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.     

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.     

Phase transitions and magnetocaloric effects in intermetallic compounds MnFeX（X=P,As,Si,Ge）

Since the discovery of giant magnetocaloric effect in MnFeP1-x As x compounds,much valuable work has been performed to develop and improve Fe2P-type transition-metal-based magnetic refrigerants.In this article,the recent progress of our studies on fundamental aspects of theoretical considerations and experimental techniques,effects of atomic substitution on the magnetism and magnetocalorics of Fe2P-type intermetallic compounds MnFeX(X=P,As,Ge,Si) is reviewed.Substituting Si(or Ge) for As leads to an As-free new magnetic material MnFeP1-xSi(Ge)x.These new materials show large magnetocaloric effects resembling MnFe(P,As) near room temperature.Some new physical phenomena,such as huge thermal hysteresis and ’virgin’ effect,were found in new materials.On the basis of Landau theory,a theoretical model was developed for studying the mechanism of phase transition in these materials.Our studies reveal that MnFe(P,Si) compound is a very promising material for room-temperature magnetic refrigeration and thermo-magnetic power generation.     

Anisotropy Properties of Mn_2P Single Crystals with Antiferromagnetic Transition

Single crystals of hexagonal structure Mn_2P are synthesized by Sn flux for the first time. Transport and magnetic properties have been performed on the single crystals, which is an antiferromagnet with Neel temperature 103 K.Obvious anisotropy of resistivity is observed below the Neel temperature, which is manifested by metallic behavior with a current along the C-axis and semiconducting behavior with a current along the α-axis. The negative slope of temperature-dependent resistivity is observed above the Neel temperature in both α and C directions. Strong anisotropy of magnetic susceptibility is also evident from the magnetization measurements. A weak metamagnetic transition is observed only in α-axis plane at high magnetic field near 50–60 K compared to the C-axis. We believe these strong anisotropies of magnetic and transport properties are due to the anisotropy of spin arrangement.Mn_2P could be a candidate for exploration of possible superconductivity due to the low spin state.     

Magnetic properties and magnetocaloric effects of Mn5Ge3-xGax

We report on the magnetic properties and magnetocaloric effects of Mn5Ge3-xGax compounds with x=0.1,0.2,0.3,0.4,0.6 and 0.9. All samples crystallize in the hexagonal Mn5Si3-type structure with space group P63/mcm and order ferromagnetically.The Curie temperature of these compounds decreases with increasing x, from 306K (x=0.1) to 274K (x=0.9).The average Mn magnetic moments increases with increasing Ga content,reaching a maximum value at x=0.6.The magnetic entropy changes in these compounds are determined from the temperature and field dependence of the magnetization using the thermodynamic Maxwell relation.The Ga substitution has two kinds of influence on the magnetocaloric effect (MCE) of Mn5Ge3.One is that the magnitude of the magnetic entropy change decreases,the other is that the MCE peak becomes broadened.     

The magnetic properties and magnetocaloric effects in binary R-T(R = Pr,Gd,Tb,Dy,Ho,Er,Tm;T = Ga,Ni,Co,Cu)intermetallic compounds

In this paper, we review the magnetic properties and magnetocaloric effects(MCE) of binary R–T(R = Pr, Gd, Tb,Dy, Ho, Er, Tm; T = Ga, Ni, Co, Cu) intermetallic compounds(including RGa series, RNi series, R_(12)Co_7 series, R_3 Co series and RCu_2series), which have been investigated in detail in the past several years. The R–T compounds are studied by means of magnetic measurements, heat capacity measurements, magnetoresistance measurements and neutron powder diffraction measurements. The R–T compounds show complex magnetic transitions and interesting magnetic properties.The types of magnetic transitions are investigated and confirmed in detail by multiple approaches. Especially, most of the R–T compounds undergo more than one magnetic transition, which has significant impact on the magnetocaloric effect of R–T compounds. The MCE of R–T compounds are calculated by different ways and the special shapes of MCE peaks for different compounds are investigated and discussed in detail. To improve the MCE performance of R–T compounds,atoms with large spin(S) and atoms with large total angular momentum(J) are introduced to substitute the related rare earth atoms. With the atom substitution, the maximum of magnetic entropy change(?SM), refrigerant temperature width(Twidth)or refrigerant capacity(RC) is enlarged for some R–T compounds. In the low temperature range, binary R–T(R = Pr, Gd,Tb, Dy, Ho, Er, Tm; T = Ga, Ni, Co, Cu) intermetallic compounds(including RGa series, RNi series,R_(12)Co_7 series, R_3 Co series and RCu_2series) show excellent performance of MCE, indicating the potential application for gas liquefaction in the future.     

Order of magnetic transition and large magnetocaloric effect in Er3Co*

We have studied the magnetic and magnetocaloric properties of the Er3 Co 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 Er3 Co compound.The giant magnetocaloric effect(MCE) without hysteresis loss around T C is found to result from the second-order ferromagnetic-to-paramagnetic transition.The maximal 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 Er3 Co as a candidate magnetic refrigerant at low temperatures.     

