Reduction of hysteresis loss in LaFe11.7Si1.3Hx hydrides with significant magnetocaloric effects

Magnetic properties and magnetocaloric effects (MCEs) have been investigated in hydrogenated LaFe_11.7 Si_1.3H _x (x=0,1.37, and 2.07) compounds. It is found that the Curie temperature, T _C, can be tuned from 192 to 338 K by adjusting the hydrogen content from 0 to 2.07. It is attractive that both thermal and magnetic hysteresis are remarkably reduced because of the weakness of the itinerant-electron metamagnetic transition after hydrogenation. The maximal hysteresis loss at T _C decreases from 33.4 to 8.8 J/kg as x increases from 0 to 2.07. For the samples with x=0,1.37, and 2.07, the maximal values of the isothermal magnetic entropy change, ΔS _M, are 20.9, 15.1, and 15.83 J/kg K for the increasing field and 20.76 J/kg K, 14.53 J/kg K and 15.61 J/kg K for the decreasing field at T _C, with efficient refrigeration capacities of 439, 330, and 304 J/kg for a field change of 0–5 T, respectively. Large reversible MCE and small hysteresis with considerable refrigeration capacity indicate the potential of LaFe_11.7Si_1.3H _x hydride as a candidate magnetic refrigerant around room temperature.     

Metamagnetic transition and magnetocaloric effect in antiferromagnetic TbPdAl compound

Magnetic properties and the magnetocaloric effect of the compound TbPdAl are investigated. The compound exhibits a weak antiferromagnetic (AFM) coupling, and undergoes two successive AFM transitions at T_N=43 K and T_t=22 K. A field-induced metamagnetic transition from AFM to ferromagnetic (FM) state is observed below T_N, and a small magnetic field can destroy the AFM structure of TbPdAl, inducing an FM-like state. The maximal value of magnetic entropy change is −11.4 J/kg K with a refrigerant capacity of 350 J/kg around T_N for a field change of 0-5 T. Good magnetocaloric properties of TbPdAl result from the high saturation magnetization caused by the field-induced AFM-FM transition.     

Magnetic entropy change involving martensitic transition in NiMn-based Heusler alloys

Our recent progress on magnetic entropy change (ΔS) involving martensitic transition in both conventional and metamagnetic NiMn-based Heusler alloys is reviewed. For the conventional alloys, where both martensite and austenite exhibit ferromagnetic (FM) behavior but show differentmagnetic anisotropies, a positive ΔS as large as 4.1 J·kg^-1·K^-1 under a field change of 0–0.9 T was first observed at martensitic transition temperature T_M ~ 197 K. Through adjusting the Ni:Mn:Ga ratio to affect valence electron concentration e/a, T_M was successfully tuned to room temperature, and a large negative ΔS was observed in a single crystal. The -ΔS attained 18.0 J·kg-1·K-1 under a field change of 0–5 T. We also focused on the metamagnetic alloys that show mechanisms different from the conventional ones. It was found that post-annealing in suitable conditions or introducing interstitial H atoms can shift the T_M across a wide temperature range while retaining the strong metamagnetic behavior, and hence, retaining large magnetocaloric effect (MCE) and magnetoresistance (MR). The melt-spun technique can disorder atoms and make the ribbons display a B2 structure, but the metamagnetic behavior, as well as the MCE, becomes weak due to the enhanced saturated magnetization of martensites. We also studied the effect of Fe/Co co-doping in Ni₄₅(Co_1-xFe_x)5Mn36.6In13.4 metamagnetic alloys. Introduction of Fe atoms can assist the conversion of the Mn–Mn coupling from antiferromagnetic to ferromagnetic, thus maintaining the strong metamagnetic behavior and large MCE and MR. Furthermore, a small thermal hysteresis but significant magnetic hysteresis was observed around T_M in Ni₅₁Mn_49-xIn_x metamagnetic systems, which must be related to different nucleation mechanisms of structural transition under different external perturbations.     

Magnetic properties and magnetic entropy change in Heusler alloys Ni50Mn35?xCuxSn15

The influence of Cu substitution for Mn on magnetic properties and magnetic entropy change has been investigated in Heusler alloys, Ni₅₀Mn_35−x Cu _x Sn₁₅ (x=2,5 and 10). With increasing Cu content from x=2 to x=5, the martensitic transition temperature, T _M , decreases from 220 K to 120 K. Further increasing Cu up to x=10 results in the disappearance of T _M . For samples Ni₅₀Mn₃₃Cu₂Sn₁₅ and Ni₅₀Mn₃₀Cu₅Sn₁₅, both martensitic and austenitic states exhibit ferromagnetic characteristics, but the magnetization of martensitic phase is notably lower than that of austenitic phase. The magnetization difference, ΔM, across the martensitic transition leads to a considerably large Zeeman energy, μ ₀ΔM⋅H, which drives a field-induced metamagnetic transition. Associated with the metamagnetic behavior, a large positive magnetic entropy change ΔS takes place around T _M . For the sample Ni₅₀Mn₃₃Cu₂Sn₁₅,ΔS reaches 13.5 J/kg⋅K under a magnetic field change from 0 to 5 T.     

