The giant magnetocaloric effect, in which large thermal changes are induced in a material on the application of a magnetic field, can be used for refrigeration applications, such as the cooling of systems from a small to a relatively large scale. However, commercial uptake is limited. We propose an approach to magnetic cooling that rejects the conventional idea that the hysteresis inherent in magnetostructural phase-change materials must be minimized to maximize the reversible magnetocaloric effect. Instead, we introduce a second stimulus, uniaxial stress, so that we can exploit the hysteresis. This allows us to lock-in the ferromagnetic phase as the magnetizing field is removed, which drastically removes the volume of the magnetic field source and so reduces the amount of expensive Nd-Fe-B permanent magnets needed for a magnetic refrigerator. In addition, the mass ratio between the magnetocaloric material and the permanent magnet can be increased, which allows scaling of the cooling power of a device simply by increasing the refrigerant body. The technical feasibility of this hysteresis-positive approach is demonstrated using Ni-Mn-In Heusler alloys. Our study could lead to an enhanced usage of the giant magnetocaloric effect in commercial applications.
We report on the adiabatic temperature changes (ΔT) associated with the magnetocaloric and barocaloric effects in a Fe49Rh51 alloy. For the magnetocaloric effect, data derived from entropy curves are compared to direct thermometry measurements. The agreement between the two sets of data provides support to the estimation of ΔT for the barocaloric effect, which are indirectly determined from entropy curves. Large ΔT values are obtained at relatively low values of magnetic field (2 T) and hydrostatic pressure (2.5 kbar). It is also shown that both magnetocaloric and barocaloric effects exhibit good reproducibility upon magnetic field and hydrostatic pressure cycling, over a considerable temperature range.
We have studied the barocaloric properties associated with the martensitic transition of a shape memory Heulser alloy Ni50Mn31.5Ti18.5 which is composed of all-d-metal elements. The composition of the sample has been tailored to avoid long range ferromagnetic order in both ausenite and martensite. The lack of ferromagnetism results in a weak magnetic contribution to the total entropy change thereby leading to a large transition entropy change. The combination of such a large entropy change and a relatively large volume change at the martensitic transition gives rise to giant barocaloric properties in this alloy. When compared to other shape memory Heusler alloys, our material exhibits values for adiabatic temperature and isothermal entropy changes significantly larger than values reported so far for this class of materials. Furthermore, our Ni50Mn31.5Ti18.5 also compares favourably to the best state-of-the-art magnetic barocaloric materials.
A giant barocaloric effect (BCE) in a molecular material Fe3(bntrz)6(tcnset)6 (FBT) is reported, where bntrz = 4‐(benzyl)‐1,2,4‐triazole and tcnset = 1,1,3,3‐tetracyano‐2‐thioethylepropenide. The crystal structure of FBT contains a trinuclear transition metal complex that undergoes an abrupt spin‐state switching between the state in which all three FeII centers are in the high‐spin (S = 2) electronic configuration and the state in which all of them are in the low‐spin (S = 0) configuration. Despite the strongly cooperative nature of the spin transition, it proceeds with a negligible hysteresis and a large volumetric change, suggesting that FBT should be a good candidate for producing a large BCE. Powder X‐ray diffraction and calorimetry reveal that the material is highly susceptible to applied pressure, as the transition temperature spans the range from 318 at ambient pressure to 383 K at 2.6 kbar. Despite the large shift in the spin‐transition temperature, its nonhysteretic character is maintained under applied pressure. Such behavior leads to a remarkably large and reversible BCE, characterized by an isothermal entropy change of 120 J kg−1 K−1 and an adiabatic temperature change of 35 K, which are among the highest reversible values reported for any caloric material thus far.
The world's growing hunger for artificial cold, on the one hand, and the ever more stringent climate targets, on the other, pose an enormous challenge to mankind. Novel, efficient, and environmentally friendly refrigeration technologies based on solid-state refrigerants can offer a way out of the problems arising from climate-damaging substances used in conventional vapor-compressors. Multicaloric materials stand out because of their large temperature changes, which can be induced by the application of different external stimuli such as a magnetic, electric, or a mechanical field. Despite the high potential for applications and the interesting physics of this group of materials, few studies focus on their investigation by direct methods. In this paper, we report on the advanced characterization of all relevant physical quantities that determine the multicaloric effect of a Ni-Mn-In Heusler compound. We have used a purpose-designed calorimeter to determine the isothermal entropy and adiabatic temperature changes resulting from the combined action of magnetic field and uniaxial stress on this metamagnetic shape-memory alloy. From these results, we can conclude that the multicaloric response of this alloy by appropriate changes of uniaxial stress and magnetic field largely outperforms the caloric response of the alloy when subjected to only a single stimulus. We anticipate that our findings can be applied to other multicaloric materials, thus inspiring the development of refrigeration devices based on the multicaloric effect.
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