μ (left-scale) and 1/χ (right-scale) under H of 1 T for (a) Ho4CoCd and (b) Tm4CoCd compounds, respectively. Insets: The M(T) curves measured in the ZFC and FC modes under H of 0.1 T for Ho4CoCd and (b) Tm4CoCd compounds. The figure/data is taken from Ref. [128]. Fig. 15. The -∆SM(T) for (a) Ho4CoCd and (b) Tm4CoCd compounds, respectively. The figure/data is taken from Ref. [128]. Fig. 16. The M(T) curves measured in the ZFC and FC modes for Tm4PdMg and Tm4PtMg compounds under H of (a) 0.05T and (b) 0.2 T, respectively. The figure/data is taken from Ref. [176]. Fig. 17. The -∆SM(T) for Tm4PdMg and Tm4PtMg compounds. The figure/data is taken from Ref. [176]. Fig. 18. The M(T) curves measured in the ZFC and FC modes for (a) TbNiBC, (b) DyNiBC and (b) HoNiBC compounds, respectively. The figure/data is taken from Ref. [193]. Fig. 19. The -∆SM(T) for (a) TbNiBC, (b) DyNiBC and (b) HoNiBC compounds, respectively. The figure/data is taken from Ref. [193].

38 / 57

Fig. 1

39 / 57

Fig. 2

40 / 57

Fig. 3

41 / 57

Fig. 4

42 / 57

Fig. 5

43 / 57

Fig. 6

44 / 57

Fig. 7

45 / 57

Fig. 8

46 / 57

Fig. 9

47 / 57

Fig. 10

48 / 57

Fig. 11

49 / 57

Fig. 12

50 / 57

Fig. 13

51 / 57

Fig. 14

52 / 57

Fig. 15

53 / 57

Fig. 16

54 / 57

Fig. 17

55 / 57

Fig. 18

56 / 57

Fig. 19

57 / 57

Research Highlights

Our recent progress related to MCE in RE-based intermetallic is reviewed Structural, magnetic and magnetocaloric properties are summarized Some of them exhibit promising cryogenic magnetocaloric performances Some of them are considerable for cryogenic magnetic refrigeration

Recent progresses in exploring magnetocaloric materials for cryogenic magnetic refrigeration Lingwei Li a, b and Mi Yan a, c a b

Institute of Advanced Magnetic Materials, Hangzhou Dianzi University, Hangzhou 310012, P. R. China

Key Laboratory of Electromagnetic Processing of Materials (Ministry of Education), Northeastern University, Shenyang 110819, P. R. China c

School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China

Declaration of interest The authors declare no conflict of interest.