This review focuses on the synthesis, protection, functionalization, and application of magnetic nanoparticles, as well as the magnetic properties of nanostructured systems. Substantial progress in the size and shape control of magnetic nanoparticles has been made by developing methods such as co-precipitation, thermal decomposition and/or reduction, micelle synthesis, and hydrothermal synthesis. A major challenge still is protection against corrosion, and therefore suitable protection strategies will be emphasized, for example, surfactant/polymer coating, silica coating and carbon coating of magnetic nanoparticles or embedding them in a matrix/support. Properly protected magnetic nanoparticles can be used as building blocks for the fabrication of various functional systems, and their application in catalysis and biotechnology will be briefly reviewed. Finally, some future trends and perspectives in these research areas will be outlined.

Magnetic nanoparticles: Synthesis, protection, functionalization, and application

The recent literature concerning the magnetocaloric effect (MCE) has been reviewed. The MCE properties have been compiled and correlations have been made comparing the behaviours of the different families of magnetic materials which exhibit large or unusual MCE values. These families include: the lanthanide (R) Laves phases (RM2, where M = Al, Co and Ni), Gd5(Si1−xGex)4 ,M n(As1−xSbx), MnFe(P1−xAsx), La(Fe13−xSix) and their hydrides and the manganites (R1−xMxMnO3, where R = lanthanide and M = Ca, Sr and Ba). The potential for use of these materials in magnetic refrigeration is discussed, including a comparison with Gd as a near room temperature active magnetic regenerator material. (Some figures in this article are in colour only in the electronic version)

https://iopscience.iop.org/article/10.1088/0034-4885/68/6/R04/pdf

Recent developments in magnetocaloric materials

In this chapter, we will restrict our attention to the ferrites and a few other closely related materials. The great interest in ferrites stems from their unique combination of a spontaneous magnetization and a high electrical resistivity. The observed magnetization results from the difference in the magnetizations of two non-equivalent sub-lattices of the magnetic ions in the crystal structure. Materials of this type should strictly be designated as “ferrimagnetic” and in some respects are more closely related to anti-ferromagnetic substances than they are to ferromagnetics in which the magnetization results from the parallel alignment of all the magnetic moments present. We shall not adhere to this special nomenclature except to emphasize effects, which are due to the existence of the sub-lattices.

Ferromagnetic materials

A new energy paradigm, consisting of greater reliance on renewable energy sources and increased concern for energy effi ciency in the total energy lifecycle, has accelerated research into energy-related technologies. Due to their ubiquity, magnetic materials play an important role in improving the effi ciency and performance of devices in electric power generation, conditioning, conversion, transportation, and other energy-use sectors of the economy. This review focuses on the state-of-the-art hard and soft magnets and magnetocaloric materials, with an emphasis on their optimization for energy applications. Specifi cally, the impact of hard magnets on electric motor and transportation technologies, of soft magnetic materials on electricity generation and conversion technologies, and of magnetocaloric materials for refrigeration technologies, are discussed. The synthesis, characterization, and property evaluation of the materials, with an emphasis on structure‐property relationships, are discussed in the context of their respective markets, as well as their potential impact on energy effi ciency. Finally, considering future bottlenecks in raw materials, options for the recycling of rare-earth intermetallics for hard magnets will be discussed.

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Magnetic materials and devices for the 21st century: Stronger, lighter, and more energy efficient

The magnetocaloric effect (MCE) in paramagnetic materials has been widely used for attaining very low temperatures by applying a magnetic field isothermally and removing it adiabatically. The effect can also be exploited for room-temperature refrigeration by using giant MCE materials. Here we report on an inverse situation in Ni-Mn-Sn alloys, whereby applying a magnetic field adiabatically, rather than removing it, causes the sample to cool. This has been known to occur in some intermetallic compounds, for which a moderate entropy increase can be induced when a field is applied, thus giving rise to an inverse magnetocaloric effect. However, the entropy change found for some ferromagnetic Ni-Mn-Sn alloys is just as large as that reported for giant MCE materials, but with opposite sign. The giant inverse MCE has its origin in a martensitic phase transformation that modifies the magnetic exchange interactions through the change in the lattice parameters.

Inverse magnetocaloric effect in ferromagnetic Ni-Mn-Sn alloys.

Magnetic refrigeration techniques based on the magnetocaloric effect (MCE) have recently been demonstrated as a promising alternative to conventional vapour-cycle refrigeration1. In a material displaying the MCE, the alignment of randomly oriented magnetic moments by an external magnetic field results in heating. This heat can then be removed from the MCE material to the ambient atmosphere by heat transfer. If the magnetic field is subsequently turned off, the magnetic moments randomize again, which leads to cooling of the material below the ambient temperature. Here we report the discovery of a large magnetic entropy change in MnFeP0.45As0.55, a material that has a Curie temperature of about 300 K and which allows magnetic refrigeration at room temperature. The magnetic entropy changes reach values of 14.5 J K-1 kg-1 and 18 J K-1 kg-1 for field changes of 2 T and 5 T, respectively. The so-called giant-MCE material Gd5Ge2Si2 (ref. 2) displays similar entropy changes, but can only be used below room temperature. The refrigerant capacity of our material is also significantly greater than that of Gd (ref. 3). The large entropy change is attributed to a field-induced first-order phase transition enhancing the effect of the applied magnetic field.