Structural and magnetic phase transitions in Pr<Subscript>0.15</Subscript>Sr<Subscript>0.85</Subscript>MnO<Subscript>3</Subscript> at high pressure

The crystal and magnetic structures of Pr_0.15Sr_0.85MnO₃ manganite have been studied by means of powder X-ray and neutron diffraction in the temperature range 10–400 K at high external pressures up to 55 and 4 GPa, respectively. A structural phase transition from cubic to tetragonal phase upon compression was observed, with large positive pressure coefficient of transition temperature dT _ct /dP = 28(2) K/GPa. The C-type antiferromagnetic (AFM) ground state is formed below T _N ≈ 260 K at ambient pressure. While at ambient pressure the structural and magnetic transition temperatures are close, T _ct ~ T _N , upon compression they become decoupled with T _N ≪ T _ct due to much weaker T _N pressure dependence with coefficient dT _N /dP = 3.8(1) K/GPa.     

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.     

Metamagnetism in Ce(Ga,Al)2

Effect of Al substitution on the magnetic properties of Ce(Ga_1−x Al _x )₂ (x=0, 0.1 and 0.5) system has been studied. The magnetic state of CeGa₂ is found to be FM with a T _C of 8 K, whereas the compounds with x=0.1 and 0.5 are AFM and possess T _N of about 9 K. These two compounds undergo metamagnetic transition and the critical fields are about 1.2 T and 0.5 T. respectively at 2 K. These variations are explained on the basis of helical spin structure in these compounds.     

Field-induced valence transition in EuPtP<Subscript>1−x</Subscript>As<Subscript>x</Subscript>

The ternary compound EuPtP exhibits two valence transitions at T ₁ = 235 K and T ₂ = 190 K. In order to examine a field-induced valence transition of Eu, we synthesized EuPtP_1−x As _x compounds with 0.05 ≤ x ≤ 0.5 and studied the magnetic and valence behavior. The substitution of As for P increases the lattice volume linearly and decreases both valence transition temperatures, T ₁ and T ₂, in contrast to the behavior under external pressures. The magnetization process in a pulsed magnetic field revealed that EuPtP_0.5As_0.5 exhibits an onset of metamagnetic transition above 50 T with a large hysteresis, which evidences a first-order field-induced valence transition. The analysis of the magnetization curves of x = 0.5 at various temperatures has demonstrated that the field-induced transition is essentially the same as the transition induced by temperature at T ₁.     

Giant magnetic refrigerant capacity in Ho3Al2 compound

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Ho₃Al₂ compound are investigated by magnetization and heat capacity measurements. Two successive magnetic transitions, a spin-reorientation (SR) transition at T_SR=31 K followed by a ferromagnetic (FM) to paramagnetic (PM) transition at T_C=40 K, are observed. Both magnetic transitions contribute to the MCE and result in a large magnetic entropy change (ΔS_M) in a wide temperature range. The maximum values of ?ΔS_M and adiabatic temperature change (ΔT_ad) reach 18.7 J/kg K and 4.8 K for the field changes of 0–5 T, respectively. In particular, a giant value of refrigerant capacity (RC) is estimated to be 704 J/kg for a field change of 5 T, which is much higher than those of many potential refrigerant materials with similar transition temperatures.     

Large low-field inverse magnetocaloric effect near room temperature in Ni50−x Mn37+x In13 Heusler alloys

Low field inverse magnetocaloric effect (IMCE) associated with first-order martensitic transition in Ni_50−x Mn_37+x In₁₃ (x=3,4,5) alloys was investigated. By tuning the composition of Ni/Mn, large change in the magnetization occurring between martensite and austenite phases in a narrow temperature interval was achieved, which results in large IMCE. Under low magnetic field change of 2 T, a large positive magnetic entropy change (ΔS _M ) of 23.5 J/kg K with a net refrigeration capacity of 53 J/kg was obtained near room temperature (308 K) in the x=3 alloy. The results show that a small variation in Ni/Mn ratio significantly influences the martensitic transition temperature and the associated magnetic and magnetocaloric properties.     

