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

The magnetic properties and magnetocaloric effects （MCE） of HoNiGa compound are investigated systematically. The HoNiGa exhibits a weak antiferromagnetic （AFM） ground state below the Neel temperature TN of 10 K, and the AFM ordering could be converted into ferromagnetic （FM） ordering by external magnetic field. Moreover, the fie/d-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 -△SM 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 μ0H2/3 dependence of ｜△SPKM｜ 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 HoNiGa compound could be a promising material for magnetic refrigeration in low temperature range.

Giant Volume Magnetostriction Caused by Itinerant Electron Metamagnetic Transition and Pronounced Invar Effects in La(Fe_xSi_(1-x))_(13) Compounds

A first-order itinerant electron metamagnetic (IEM) transition above the Curie temperature Tc for ferromagnetic La(Fe_xSi_1-x)13 compounds has been confirmed by applying magnetic field. The volume change just above T_C for x=0.88 is huge of about 1.5%, which is caused by a large magnetic moment induced by the IEM transition. These compounds have a possibility for practical applications as giant magnetostrictive materials. Pronounced Invar effects bring about a negative thermal expansion below TC, closely correlated with the negative mode-mode coupling among spin fluctuations.

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

HoBi single crystal and polycrystalline compounds with Na Cl-type structure are successfully obtained,and their magnetic and magnetocaloric properties are studied in detail.With temperature increasing,Ho Bi compound undergoes two magnetic transitions at 3.7 K and 6 K,respectively.The transition temperature at 6 K is recognized as an antiferromagneticto-paramagnetic(AFM–PM)transition,which belongs to the first-order magnetic phase transition(FOMT).It is interesting that the Ho Bi compound with FOMT exhibits good thermal and magnetic reversibility.Furthermore,a large inverse and normal magnetocaloric effect(MCE)is found in Ho Bi single crystal in the H||[100]direction,and the positive?SMpeak reaches 13.1 J/kg·K under a low field change of 2 T and the negative?S_(M)peak arrives at-18 J/kg·K under a field change of5 T.These excellent properties are expected to be applied to some magnetic refrigerators with special designs and functions.

Magnetic transition and large reversible magnetocaloric effect in EuCu_(1.75)P_2 compound

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

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 MnNil_χFexGe alloy. Owing to the enhanced ferromagnetic coupling induced by the substitution of Fe, metamagnetic behaviour is also observed in TiNiSi-type phase of MnNil-xFezGe alloys at temperature below the structural transition temperature.

Order of magnetic transition and large magnetocaloric effect in Er_3Co

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 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.

Magnetic properties and magnetocaloric effects in NaZn_(13)-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 LaFe13 -xAlx can be converted to an FM one by substituting Si for A1, 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 LaFel 1.5All.5Co.2Hl.o 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.

Magnetic properties and magnetocaloric effects in(Ho_(1-x)Y_x)_5Pd_2 compounds

The crystal structure, magnetic and magnetocaloric properties of(Ho_(1-x) Y_(0.5))_5 Pd_2 compounds are investigated. All the compounds crystallize in a cubic Dy_5 Pd_2-type structure with the space group Fd3 m and undergo a second order transition from spin glass(SG) state to paramagnetic(PM) state. The spin glass transition temperatures T_g decrease from 26 K for x = 0 to 13 K for x = 0.5. In the PM region, the reciprocal susceptibilities for all the compounds obey the Curie–Weiss law. The paramagnetic Curie temperatures(θp) for Ho_5 Pd_2,(Ho_(0.75) Y_(0.25)_5 Pd_2, and(Ho_(0.5) Y_(0.5))_5 Pd_2 are determined to be 32 K, 30 K, and 22 K, respectively, and the corresponding effective magnetic moments(μeff) are10.8 μB/Ho, 10.3 μB/RE, and 7.5 μB/RE, respectively. Magnetocaloric effect(MCE) is anticipated according to the Maxwell relation, based on the isothermal magnetization curves. For a magnetic field change of 0–5 T, the maximum values of the isothermal magnetic entropy change-?SMof the(Ho_(1-x)Y_x)_5 Pd_2(x = 0, 0.25, and 0.5) compounds are determined to be 11.5 J·kg^(-1)·K^(-1), 11.1 J·kg^(-1)·K^(-1), and 8.9 K J·kg^(-1)·K^(-1), with corresponding refrigerant capacity values of 382.3 J·kg^(-1), 336.2 J·kg^(-1), and 242.5 J·kg^(-1), respectively.

