Magnetic properties and magnetic entropy changes of La1-xPrxFe11.5Si1.5 compounds with 0 ≤ x ≤ 0.5

Magnetic properties and magnetic entropy changes in LaFe11.5Si1.5 have been investigated by partially substituting Pr by La. It is found that La1-xPrxFe11.5Si1.5 compounds remain cubic NaZn13-type structures even when the Pr content is increased to 0.5, i.e. x = 0.5. Substitution of Pr for La leads to a reduction in both the crystal constant and the Curie temperature. A stepwise magnetic behaviour in the isothermal magnetization curves is observed, indicating that the characteristic of the itinerant electron metamagnetic （IEM） transition above Tc becomes more prominent with the Pr content increasing. As a result, the magnetic entropy change is remarkably enhanced from 23.0 to 29.4 J/kg·K as the field changes from 0 to 5T, with the value of x increasing from 0 to 0.5. It is more attractive that the magnetic entropy changes for all samples are shaped into high plateaus in a wide range of temperature, which is highly favourable for Ericsson-type magnetic refrigeration.

Magnetic entropy change and magnetic phase transition of LaFe11.4Al1.6Cx （x=0-0.8） compounds

The unit cell volume and phase transition temperature of LaFe11.4Al1.6Cx compounds have been studied. The magnetic entropy change, refrigerant capacity and the type of magnetic phase transition are investigated in detail for LaFe11.4Al1.6Cx with x=0.1, All the LaFe11.4Al1.6Cx （x=0-0.8） compounds have the cubic NaZn13-type structure. The addition of carbon atoms brings about a considerable increase in the lattice parameter. The bulk expansion results in the change of phase transition temperature （Tc）, Tc increases from 187K to 269 K with x varying from 0.1 to 0.8, Meanwhile an increase in the lattice parameter can also cause a change of the magnetic ground state from antiferromagnetic to ferromagnetic. Large magnetic entropy change IASI is found over a large temperature range around Tc and the refrigerant capacity is about 322J/kg for LaFe11.4Al1.6C0.1. The magnetic phase transition belongs in weakly first-order one for x=0.1.

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

Our recent progress on magnetic entropy change（S） 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 different magnetic anisotropies,a positive S 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 S was observed in a single crystal.The △S 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 Ni 45（Co1-xFex）5 Mn36.6In13.4 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 TM in Ni51Mn49-xInx metamagnetic systems,which must be related to different nucleation mechanisms of structural transition under different external perturbations.

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.

Martensitic transformation and giant magnetic entropy change in Ni_(42.8)Mn_(40.3)Co_(5.7)Sn_(11.2) alloy

The crystal structure, phase transition, and magnetocaloric effect in Ni42.8Mn40.3Co5.7Sn11.2 alloy are investigated by structure analysis and magnetic measurements. A large magnetic entropy change of 45.6 J/kg.K is obtained at 215 K under a magnetic field of 30 kOe （1 Oe = 79.5775 A.m-1）. The effective refrigerant capacity of Ni42.8Mn40.3Co5.7Sn11.2 alloy reaches 72.1 J/kg under an applied field changing from 0 to 30 kOe. The external magnetic field shifts the martensitic transition temperature about 3-4 K/10 kOe towards low temperature, indicating that magnetic field can retard the phase transition to a certain extent. The origin of large magnetic entropy change is discussed in the paper.

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

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

Magnetic Transition and Magnetic Entropy Change of Gd_5Si_(1.75)Ge_(1.75)Sn_(0.5)

Gd5Si1.75 Ge1.75 Sn0.5 was prepared by arc melting method. The crystal structure and magnetic properties were investigated by XRD and VSM, respectively. The magnetization of the Gd5Si1.75 Ge1.75 Sn0.5 alloy changes abruptly near its corresponding Curie temperature 269 K, possesses a typical first which means that the alloy order phase transition. The Gd5Si1.75Ge1.75 Sn0.5 adopts in Gd5Si2Ge2-type monoclinic structure at room temperature, the maximal magnetic entropy change at a magnetic field change of 1.8 T is as large as 16.7 J·kg^-1·K^-1, exceeding that of Gd about two times and is a little larger than that of Gd5Si2Ge2.