Transition-metal-based magnetic refrigerants for room-temperature applications

We have studied the magnetocaloric properties of a variety of compounds, like Gd5(Si1−xGex)4 with x=0.576 and 0.5875, MnFeP1−xAsx with x between 0.25 and 0.65, RTiGe with R=Tb, Dy, Ho, Er and Tm, Ni53Mn22Ga25, Mn5Si3, and Mn1.95Cr0.05Sb. These compounds have in common that they exhibit either temperature- or field-induced first-order magnetic-phase transitions. Gd5(Si1−xGex)4 exhibits simultaneously a magnetic and a structural transition, which is accompanied by a huge magnetic-entropy change. A temperature-induced ferromagnetic (FM) to paramagnetic (PM) transition and a magnetic-field-induced PM to FM transition which are both of first order are observed in MnFeP1−xAsx compounds. Here the magnetic-phase transitions are not accompanied by structural transitions. Nevertheless, a large magnetic-entropy change, comparable with that in Gd5(Si1−xGex)4, is observed in the MnFeP1−xAsx compounds. In several of the RTiGe compounds, an applied magnetic field induces an antiferromagnetic (AF) to FM phase transition. Here, we observed a magnetic anisotropy dependence of the magnetic-entropy change. The Heusler alloy Ni53Mn22Ga25 exhibits a first-order martensitic transformation accompanied by a magnetic-phase transition around 220 K. The magnitude and the shape of the magnetic-entropy changes observed for this compound are quite different. Mn5Si3 compound exhibits two successive first-order magnetic-phase transitions and shows a different type of magnetocaloric effect (MCE). Mn1.95Cr0.05Sb exhibits an AF to FM phase transition and a negative MCE. The relationship between the magnetic-phase transitions and the MCE is discussed, based on the comparison of the observed MCEs and the exchange interactions in these materials.

Magnetic-phase transitions and magnetocaloric effects

Magnetic refrigeration employing magnetically ordered materials is a relatively novel technique, differing in some respects from magnetic cooling by means of adiabatic demagnetization of paramagnetic substances. Magnetic refrigeration has been known for more than a century and is based on the magnetocaloric effect. It has received new impetus recently because it has several advantages over vapor-compression refrigeration. In the last few years the magnetic and magnetocaloric properties of a large number of intermetallic compounds were investigated, in which the magnetic moments are carried by atoms of 3d transition elements. In the present paper we will focus on intermetallic compounds in which one of the components is Mn. The results obtained on several groups of such intermetallic compounds will be reviewed. By far the most promising materials of this group of intermetallics are compounds of the type MnFeP1−xAsx. Although it is understood that these compounds are probably nontoxic, the presence of As atoms in them might form a mental barrier to exploit these materials on a commercial basis. Special attention will therefore be paid to efforts attempting to substitute other elements for As in MnFeP1−xAsx with the proviso that the favorable magnetocaloric properties be retained.

A review on Mn based materials for magnetic refrigeration: Structure and properties

Modern society relies very much on readily available cooling. Magnetic refrigeration based on the magneto-caloric effect (MCE) has become a promising competitive technology for the conventional gas-compression/expansion technique in use today. Recently, there have been two breakthroughs in magnetic-refrigeration research: one is that American scientists demonstrated the world's first room-temperature, permanent-magnet, magnetic refrigerator; the other one is that we discovered a new class of magnetic refrigerant materials for room-temperature applications. The new materials are manganese–iron–phosphorus–arsenic (MnFe(P,As)) compounds. This new material has important advantages over existing magnetic coolants: it exhibits a huge MCE, which is larger than that of Gd metal; and its operating temperature can be tuned from about 150 to about 335 K by adjusting the P/As ratio. Here we report on further improvement of the materials by increasing the Mn content. The large entropy change is attributed to a field-induced first-order phase transition enhancing the effect of the applied magnetic field. Addition of Mn reduces the thermal hysteresis, which is intrinsic to the first-order transition. This implies that already moderate applied magnetic fields of below 2 T may suffice.

O. Tegus

Papers

Transition-metal-based magnetic refrigerants for room-temperature applications

Magnetic-phase transitions and magnetocaloric effects

A review on Mn based materials for magnetic refrigeration: Structure and properties

Magnetic refrigeration—towards room-temperature applications

Magnetocaloric refrigeration near room temperature (invited)