Successive magnetic transitions and low temperature magnetocaloric effect in RE2Ni7 (RE=Dy, Ho)

Magnetic properties of rare-earth intermetallics RE₂Ni₇ (RE=Dy, Ho) are reported. Both the samples undergo two successive magnetic transitions at T_h (paramagnetic to ferromagnetic) and T_l (spin reorientation) below 100 K. The transitions are found to be second order in nature as evident from the Arrot plot analysis. Large reversible magnetocaloric effect (MCE) was observed at low temperature in the studied samples. The maximum value of the magnetic entropy change in Ho₂Ni₇ is found to be −12.5 J/kg K (for 0 to 50 kOe of field change) around 25 K with a high relative cooling power (RCP) of 534 J/kg. The Dy counterpart also shows moderately large values of MCE (−7.3 J/kg K) and RCP (475 J/kg) around the magnetic transition region for similar change in the magnetic field. RE₂Ni₇ compounds can be promising materials for magnetic refrigeration in the temperature range of helium and hydrogen liquefaction.     

Magnetocaloric effect in manganites

The magnetocaloric effect (MCE) in La_{1 ? x} Sr _x MnO₃, Sm_0.55Sr_0.45MnO₃, and PrBaMn₂O₆ compounds is studied. The maximum values of MCE (??T _max) determined by a direct method in the second and third compositions and in La_0.9Sr_0.1MnO₃ are found to be much lower than those calculated from the change of the magnetic part of entropy in the Curie temperature (T _C) and the Néel temperature (T _N) range. The negative contribution of the antiferromagnetic (AFM) part of a sample in the La_{1 ? x} Sr _x MnO₃ system at 0.1 ?? x ?? 0.3 decreases ??T _max and changes the ??T(T) curve shape, shifting its maximum 20?C40 K above T _C. Lower values of ??T _max are detected in the range T _C = 130?142 K in polycrystalline and single-crystal Sm_0.55Sr_0.45MnO₃ samples cooled in air. If such samples were cooled in an oxygen atmosphere (which restores broken Mn-O-Mn bonds and, thus, increases the volume of CE-type AFM clusters), the maximum in the temperature dependence of MCE is located at T _N (243 K) for CE-type AFM clusters. A magnetic field applied to a sample during the MCE measurements transforms these clusters into a ferromagnetic (FM) state, and both types of clusters decompose at T = T _N. The PrBaMn₂O₆ composition undergoes an AFM-FM transition at 231 K, and the temperature dependence of its MCE has a sharp minimum at T = 234 K, where MCE is negative, and a broad maximum covering T _C. The absolute values of MCE at both extrema are several times lower than those calculated from the change in the magnetic entropy. These phenomena are explained by the presence of a magnetically heterogeneous FM-AFM state in these manganites.     

Large magnetocaloric effect in HoFeO3 single crystal

Magnetocaloric properties of HoFeO₃ single crystal are investigated along the direction [100]. Magnetic field dependent magnetization isotherms at different temperatures undergo a metamagnetic transition, entropy change as large as 19.2 J/kg K and 15.8 J/kg K are obtained at 7 T in the vicinity of antiferromagnetic ordering temperature of Ho³⁺ and the metamagnetic transition, respectively. The coupling of Ho and Fe spins generates the compensation behavior at 6.5 K, separating the two large magnetic entropy change. Its refrigeration capacity (RC) value, as high as 220 J/kg, is appreciable and can be considered as a promising magnetic refrigerant. New evidence for spin reorientation of Fe³⁺ in HoFeO₃ is also provided by the change of magnetic entropy.     

Antiferromagnetic ordering and metamagnetism in PrCuSi

A variety of physical properties measured on the hexagonal rare-earth intermetallic compound PrCuSi are presented. We provide compelling evidence for antiferromagnetic ordering at T_N = 5.1 K in this compound, in contrast to the former claim of ferromagnetic ordering at 14 K. The antiferromagnetic order is, however, found to be unstable in applied magnetic fields, becoming ferromagnetic beyond a metamagnetic transition at a field of 0.7 T at 2 K. It is argued that the magnetism in PrCuSi has the ingredients of a tricritical phase transition at the intersection of paramagnetism, ferromagnetism, and antiferromagnetism.     

Magnetic properties of Nd1−xKxMnO3 compounds

Polycrystalline Nd_1−xK_xMnO₃ (x=0.10–0.20) compounds have been prepared in single phase form with Pbnm space group. The magnetic properties were studied by measuring dc magnetization and ac susceptibility. They exhibit paramagnetic to ferromagnetic transition with transition temperature ranging from 116 to 128 K. The magnetization data have been analyzed by using Brillouin function model and by taking into account the ferromagnetic interaction. The effective spin contribution towards ferromagnetic interaction and spin canting angle have been estimated. The spin canting angle is found to decrease with increase in doping. Magneto-caloric effect (MCE) has been studied and the maximum change in entropy was found to be 1.76 J/kg K for 1 T field. Metal–insulator transition and colossal magnetoresistance of the order of 60% for 1 T field have been observed for x=0.20 sample.     