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.     

Magnetic properties and magnetocaloric effects in NaZn13-type La（Fe, Al）13-based compounds

In this article,our recent progress concerning the effects of atomic substitution,magnetic field,and temperature on the magnetic and magnetocaloric properties of the LaFe13-xAlx compounds are reviewed.With an increase of the aluminum content,the compounds exhibit successively an antiferromagnetic(AFM) state,a ferromagnetic(FM) state,and a mictomagnetic state.Furthermore,the AFM coupling of LaFe 13-xAlx can be converted to an FM one by substituting Si for Al,Co for Fe,and magnetic rare-earth R for La,or introducing interstitial C or H atoms.However,low doping levels lead to FM clusters embedded in an AFM matrix,and the resultant compounds can undergo,under appropriate applied fields,first an AFM-FM and then an FM-AFM phase transition while heated,with significant magnetic relaxation in the vicinity of the transition temperature.The Curie temperature of LaFe13-xAlx can be shifted to room temperature by choosing appropriate contents of Co,C,or H,and a strong magnetocaloric effect can be obtained around the transition temperature.For example,for the LaFe 11.5Al1.5C0.2H1.0 compound,the maximal entropy change reaches 13.8 J·kg-1 ·K-1 for a field change of 0-5 T,occurring around room temperature.It is 42% higher than that of Gd,and therefore,this compound is a promising room-temperature magnetic refrigerant.     

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

The structure and magnetic properties of Mn Co Si1-xPx(x = 0.05–0.50) 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 lowermagnetization 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 hightemperature 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-1at 5 T) with a large temperature span(190 K at 5 T) compared with the scenario of Mn Co Si.The changes in the order of metamagnetic transition and structure make P-doped Mo Co Si compounds good candidates for the study of magnetoelastic coupling and the modulation of magnetic phase transition.     

Influences of La and Ce doping on giant magnetocaloric effect of EuTiO

Giant reversible magnetocaloric effects and magnetic properties in Eu_(0.9)R_(0.1)TiO_3 (R = La, Ce) are investigated. The antiferromagnetic ordering of pure Eu TiO_3 can significantly change to be ferromagnetic as substitution of La(x = 0.1)and Ce(x = 0.1) ions for Eu~(2+) ions. The values of-?S_M and RC are evaluated to be 10.8 J/(kg·K) and 51.8 J/kg for Eu_(0.9)Ce_(0.1)TiO_3 and 11 J/(kg·K) and 39.3 J/kg for Eu_(0.9)La_(0.1)TiO_3 at a magnetic field change of 10 kOe, respectively. The large low-field enhancements of-?S_M and RC can be attributed to magnetic phase transition. The giant reversible MCE and large RC suggest that Eu_(0.9)R_(0.1)TiO_3 (R = La, Ce) compounds could be promising materials in low temperature and low magnetic field refrigerants.     

Non—conservation of energy arising from atomic dipole interactions and its effects on light field and coupled atoms

The interactions between coupled atoms and a single mode of a quantized electromagnetic field, which involve the terms originating from the dipole interactions, are discussed. In the usual Jaynes－Cummings model for coupled atoms, the terms of non-conservation of energy originating from dipole interactions are neglected, however, we take them into consideration in this paper. The effects of these terms on the evolutions of quantum statistic properties and squeezing of the field, the squeezing of atomic dipole moments and atomic population inversion are investigated. It has been shown that the coupling between atoms modulates these evolutions of fields and atoms. The terms of non-conservation of energy affect these evolutions of fields and atoms slightly. They also have effects on the squeezing of the field, the squeezing of atomic dipole and atomic population inversions. The initial states of atoms also affect these properties.     

Magnetotransport properties and magnetocaloric effects of Mn1.95Cr0.05Sb0.95Ga0.05 compound

The magnetotransport properties and magnetocaloric effects of the compound Mn_{1.95}Cr_{0.05}Sb_{0.95}Ga_{0.05} have been studied. With decreasing temperature, a spontaneous first-order magnetic phase transition from ferrimagnetic (FI) to antiferromagnetic (AF) state takes place at T_s=200K. A metamagnetic transition from the AF to FI state can be induced by an external field, accompanied by a giant magnetoresistance effect of 57%. The magnetic entropy changes are determined from the temperature and field dependence of the magnetization using the thermodynamic Maxwell relation. Mn_{1.95}Cr_{0.05}Sb_{0.95}Ga_{0.05} exhibits a negative magnetocaloric effect, and the absolute values of ΔS_M^{max}(T,ΔH) are 4.4, 4.1, 3.6, 2.8 and 1.5 J/(kg·K) for magnetic field changes of 0－5T, 0－4T, 0－3T, 0－2T and 0－1T, respectively.     

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.     