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.

Itinerant-electron metamagnetic transition and giant magnetic entropy change in La_(0.8)Ce_(0.2)Fe_(11.4)Si_(1.6) compound

The crystal structure, itinerant-electron metamagnetic transition (IEMT) and magnetocaloric effect (MCE) in the iron-based rare-earth intermetallic compound La0.8Ce0.2Fe11.4Si1.6 have been investi- gated. The powder X-ray diffraction revealed that the ingot of La0.8Ce0.2Fe11.4Si1.6 annealed at 1373 K in vacuum for only 5 days could be crystallized in the cubic NaZn13-type structure. The La0.8Ce0.2Fe11.4Si1.6 compound exhibited giant values of the isothermal entropy change ?SM around the Curie temperature TC (about 186 K). And the maximum value ΔS M max is about 78.29 J/(kg·K) under a field change of 0—3 T, which can be calculated by the magnetization iso- therms around TC. Such a large MCE is attributed to the sharp change of magnetization and susceptibility around TC and the first-order magnetic transition of field-induced IEMT above TC.

Large magnetocaloric effect in metamagnetic HoPdAl

Magnetic properties and magnetocaloric effects （MCEs） of the HoPdA1 compounds with the hexagonal ZrNiAl-type and the orthorhombic TiNiSi-type structures are investigated. Both the compounds are found to be antiferromagnet with the Nrel tem- perature TN=12 and 10 K, respectively. A field-induced metamagnetic transition from antiferromagnetic （AFM） state to ferro- magnetic （FM） state is observed below TN. For the hexagonal HoPdA1, a small magnetic field can induce an FM-like state due to a weak AFM coupling, which leads to a high saturation magnetization and gives rise to a large MCE around TN. The maxi- mal value of magnetic entropy change （ASM） is -20.6 J/kg K with a refrigerant capacity （RC） value of 386 J/kg for a field change of 0-5 T. For the orthorhombic HoPdA1, the critical field required for metamagnetic transition is estimated to be about 1.5 T, showing a strong AFM coupling. However, the maximal ASM value is still -13.7 J/kg K around TN for a field change of 0-5 T. The large reversible ASM and considerable RC suggest that HoPdA1 may be an appropriate candidate for magnetic re- frigerant in a low temperature range.

Magnetocaloric effects in RT X intermetallic compounds(R = Gd–Tm, T = Fe–Cu and Pd, X = Al and Si)

The magnetocaloric effect（MCE） of RT Si and RT Al systems with R = Gd–Tm, T = Fe–Cu and Pd, which have been widely investigated in recent years, is reviewed. It is found that these RT X compounds exhibit various crystal structures and magnetic properties, which then result in different MCE. Large MCE has been observed not only in the typical ferromagnetic materials but also in the antiferromagnetic materials. The magnetic properties have been studied in detail to discuss the physical mechanism of large MCE in RT X compounds. Particularly, some RT X compounds such as Er Fe Si,Ho Cu Si, Ho Cu Al exhibit large reversible MCE under low magnetic field change, which suggests that these compounds could be promising materials for magnetic refrigeration in a low temperature range.

Large reversible cryogenic magnetocaloric effect in rare earth iron carbides of composition RE_(2)FeC_(4)(RE=Ho,Er,and Tm)

At cryogenic temperatures,the investigations of magnetic phase transition and magnetocaloric effect in RE_(2)FeC_(4)(RE=Ho,Er,and Tm) compounds were performed.Ho_(2)FeC_(4)and Er_(2)FeC_(4)compounds undergo two magnetic phase transitions with the temperature decreasing:from paramagnetic(PM) to ferromagnetic(FM) transition at their respective Curie temperature(Tc) and from FM to antiferromagnetic(AFM) or ferrimagnetic(FIM) transition below 2 K.Tm_(2)FeC_(4)compound exhibits only a second-order PM to FM phase transition at TC=K.Large reversible MCE without hysteresis loss is observed in RE_(2)FeC_(4)(RE=Ho,Er,and Tm) compounds.Particularly,the maximum value of magnetic entropy change(-ASM)is 21.62 J/(kg K) under the magnetic field change(Δ_(μ0)H) of 0-5 T for Er_(2)FeC_(4).The Er_(2)FeC_(4)compound presenting excellent magnetocaloric performance makes it a competitive cryogenic magnetic refrigeration material.