Magnetic transition and large reversible magnetocaloric effect in EuCu1.75P2 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.     

Magnetocaloric effect in polycrystalline La0.65Ba0.3M0.05MnO3 (M=Na, Ag, K) manganites

The effects of monovalent doping on the crystallographic, magnetic and magnetocaloric properties of La_0.65Ba_0.3M_0.05MnO₃ (M=Na, Ag, K) powder samples, elaborated using the solid state reaction method at high temperature, have been investigated. In our three samples the Mn⁴⁺ amount remains constant equal to 40%. The Rietveld refinement of the X-ray powder diffraction shows that all our synthesized samples are single phase and crystallize in the distorted rhombohedral system with R3¯c space group. All our studied samples undergo a paramagnetic–ferromagnetic transition with decreasing temperature. Using the Arrott plot, the second-order transition Curie temperature T_C for M=Na, Ag and K is found to be 310, 300 and 290 K, respectively. The magnetic entropy change, deduced from isothermal magnetization curves, exhibits a maximum |ΔS_M^Max| of about 2.65, 2.82 and 2.66 J/kg K for M=Na, Ag and K, respectively, in a magnetic applied field change of 5 T. Although these values are modest, the magnetocaloric effect extends over a large temperature range leading to an important value of the relative cooling power (RCP). The RCP values exhibit a nearly linear dependence with the magnetic applied field. The refrigeration capacity in a magnetic applied field of 1 T is found to be 28.8, 27.8 and 25.6 J/kg for M=Na, Ag and K compounds.     

Quasi-one-dimensional antiferromagnet LiCuVO4

An antiferromagnetic transition is observed in the quasi-one-dimensional metal-oxide compound LiCuVO₄. A wide peak is observed in the temperature dependence of the magnetic susceptibility at T _M =28 K, and the magnetic susceptibility exhibits a sharp drop at T _N ≈4 K. As the magnetic field increases, the antiferromagnetic-ordering temperature T _N =2.3 K at first increases somewhat and then decreases rapidly. The exchange interaction in the chains of copper-oxygen octahedra is estimated to be J ₁=22.5 K. The interchain interaction is estimated to be J ₂∼1 K. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 11, 828–831 (10 June 1999)     

Magnetoresistances and magnetic entropy changes associated with negative lattice expansions in NaZn13-type compounds LaFeCoSi

Magnetoresistances and magnetic entropy changes in NaZn13-type compounds La（Fel-xCox）11.9Si1.1 （x=0.04, 0.06, and 0.08） with Curie temperatures of 243 K, 274 K, and 301 K, respectively, are studied. The ferromagnetic ordering is accompanied by a negative lattice expansion. Large magnetic entropy changes in a wide temperature range from ～230 K to ～320 K are achieved. Raising Co content increases the Curie temperature but weakens the magnetovolume effect, thereby causing a decrease in magnetic entropy change. These materials exhibit a metallic character below Tc, whereas the electrical resistance decreases abruptly and then recovers the metal-like behaviour above Tc. Application of a magnetic field retains the transitions via increasing the ferromagnetic ordering temperature. An isothermal increase in magnetic field leads to an increase in electrical resistance at temperatures near but above Tc, which is a consequence of the field-induced metamagnetic transition from a paramagnetic state to a ferromagnetic state.     

Structural,magnetic, and magnetothermal properties of the Tb<Subscript>0.3</Subscript>Dy<Subscript>0.7</Subscript>Co<Subscript>2</Subscript> compound

A complex investigation of the structural, magnetic, and magnetothermal properties of the Tb_0.3Dy_0.7Co₂ compound synthesized with the use of high-purity rare-earth metals has been performed. The phase composition has been controlled using the X-ray structural analysis, and the topology of the alloy surface has been investigated using atomic-force microscopy. It has been established that the Tb_0.3Dy_0.7Co₂ compound is single-phase, while the samples selected for measurements possess a clearly pronounced texture. The magnetization has been measured using a vibrating-sample magnetometer in the fields up to 100 kOe in a temperature range from 4.2 to 200 K. The Curie temperature of the compound is 170 K. The data on the temperature dependence of heat capacity of Tb_0.3Dy_0.7Co₂ have been obtained. The magnetocaloric effect ΔT has been measured by a direct method in the fields up to 18 kOe applied both along and perpendicularly to the texture axis. The anisotropic behavior of the magnitude ΔT for this compound, which possesses the cubic structure, has been found. The maximum value of the magnetocaloric effect ΔT = 2.3 K (ΔH = 18 kOe) has been observed upon applying the magnetic field along the texture axis.