Observation of giant magnetocaloric effect under low magnetic fields in EuTi_(1-x)Co_xO_3

The magnetic properties and magnetocaloric effect(MCE) in EuTi_(1-x)Co_xO_3(x = 0, 0.025, 0.05, 0.075, 0.1) compounds have been investigated. When the Ti~(4+) ions were substituted by Co2+ions, the delicate balance was changed between antiferromagnetic(AFM) and ferromagnetic(FM) phases in the EuTiO_3 compound. In EuTi_(1-x)Co_xO_3 system, a giant reversible MCE and large refrigerant capacity(RC) were observed without hysteresis. The values of -?S_M~(max) were evaluated to be around 10 J·kg~(-1)·K~(-1) for EuTi_(0.95)Co_(0.05)O_3 under a magnetic field change of 10 kOe. The giant reversible MCE and large RC suggests that EuTi_(1-x)Co_xO_3 series could be considered as good candidate materials for low-temperature and low-field magnetic refrigerant.     

Giant low-field magnetocaloric effect in EuTi(1-x)NbxO3(x = 0.05, 0.1, 0.15, and 0.2) compounds

The magnetic properties and magnetocaloric effect(MCE)of EuTi(1-x)NbxO3(x=0.05,0.1,0.15,and 0.2)compounds are investigated.Owing to electronic doping,parts of Ti ions are replaced by Nb ions,the lattice constant increases and a small number of Ti⁴⁺(3d^0)ions change into Ti³⁺(3d^1).It is the ferromagnetism state that is dominant in the derivative balance.The values of the maximum magnetic entropy change(-?SM^max)are 10.3 J/kg·K,9.6 J/kg·K,13.1 J/kg·K,and 11.9 J/kg·K for EuTi(1-x)NbxO3(x=0.05,0.1,0.15,and 0.2)compounds and the values of refrigeration capacity are 36,33,86,and 80 J/kg as magnetic field changes in a range of 0 T–1 T.The EuTi(1-x)NbxO3(x=0.05,0.1,0.15,and 0.2)compounds with giant reversible MCE are considered as a good candidate for magnetic refrigerant working at lowtemperature and low-field.     

Magnetic interactions in a proposed diluted magnetic semiconductor(Ba_(1-x)K_x)(Zn_(1-y)Mn_y)_2P_2

By using first-principles electronic structure calculations, we have studied the magnetic interactions in a proposed BaZn_2P_2-based diluted magnetic semiconductor(DMS). For a typical compound Ba(Zn_(0.944)Mn_(0.056))_2P_2 with only spin doping, due to the superexchange interaction between Mn atoms and the lack of itinerant carriers, the short-range antiferromagnetic coupling dominates. Partially substituting K atoms for Ba atoms, which introduces itinerant hole carriers into the p orbitals of P atoms so as to link distant Mn moments with the spin-polarized hole carriers via the p–d hybridization between P and Mn atoms, is very crucial for the appearance of ferromagnetism in the compound. Furthermore, applying hydrostatic pressure first enhances and then decreases the ferromagnetic coupling in(Ba0.75 K0.25)(Zn_(0.944)Mn_(0.056))_2P_2 at a turning point around 15 GPa, which results from the combined effects of the pressure-induced variations of electron delocalization and p–d hybridization. Compared with the BaZn_2 As_2-based DMS, the substitution of P for As can modulate the magnetic coupling effectively. Both the results for BaZn_2 P_2-based and BaZn_2As_2-based DMSs demonstrate that the robust antiferromagnetic(AFM) coupling between the nearest Mn–Mn pairs bridged by anions is harmful to improving the performance of these Ⅱ–Ⅱ–Ⅴ based DMS materials.     

Low field induced giant anisotropic magnetocaloric effect in DyFeO_3 single crystal

We have investigated the anisotropic magnetocaloric effect and the rotating field magnetic entropy in Dy FeO3 single crystal. A giant rotating field entropy change of -ΔS R M= 16.62 J/kg·K was achieved from b axis to c axis in bc plane at 5 K for a low field change of 20 k Oe. The large anisotropic magnetic entropy change is mainly accounted for the 4 f electron of rare-earth Dy3+ ion. The large value of rotating field entropy change, together with large refrigeration capacity and negligible hysteresis, suggests that the multiferroic ferrite Dy FeO3 singlecrystal could be a potential material for anisotropic magnetic refrigeration at low field, which can be realized in the practical application around liquid helium temperature region.     

Magnetocaloric effect in Gd6Co1.67Si3 compound with a second-order phase transition

The magnetic properties and the magnetic entropy change AS have been investigated for Gd6Co1.67Si3 compounds with a second-order phase transition. The saturation moment at 5 K and the Curie temperature TC are 38.1μB and 298 K, respectively. The AS originates from a reversible second-order magnetic transition around TC and its value reaches 5.2 J/kg.K for a magnetic field change from 0 to 5T. The refrigerant capacity （RC） of Gd6Co1.67Si3 are calculated by using the methods given in Refs.[12] and [21], respectively, for a field change of 0 5T and its values are 310 and 440 J/kg, which is larger than those of some magnetocaloric materials with a first-order phase transition.