Study on structure and magnetic entropy changes of Ce_(2-x)Pr_xFe_(16.5)Co_(0.5) alloys

A series of Ce2-xPrxFe16.5Co0.5 alloys were prepared by arc melting under purified argon atmosphere. The structure and magnetic entropy changes in Ce2-xPrxFe16.5Co0.5 alloys were investigated by means of X-ray diffraction pattern and MPMS XL-7 magnetometer. The experimental results show that the crystal structure of Ce2-xPrxFe16.5Co0.5 alloys keeps in Th2Zn17-type rhombohedral, and the Curie temperature of Ce2-xPrxFe16.5Co0.5 alloys can be shifted to room temperature around by a composition adjustment. The magnetic entropy changes (-ΔSM) in Ce2-xPrxFe16.5Co0.5 alloys are relatively large, and a platform of magnetic entropy changes appears near the temperature TC. Ce2-xPrxFe16.5Co0.5 alloys are the potential working media for magnetic refrigeration with their stable chemical properties and especially low price.

Magnetic Phase Transition and Magnetic Entropy Change in La_(0.8)Pr_(0.2)Fe_(11.4)Si_(1.6) Compound

The magnetic properties and the phase transformation of the partial substitution of Pr for La in LaFe11.4Si1.6 have been investigated by the means of X-ray diffraction (XRD) and vibrating sample magnetic (VSM). The results indicated that the single phase NaZn13-type cubic structure is stabilized for the compound La0.8Pr0.2Fe11.4Si1.6 and large values of the isothermal magnetic entropy change SM around the curie temperature TC～194 K in relative low magnetic fields. The maximum value︱SM︱max～37.07 J/kg·K-1 under a field of 1.5 T. Such large MCEs are attributed to the sharp change of the magnetization at the Curie temperature, the field-induced IEM transition and a strong temperature dependence of the critical field BC.

Adiabatic Temperature Changes in (Gd_(1-x)Ho_x)_5Si_4 Magnetic Refrigeration Materials

A series of alloys (Gd1-xHox)5Si4(x=0, 0.05, 0.15, 0.25) have been prepared. Adiabatic temperature changes of(Gd1-xHox)5Si4 alloys is exactly investigated by a control and analysis system for ΔH=1.4 T, and the measurement results are trustworthy. Curie temperatures of these alloys are tunable in a wide temperature region, and decrease almost linearly with the increasing of Ho content. Magnetic entropy changes in the (Gd1-xHox)Si4 compounds are about 2.35 J/(kg·K) when magnetic field change are 0～1.4 T. The adiabatic temperatures of these alloys at Curie Points are larger than 1 K about 40% of that of Gd in a field change 0～1.4 T, and the curves of ΔTad are as wide as that of Gd. The relative cooling power RCP(S) or RCP(T) of these alloys are about 0.5～0.7 J·cm-3 and 42～50 K2 on the field 0～1.4 T, about 58% and 55% of that of Gd respectively. These alloys are potential magnetic refrigerants working in a refrigerator at room temperatures.

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.

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.

Giant magnetocaloric effect in the Gd_5 Ge_(2.025)Si_(1.925)In_(0.05) compound

The magnetocaloric properties of the GdsGe2.025Si1.925In0.05 compound have been studied by x-ray diffraction, magnetic and heat capacity measurements. Powder x-ray diffraction measurement shows that the compound has a dominant phase of monoclinic Cd5Ge2Si2-type structure and a small quantity of Gds（Ge,Si）3-type phase at room temperature. At about 270 K, this compound shows a first order phase transition. The isothermal magnetic entropy change （△SM） is calculated from the temperature and magnetic field dependences of the magnetization and the temperature dependence of MCE in terms of adiabatic temperature change （△Tad） is calculated from the isothermal magnetic entropy change and the temperature variation in zero-field heat-capacity data. The maximum △SM is -13.6 J·kg^-1.K^- 1 and maximum ATad is 13 K for the magnetic field change of 0 5 T. The Debye temperature （θD） of this compound is 149 K and the value of DOS at the Fermi level is 1.6 states/eV.atom from the low temperature zero-field heat-capacity data. A considerable isothermal magnetic entropy change and adiabatic temperature change under a field change of 0-5 T jointly make the Gd5Ge2.025Si1.925In0.05 compound an attractive candidate for a magnetic refrigerant.

