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.

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.

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.

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.

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.

Effect of impurity phase on corrosion resistance and magnetic entropy change for LaFe_(11.3)Co_(0.4)Si_(1.3)C_(0.15) magnetocaloric compound

Effect of impurity phase（α-Fe phase and La-rich phase） on corrosion resistance and magnetic entropy change of LaFe_（11.3）Co_（0.4）Si_（1.3）C_（0.15） compound was studied using scanning electron microscopy, potentiodynamic polarization, electrochemical impedance spectroscopy techniques and magnetism testing. With the decrease of impurity phase, the corrosion resistance of LaFe_（11.3）Co_（0.4）Si_（1.3）C_（0.15） compound was first enhanced and then slightly impaired. Corrosion resistance could be significantly improved by the decrease of α-Fe phase. However, the matrix phase was corroded if the La-rich phase as anode was too few. This caused the corrosion resistance to decrease slightly. After immersing the sample in distilled water for 15 d, -？S_（max） of the samples annealed for 3, 12 h, 3 and 7 d decreased about 50%, 41%, 16% and 17%, respectively.

Effect of proportion change of aluminum and silicon on magnetic entropy change and magnetic properties in La0.8Ce0.2Fe11.5Al1.5-xSix compounds

The microstructure, magnetic entropy changes, hysteresis and magnetic properties of La_（0.8）Ce_（0.2）Fe_（11.5）Al_（1.5–x）Si_x（x=0.4, 0.5, 0.6, 0.7） compounds were studied by X-ray diffraction（XRD） and a superconducting quantum interference device magnetometer（SQUID）. The results showed that all the compounds presented cubic Na Zn13-type structure. Their Curie temperatures changed complicatedly with decreasing Al content due to changes of antiferromagnetic and ferromagnetic interaction. Under a field change from 0 to 2 T, the maximum magnetic entropy change for La_（0.8）Ce_（0.2）Fe_（11.5）Al_（1.1）Si_（0.4）, La_（0.8）Ce_（0.2）Fe_（11.5）Al_（1.0）Si_（0.5）, La_（0.8）Ce_（0.2）Fe_（11.5）Al_（0.9）Si_（0.6） and La_（0.8）Ce_（0.2）Fe_（11.5）Al_（0.8）Si_（0.7） were found to be –9.6, –4.8, –5.8 and –11.7 J/（kg·K）, respectively. Moreover, their hysteresis losses were 1.13 J/（kg·K） or less. The large magnetic entropy changed and small hysteresis losses made them potential candidates for practical magnetic refrigeration application.

Large magnetic entropy change and adiabatic temperature rise of a ternary Gd_(34)Ni_(33)Al_(33) metallic glass

A low cost Gd_(34)Ni_(33)Al_(33) metallic glass with excellent magnetocaloric properties was successfully prepared in the present work.The magnetic properties of the ribbons were measured by constructing the relationship of magnetic entropy change(-ΔS_(m)) on temperature as well as magnetic field.The amorphous alloy shows typical magnetocaloric behaviors,large maximum-ΔS_(m)(11.06 J/(kg·K) under 5 T)and adiabatic temperature rise(4.3 K under 5 T) near 40 K,indicating that the low cost Gd_(34)Ni_(33)Al_(33) metallic glass is a good candidate material for low temperature 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.

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 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.

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.

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.

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 effect of (Gd_(1-x)Ce_x)Co_2 compounds in low magnetic fields

The phases in the compounds （Gd1-xCex）Co2 with x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 were investigated by X-ray diffraction, and the magnetocaloric effect for x = 0-0.4 was studied by magnetization measurements. The samples are almost single phase with a cubic MgCu2-type structure for x = 0-0.5. The magnetization decreases with an increase in Ce content. There is almost no magnetic transition for x = 0.5 at 100-350 K. The Curie temperature （To） of the （Gd1-xCex）Co2compounds with x from 0.1 to 0.4 are 350, 344, 340, and 338 K respectively. The maximum magnetic entropy change is 2.34 J·kg^-1·K^-1 when x = 0.3. The results of Arrott plots show that the magnetic phase transition is second-order magnetic phase transition in these compounds.

Study on Gd-Al-Dy System Magnetic Refrigeration Materials

d-Al-Dy system materials were prepared by the technique of powder sintering. Twolayers gradient function materials with compositions of (Gd_0.9Dy_0.1)_3Al_2 and Gd_3Al_2 respectively were studied. The results show that the Curie temperature (Tc) of the monolayer material decreases with the increment of Dy content. The Tc values of the twolayer gradient function material agree well with the layer numbers and corresponding to Dy content. For the Tc gradiently changed twolayers Gd-Al-Dy system material, its ΔSm changes smoothly with temperature. Therefore, the magnetic refrigeration is improved.