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.

Simple rules for the understanding of Heusler compounds

Magnetic cooling could be a radically different energy solution that could replace conventional vapour compression refrigeration in the future. It is now shown that a Heusler-type magnetocaloric alloy exhibits a remarkable cooling capability due to the effect of a sharp structural transformation at a specific temperature. The finding may be of relevance beyond Heusler alloys and represents an important step towards the implementation of cooling systems based on magnetocaloric materials.

Giant magnetocaloric effect driven by structural transitions

A magnetically, electrically or mechanically responsive material can undergo significant thermal changes near a ferroic phase transition when its order parameter is modified by the conjugate applied field. The resulting magnetocaloric, electrocaloric and mechanocaloric (elastocaloric or barocaloric) effects are compared here in terms of history, experimental method, performance and prospective cooling applications.

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Caloric materials near ferroic phase transitions

Structural and magnetic transformations in the Heusler-based system ${\mathrm{Ni}}_{0.50}{\mathrm{Mn}}_{0.50\ensuremath{-}x}{\mathrm{Sn}}_{x}$ are studied by x-ray diffraction, optical microscopy, differential scanning calorimetry, and magnetization. The structural transformations are of austenitic-martensitic character. The austenite state has an $L{2}_{1}$ structure, whereas the structures of the martensite can be $10M$, $14M$, or $L{1}_{0}$ depending on the Sn composition. For samples that undergo martensitic transformations below and around room temperature, it is observed that the magnetic exchange in both parent and product phases is ferromagnetic, but the ferromagnetic exchange, characteristic of each phase, is found to be of different strength. This gives rise to different Curie temperatures for the austenitic and martensitic states.

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Martensitic transitions and the nature of ferromagnetism in the austenitic and martensitic states of Ni-Mn-Sn alloys

The magnetic and structural transformations in the Heusler-based system ${\mathrm{Ni}}_{0.50}{\mathrm{Mn}}_{0.50\ensuremath{-}x}{\mathrm{In}}_{x}$ are studied in the composition range $0.05\ensuremath{\leqslant}x\ensuremath{\leqslant}0.25$. While the cubic phase is preserved in the range $0.165\ensuremath{\leqslant}x\ensuremath{\leqslant}0.25$, we find the presence of martensitic transformations in alloys with $x\ensuremath{\leqslant}0.16$. In a critical composition range $0.15\ensuremath{\leqslant}x\ensuremath{\leqslant}0.16$, the magnetic coupling in both austenitic and martensitic states is ferromagnetic. Magnetic field-induced structural transitions are also found in the $x=0.16$ alloy, whereby the structural transition temperature shifts by $42\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ in a field of $50\phantom{\rule{0.3em}{0ex}}\mathrm{kOe}$.

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Ferromagnetism in the austenitic and martensitic states of Ni-Mn-In alloys

Applying a magnetic field to a ferromagnetic Ni{sub 50}Mn{sub 34}In{sub 16} alloy in the martensitic state induces a structural phase transition to the austenitic state. This is accompanied by a strain which recovers on removing the magnetic field, giving the system a magnetically superelastic character. A further property of this alloy is that it also shows the inverse magnetocaloric effect. The magnetic superelasticity and the inverse magnetocaloric effect in Ni-Mn-In and their association with the first-order structural transition are studied by magnetization, strain, and neutron-diffraction studies under magnetic field.

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Magnetic superelasticity and inverse magnetocaloric effect in Ni-Mn-In

At certain compositions Ni-Mn-$X$ Heusler alloys ($X$: group IIIA-VA elements) undergo martensitic transformations, and many of them exhibit inverse magnetocaloric effects. In alloys where $X$ is Sn, the isothermal entropy change is largest among the Heusler alloys, particularly in Ni$_{50}$Mn$_{37}$Sn$_{13}$ where it reaches a value of 20 Jkg$^{-1}$K$^{-1}$ for a field of 5T. We substitute Ni with Fe and Co in this alloy, each in amounts of 1 at% and 3 at% to perturb the electronic concentration and examine the resulting changes in the magnetocaloric properties. Increasing both Fe and Co concentrations causes the martensitic transition temperature to decrease, whereby the substitution by Co at both compositions or substituting 1 at% Fe leads to a decrease in the magnetocaloric effect. On the other hand, the magnetocaloric effect in the alloy with 3 at% Fe leads to an increase in the value of the entropy change to about 30 Jkg$^{-1}$K$^{-1}$ at 5T.

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Thorsten Krenke

Papers

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

Martensitic transitions and the nature of ferromagnetism in the austenitic and martensitic states of Ni-Mn-Sn alloys

Ferromagnetism in the austenitic and martensitic states of Ni-Mn-In alloys

Magnetic superelasticity and inverse magnetocaloric effect in Ni-Mn-In

Effect of Co and Fe on the inverse magnetocaloric properties of Ni-Mn-Sn