Structure and magnetocaloric effect in melt-spun La(Fe,Si)_(13) and MnFePGe compounds

The magnetocaloric properties of melt-spun La(Fe,Si)13 and MnFePGe compounds were investigated. Very large value of magnetic entropy change ｜ΔS｜=31 and 35.4 J·(kg·K)-1 under 5 T were obtained at 201 K in LaFe11.8Si1.2 melt-spun ribbons and at around 317 K in Mn1.1Fe0.9P0.76Ge0.24 melt-spun ribbons, respectively. The large magnetocaloric effect results from a more homogenous element distribution related to the very high cooling rate during melt-spinning. The excellent MCE properties, the low materials cost and the accelerated aging regime make the melt-spun-type La(Fe,Si)13 and MnFePGe materials an excellent candidate for magnetic refrigerant applications.

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.

Magnetocaloric Effect in Colossal Magnetoresistance Material (La_(0.6)Dy_(0.1))Sr_(0.3)MnO_3

The magnetocaloric effect in the A-site doping colossal magnetoresistance material (La_(0.6)Dy_(0.1))Sr_(0.3)MnO_3 was studied. From the measurement and calculation of isothermal magnetization (M-H) curves under various temperatures, a large magnetocaloric effect with ferromagnetic-paramagnetic transition, additional magnetism exchange action introduces additional magnetic entropy change was discovered. This result suggests that (La_(0.6)Dy_(0.1))Sr_(0.3)MnO_3 is a suitable candidate as working substance at room temperature in magnetic refrigeration technology.

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

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

Review of magnetocaloric effect in perovskite-type oxides

We survey the magnetocaloric effect in perovskite-type oxides （including doped ABO3-type manganese oxides, A3B2OT-type two-layered perovskite oxides, and A2B＇B＇＇O6-type ordered double-perovskite oxides）. Magnetic entropy changes larger than those of gadolinium can be observed in polycrystalline La1-xCaxMnO3 and alkali-metal （Na or K） doped La0.8Ca0.2MnO3 perovskite-type manganese oxides. The large magnetic entropy change produced by an abrupt reduction of magnetization is attributed to the anomalous thermal expansion at the Curie temperature. Considerable mag- netic entropy changes can also be observed in two-layered perovskites Lal.6Cal.4Mn207 and La2.5-xK0.5＋xMn2O7＋6 （0 〈 x 〈 0.5）, and double-perovskite Ba2Fe1＋xMol-xO6 （0 〈 x 〈 0.3） near their respective Curie temperatures. Com- pared with rare earth metals and their alloys, the perovskite-type oxides are lower in cost, and they exhibit higher chemical stability and higher electrical resistivity, which together favor lower eddy-current heating. They are potential magnetic refrigerants at high temperatures, especially near room temperature.

Hydrogenation, structure and magnetic properties of La(Fe_(0.91)Si_(0.09))_(13) hydrides and deuterides

Hydrogenation, crystal structure and magnetic properties of La（Fe0.91Si0.09）13H（D）y have been studied by pressure-composition isotherms （PCI）, X-ray diffraction （XRD）, differential scanning calorimetry （DSC） and magnetization measurements. The maximum absorption capacity is found to be 1.9 H（D） atoms per formula unit as a solid solution. All hydrides and deuterides crystallize in the NaZnl3-type cubic structure with the lattice parameter increasing linearly with H（D） concentration. The H（D） absorption enhances the Curie temperature significantly. The magnetic entropy change of the highly H-absorbed compound La（Feo.91Sio.09）13H1.81 reaches -26 J/kg-K under a magnetic field change of 5 T near the Curie temperature Tc =350 K. No observable isotope effect seems to imply that only the magnetovolume effect is responsible for the strong interplay between magnetism and lattice.

Magnetic properties and magnetocaloric effects in HoPd intermetallic

A large reversible magnetocaloric effect accompanied by a second order magnetic phase transition from PM to FM is observed in the Ho Pd compound. Under the magnetic field change of 0–5 T, the magnetic entropy change-ΔS max M and the refrigerant capacity RC for the compound are evaluated to be 20 J/（kg·K） and 342 J/kg, respectively. In particular,large-ΔS max M（11.3 J/（kg·K）） and RC（142 J/kg） are achieved under a low magnetic field change of 0–2 T with no thermal hysteresis and magnetic hysteresis loss. The large reversible magnetocaloric effect（both the large-ΔS M and the high RC）indicates that Ho Pd is a promising material for magnetic refrigeration at low temperature.