Observation of table-like magnetocaloric effect and large refrigerant capacity in Nd_(6)Fe_(13)Pd_(1-x)Cu_(x) compounds

The table-like magnetocaloric effect is significant for the magnetic refrigeration applications above 20 K based on the Ericsson cycle.Herein,we prepared a series of Nd_(6)Fe_(13)Pd_(1-x)Cu_(x)(x=0.05,0.1,0.15)compounds by the arc-melting method.These compounds show the single crystalline phase in the tetragonal Nd_(6)Fe_(13)Si-type structure with the space group I4/mcm.A magnetic phase transition from ferromagnetism to antiferromagnetism and a metamagnetic transition from the antiferromagnetic state to the ferromagnetic state are observed in each of the compounds.The compounds exhibit table-like magnetocaloric effects with large refrigerant capacities.A constantΔSM in a temperature span of 40 K in the Nd_(6)Fe_(13)Pd_(0.85)Cu_(0.15) compound are observed.For a field change of 0–5 T,the peak values of–ΔS_(M) for the Nd_(6)Fe_(13)Pd_(0.95)Cu_(0.05),Nd_(6)Fe_(13)Pd_(0.90)Cu_(0.10),and Nd_(6)Fe_(13)Pd_(0.85)Cu_(0.15) compounds are estimated to be 4.8,4.6 and 4.4 J/(kg·K)with corresponding refrigerant capacity values of 323,331 and 316 J/kg,respectively.The obtained table-like magnetocaloric effects with large refrigerant capacities as well as fairly small thermal and magnetic hysteresis deem these series of compounds good candidates for single-phase magnetic refrigeration based on the Ericsson cycle.

Magnetocaloric effect in ErCo2 compound

The ErCo2 compound is prepared by arc-melting and its entropy changes are calculated using Maxwell relation. Its entropy change reaches 38 J/（kg·K） and its refrigerant capacity achieves 291 J/kg at 0-5 T. The mean field approximation is used to calculate the magnetic entropy of ErCo2 compound. Results estimated by using the Maxwell relation deviate from mean field approximation calculations in ferrimagnetic state; however, the data obtained by the two ways are consistent in the vicinity of phase transition or at higher temperatures. This indicates that entropy changes are mainly derived from magnetic degree of freedom, and the lattice has almost no contribution to the entropy change in the vicinity of phase transition but its influence is obvious in the ferrimagnetic state below TC.

Influences of P doping on magnetic phase transition and structure in MnCoSi ribbon

The structure and magnetic properties of MnCoSil_xPx （x = 0.054）.50） are systematically investigated. With P content increasing, the lattice parameter a increases monotonically while both b and c decrease. At the same time, the temperature of metamagnetic transition from a low-temperature non-collinear ferromagnetic state to a high-temperature ferromagnetic state decreases and a new magnetic transition from a higher-magnetization ferromagnetic state to a lower- magnetization ferromagnetic state is observed in each of these compounds for the first time. This is explained by the changes of crystal structure and distance between Mn and Si atoms with the increase of temperature according to the high- temperature XRD result. The metamagnetic transition is found to be a second-order magnetic transition accompanied by a low inversed magnetocaloric effect （1.0 J·kg-1 ·K- 1 at 5 T） with a large temperature span （190 K at 5 T） compared with the scenario of MnCoSi. The changes in the order of metamagnetic transition and structure make P-doped MoCoSi compounds good candidates for the study of magnetoelastic coupling and the modulation of magnetic phase transition.

