F. X. Hu

Influence of negative lattice expansion and metamagnetic transition on magnetic entropy change in the compound LaFe11.4Si1.6

Magnetization of the compound LaFe11.4Si1.6 with the cubic NaZn13-type structure was measured as functions of temperature and magnetic field around its Curie temperature TC of ∼208 K. It is found that the magnetic phase transition at TC is completely reversible. Magnetic entropy change ΔS, allowing one to estimate the magnetocaloric effect, was determined based on the thermodynamic Maxwell relation. The achieved magnitude of |ΔS| reaches 19.4 J/kg K under a field of 5 T, which exceeds that of most other materials involving a reversible magnetic transition in the corresponding temperature range. The large entropy change is ascribed to the sharp change of magnetization, which is caused by a large negative lattice expansion at the TC. An asymmetrical broadening of |ΔS| peak with increasing field was observed, which is resulted from the field-induced itinerant-electron metamagnetic transition from the paramagnetic to ferromagnetic state above the TC.

Magnetic entropy change in Ni51.5Mn22.7Ga25.8 alloy

A considerable magnetic entropy change has been observed in Ni51.5Mn22.7Ga25.8 alloys under a field of 0.9 T. This change originates from a sharp magnetization jump which is associated with a martensitic to austenitic structure transition. The large low field entropy change and the adjustable martensic–austensic transition temperature indicate a great potential of Ni–Mn–Ga as working materials for magnetic refrigerants in a wide temperature range.

Determination of the entropy changes in the compounds with a first-order magnetic transition

Entropy changes in the compounds of La1−xPrxFe11.5Si1.5 (x=0.3 and 0.4) have been experimentally studied. A tower-shaped entropy change of the height of ∼27J∕kgK is obtained based on the analyses of heat capacity, while the Maxwell relation predicts an extra entropy peak of the height of ∼99J∕kgK, slightly varying with Pr content. A careful study indicates that the Maxwell relation cannot be used in the vicinity of the Curie temperature because of the coexistence of paramagnetic and ferromagnetic phases, and the huge entropy peak is a spurious result. Similar conclusions are applicable to MnAs and Mn1−xFexAs, for which huge entropy changes have been reported. Appropriate methods for the determination of entropy change of the compound with phase separation are discussed based on the magnetic data.

Very large magnetic entropy change near room temperature in LaFe11.2Co0.7Si1.1

A very large magnetic entropy change ΔS has been observed in Fe-based cubic NaZn13-type compound LaFe11.2Co0.7Si1.1 near the Curie temperature TC of 274 K. The value of the entropy change is ∼20.3 J/kg K under a magnetic field of 5 T at TC=274 K. It markedly exceeds that of pure Gd at the corresponding temperature range [V. K. Pecharsky & K. A. Gschneidner, Jr., Phys. Rev. Lett. 78, 4494 (1999)]. The great entropy change produced by the sharp change of magnetization is associated with a large negative lattice expansion at TC. The very large magnetic entropy change and low cost suggest that the compound LaFe11.2Co0.7Si1.1 has great potential for applications as magnetic refrigerants near room temperature.

Giant reversible magnetocaloric effect in metamagnetic HoCuSi compound

The magnetic properties and magnetocaloric effect (MCE) of antiferromagnetic HoCuSi compound have been studied. It is found that HoCuSi undergoes a field-induced first order metamagnetic transition from antiferromagnetic (AFM) to ferromagnetic (FM) states below the Neel temperature (TN). A giant MCE without hysteresis loss is observed in HoCuSi around TN. The maximal magnetic entropy change (−ΔSM) and refrigerant capacity are 33.1 J/kgK and 385 J/kg, respectively, for a field change of 0–5 T. The excellent magnetocaloric properties can result from the field-induced AFM-FM transition below TN and the increase in magnetization change caused by the change in lattice volume at TN.

Large reversible magnetocaloric effect caused by two successive magnetic transitions in ErGa compound

Intermetallic compound ErGa exhibits two successive magnetic transitions: spin-reorientation transition at TSR=15 K and ferromagnetic-paramagnetic transition at TC=30 K. Both transitions contribute greatly to the magnetic entropy change (ΔSM), each yielding a significant peak on their ΔSM-T curve and thus a considerable value of refrigerant capacity (RC) without hysteresis loss. For a magnetic field change of 5 T, the maximal values of −ΔSM are 21.3 J/kg K at TC and 16.5 J/kg K at TSR, with an RC value of 494 J/kg. Large reversible magnetocaloric effect and RC indicate the potentiality of ErGa as a candidate magnetic refrigerant at low temperatures.

