Control of interfacial reaction and defect formation in Gd/Bi_(2)Te_(2.7)Se_(0.3) composites with excellent thermoelectric and magnetocaloric properties

The method to combine thermoelectric(TE)and magnetocaloric(MC)cooling techniques lies in developing a new material that simultaneously possesses a large TE and good MC cooling performance.In this work,using n-type Bi_(2)Te_(2.7)Se_(0.3)(BTS)as the TE base material and Gd as the second-phase MC material,Gd/BTS composites were prepared by the spark plasma sintering method.In the composites,interfacial reaction between Gd and BTS was identified,resulting in the formation of Gd Te,which has a large impact on the electron concentration through the adjustment of defect concentration.The MC/TE composite containing 2.5 wt%Gd exhibited a ZT value of 0.6 at 300 K,essentially retaining the original TE performance,while all the composites largely maintained the excellent MC performance of Gd.This work provides a potential pathway to achieving high performance in MC/TE composites.

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 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 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.

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.

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.

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.

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.

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.

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.

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

Giant reversible magnetocaloric effects and magnetic properties in Euo.9Ro.lTiO3 （R = La, Ce） are investigated. The antiferromagnetic ordering of pure EuTiO3 can significantly change to be ferromagnetic as substitution of La （x = 0.1） and Ce （x = 0.1） ions for Eu2＋ ions. The values of -ASM and RC are evaluated to be 10.8 J/（kg.K） and 51.8 J/kg for Euo.gCeo.lTiO3 and 11 J/（kg.K） and 39.3 J/kg for Euo.9Lao.lTiO3 at a magnetic field change of I0 kOe, respectively. The large low-field enhancements of --ASM and RC can be attributed to magnetic phase transition. The giant reversible MCE and large RC suggest that Euo.9Ro.ITiO3 （R = La, Ce） compounds could be promising materials in low temperature and low magnetic field refrigerants.

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.

Magnetocaloric effect in Gd_6Co_(1.67)Si_3 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.

Phase transition and magnetocaloric effect of Ni_(55.2)Mn_(18.6)Ga_(26.2-x)Gd_x (x=0,0.05,0.15) alloys

Phase transition process and magnetic entropy change -Delta S of Ni55.2Mn18.6Ga26.2-xGdx(x=0, 0.05, 0.15) alloys were studied. Ni55.2Mn18.6Ga26.2-xGdx(x=0, 0.05, 0.15) alloys still underwent simultaneous structural and magnetic transitions and transform from ferro-magnetic martensitic phase to paramagnetic austenitic phase during heating. Under a field of 2 T, the maximum magnetic entropy change -Delta S-M of Ni55.2Mn18.6Ga26.15Gd0.05 alloy was 7.7 J/kg.K at 317 K during heating and 8.6 J/kg.K at 314 K during cooling while it was 11.8 J/kg.K at 317 K in Ni55.2Mn18.6Ga26.05Gd0.15 alloy during heating.

Estimation on Magnetic Refrigeration Material (Gd_(1-x)RE_x)_5Si_4 (RE=Dy,Ho)

A systematic （Gd1-xREx）sSi4 （RE=Dy, Ho） alloys are investigated to estimate their magnetocaloric effect. The Curie points of （Gd1-xREx）Si4 alloys can tunable from 266 K to 336 K when RE=Dy, Ho; z=0N0.35 and 0-0.15, respectively, and decrease nearly linearly with increasing x. These alloys keep orthorhombic structures GesSm4 and exhibit second order transition when they experience in a change magnetic field at about Curie points. The weight and voluminal magnetic entropy changes are about 3.5 J/（kg.K） and 23-29 mJ/（cm^3.K） when magnetic field changes 0-2 T. The adiabatic temperatures changes （△Tad） of these alloys at Curie points are larger than 1 K in a field change 0-1.4 T, the curve of ATad is wide as that of Gd. The relative cooling power is about 0.8-0.9 J/cm^3 when field changes 0-2 T, 55% of that of Gd. Comparing with Gds（Si1-xGex）4, these alloys do not contain expensive element Ge, so that their cost are lower than the former. Because they could work at temperature region 260-340 K due to their Curie points can be tuned, which is an advantage comparing with Gd, these alloys are potential magnetic refrigerants working in a magnetic refrigerator with a low magnetic field at room temperatures.

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.