Magnetic phase transition and continuous spin switching in a high-entropy orthoferrite single crystal

Rare-earth orthoferrite REFeO_(3)(where RE is a rare-earth ion)is gaining interest.We created a high-entropy orthoferrite(Tm_(0.2)Nd_(0.2)Dy_(0.2)Y_(0.2)Yb_(0.2))FeO_(3)(HEOR)by doping five RE ions in equimolar ratios and grew the single crystal by optical floating zone method.It strongly tends to form a single-phase structure stabilized by high configurational entropy.In the low-temperature region(11.6‒14.4 K),the spin reorientation transition(SRT)ofΓ_(2)(F_(x),C_(y),G_(z))‒Γ_(24)‒Γ_(4)(G_(x),A_(y),F_(z))occurs.The weak ferromagnetic(FM)moment,which comes from the Fe sublattices distortion,rotates from the a-to c-axis.The two-step dynamic processes(Γ_(2)‒Γ_(24)‒Γ_(4))are identified by AC susceptibility measurements.SRT in HEOR can be tuned in the range of 50‒60000 Oe,which is an order of magnitude larger than that of orthoferrites in the peer system,making it a candidate for high-field spin sensing.Typical spin-switching(SSW)and continuous spin-switching(CSSW)effects occur under low magnetic fields due to the strong interactions between RE‒Fe sublattices.The CSSW effect is tunable between 20‒50 Oe,and hence,HEOR potentially can be applied to spin modulation devices.Furthermore,because of the strong anisotropy of magnetic entropy change()and refrigeration capacity(RC)based on its high configurational entropy,HEOR is expected to provide a novel approach for refrigeration by altering the orientations of the crystallographic axes(anisotropic configurational entropy).

Effects of magnetic field and hydrostatic pressure on the antiferromagnetic-ferromagnetic transition and magneto-functional properties in Hf_(1-x)Ta_(x)Fe_(2)alloys

In this study,the thermal expansion of Hf_(1-x)Ta_(x)Fe_(2)(x=0.10,0.13,0.15)compounds by adjusting the Ta concentration was successfully regulated.The magnetocaloric properties,hydrostatic pressure affecting the antiferromagnetic-ferromagnetic transition,and magnetostriction in the low magnetic field were studied.TheΔS_(M)values of 3.3 J·(kg-K)^(-1)and 3.6 J·(kg·K)^(-1)were obtained under magnetic fields of 10 kOe and 15 kOe in the Hf_(0.85)Ta_(0.15)Fe_(2),respectively.In the antiferromagnetic-ferromagnetic state transformation process under hydrostatic pressure up to 0.8 GPa,the state temperature does not decrease in a strictly linear manner.Outstanding magnetostrictive properties of 0.12%were obtained at a magnetic field of 10 kOe.This kind of alloy is supposed to be controlled under hydrostatic pressure to obtain good magnetic refrigeration performance and magnetostrictive properties.

First-and second-order phase transitions in RE_(6)Co_(2)Ga(RE=Ho,Dy or Gd)cryogenic magnetocaloric materials

Rare-earth(RE)rich intermetallics crystallizing in orthorhombic Ho_(6)Co_(2)Ga-type crystal structure exhibit peculiar magnetic properties that are not widely reported for their magnetic ordering,order of magnetic phase transition,and related magnetocaloric behavior.By tuning the type of RE element in RE_(6)Co_(2)Ga(RE=Ho,Dy or Gd)compounds,metamagnetic anti-to-paramagnetic(AF to PM)phase transitions could be tuned to ferro-to-paramagnetic(FM to PM)phase transitions.Furthermore,the FM ground state for Gd_(6)Co_(2)Ga is confirmed by density functional theory calculations in addition to experimental observations.The field dependence magnetocaloric and Banerjee’s criteria demonstrate that Ho_(6)Co_(2)Ga and Dy_(6)Co_(2)Ga undergo a first-order phase transition in addition to a second-order phase transition,whereas only the latter is observed for Gd_(6)Co_(2)Ga.The two extreme alloys of the series,Ho_(6)Co_(2)Ga and Gd_(6)Co_(2)Ga,show maximum isothermal entropy change(|ΔS_(iso)^(max)(5T)|)of 10.1 and 9.1 J kg^(-1)K^(-1)at 26 and 75 K,close to H_(2)and N_(2)liquefaction,respectively.This outstanding magnetocaloric effect performance makes the RE6 Co_(2)Ga series of potential for cryogenic magnetic refrigeration applications.