Giant negative thermal expansion in bonded MnCoGe-based compounds with Ni2In-type hexagonal structure.

MnCoGe-based compounds undergo a giant negative thermal expansion (NTE) during the martensitic structural transition from Ni2In-type hexagonal to TiNiSi-type orthorhombic structure. High-resolution neutron diffraction experiments revealed that the expansion of unit cell volume can be as large as ΔV/V ∼ 3.9%. The optimized compositions with concurrent magnetic and structural transitions have been studied for magnetocaloric effect. However, these materials have not been considered as NTE materials partially due to the limited temperature window of phase transition. The as-prepared MnCoGe-based compounds are quite brittle and naturally collapse into powders. By using a few percents (3-4%) of epoxy to bond the powders, we introduced residual stress in the bonded samples and thus realized the broadening of structural transition by utilizing the specific characteristics of lattice softening enforced by the stress. As a result, giant NTE (not only the linear NTE coefficient α but also the operation-temperature window) has been achieved. For example, the average α̅ as much as -51.5 × 10(-6)/K with an operating temperature window as wide as 210 K from 122 to 332 K has been observed in a bonded MnCo0.98Cr0.02Ge compound. Moreover, in the region between 250 and 305 K near room temperature, the α value (-119 × 10(-6)/K) remains nearly independent of temperature. Such an excellent performance exceeds that of most other materials reported previously, suggesting it can potentially be used as a NTE material, particularly for compensating the materials with large positive thermal expansions.

Large reversible magnetocaloric effects in ErFeSi compound under low magnetic field change around liquid hydrogen temperature

Magnetic properties and magnetocaloric effects (MCEs) of ternary intermetallic ErFeSi compound have been investigated in detail. It is found that ErFeSi exhibits a second-order magnetic transition from ferromagnetic to paramagnetic states at the Curie temperature TC = 22 K, which is quite close to the liquid hydrogen temperature (20.3 K). A thermomagnetic irreversibility between zero-field-cooling and field-cooling curves is observed below TC in low magnetic field, and it is attributed to the narrow domain wall pinning effect. For a magnetic field change of 5 T, the maximum values of magnetic entropy change (−ΔSM) and adiabatic temperature change (ΔTad) are 23.1 J/kg K and 5.7 K, respectively. Particularly, the values of −ΔSM and refrigerant capacity reach as high as 14.2 J/kg K and 130 J/kg under a magnetic field change of 2 T, respectively. The large MCE without hysteresis loss for relatively low magnetic field change suggests that ErFeSi compound could be a promising material for magnetic refrigeration...

Magnetic entropy change and its temperature variation in compounds La(Fe1−xCox)11.2Si1.8

Magnetic entropy change ΔS of compounds La(Fe1−xCox)11.2Si1.8 with the cubic NaZn13-type structure was investigated around their Curie temperature TC. It is found that the phase transition is completely reversible, indicating a nature of second order phase transition. The maximum value of |ΔS|∼13.0 J/kg K under a field of 5 T was achieved in compound LaFe11.2Si1.8 at its TC of ∼222 K, which exceeds that of most materials involving a second order transition at the corresponding temperature. With increasing substitution of Co for Fe from x=0 to x=0.8, TC shifts from 222 to 307 K and entropy change decreases. However, |ΔS| still has a considerable magnitude near room temperature. The large magnetic entropy change is believed to be due to the abrupt change of magnetization at TC, which is associated with the strong structural and magnetic interplay in the compounds.

Large magnetic entropy change inLa(Fe,Co)11.83Al1.17

Large magnetic entropy change with comparable magnitude to that of pure Gd has been observed in compounds La(Fe12xCox)11.83Al1.17 (x50.06,0.08) at their Curie temperatures of ;273 K and ;303 K, respectively. These compounds are of a cubic NaZn 13-type structure with soft ferromagnetism. The magnetic entropy change is reversible in the whole experimental temperature range from ;230 to ;330 K. The most interesting feature is that the Curie temperature can be easily tuned by adjusting the substitution of Co for Fe. It is suggested that the present compounds are suitable candidates for magnetic refrigerants in a wide range near room temperature. The calculated DS curve in the molecular field approximation is in a satisfactory agreement with the experimental one.