Mn compounds presenting magneto-structural phase transitions are currently intensively studied for their giant magnetocaloric effect; nevertheless, several parameters remain to be further optimized. Here, we explore the Mn(Fe,Ni)(Si,Al) series, which presents two advantages. The Mn content is fixed to unity ensuring a large saturation magnetization, and it is based on non-critical Si and Al elements instead of the more commonly employed Ge. Structural and magnetic properties of MnFe_0.6 Ni_0.4 Si_1-x Al_x compounds are investigated using powder X-ray diffraction, SEM, EDX, DSC, and magnetic measurements. We demonstrate that a magneto-structural coupling leading to transformation from ferromagnetic with orthorhombic TiNiSi-type structure to a paramagnetic hexagonal Ni₂ In-type phase can be realized for 0.06 < x ≤ 0.08. Unfortunately, the first-order transition is relatively broad and incomplete, likely as the result of insufficient sample homogeneity. A comparison between samples synthesized in different conditions (as-cast, quenched from 900^◦ C, or quenched from 1100^◦ C) reveals that Mn(Fe,Ni)(Si,Al) samples decompose into a Mn₅ Si₃-type phase at intermediate temperatures, preventing the synthesis of high-quality samples by conventional methods such as arc-melting followed by solid-state reaction. By identifying promising MnFe_0.6 Ni_0.4 Si_1-x Al_x compositions, this study paves the way toward the realization of a giant magnetocaloric effect in these compounds using alternative synthesis techniques.

While rare-earth magnets exhibit unchallenged hard-magnetic properties, looking for alternatives based on inexpensive elements of non-critical supply remains of utmost interest. Here, we demonstrate that (Fe,Co)₂(P,Si) single crystals combine a large magnetocrystalline anisotropy (K₁ ≈ 0.9 MJ m⁻³ at 300 K), high Curie temperatures (T_C up to 560 K) and an appreciable saturation specific magnetization (101 A m² kg⁻¹) leading to a theoretical |BH|_max ≈ 165 kJ m^-3, making them promising candidate materials as rare-earth-free permanent magnets. Our comparison between (Fe,Co)₂P and (Fe,Co)₂(P,Si) single crystals highlights that Si substitution reduces the low-temperature magnetocrystalline anisotropy, but strongly enhances T_C, making the latter quaternary alloys most favorable for room temperature applications. Submicron-sized particles of Fe_1.75Co_0.20P_0.75Si_0.25 were prepared by a top-down ball-milling approach. While the energy products of bonded particles are to this point modest, they demonstrate that permanent magnetic properties can be achieved in (Fe,Co)₂(P,Si) quaternary alloys. This work correlates the development of permanent magnetic properties to a control of the microstructure. It paves the way toward the realization of permanent magnetic properties in (Fe,Co)₂(P,Si) alloys made of economically competitive Fe, P and Si elements, making these materials desirable for applications.

We explore the crystal structure and magnetic properties of quaternary materials deriving from the hexagonal Fe₂P, an iron binary known to present a particularly large magnetocrystalline anisotropy potentially interesting for permanent magnets, but with unfortunately a Curie temperature far too low for applications. Using simultaneous metal and metalloid substitutions in Fe_2-zCo_zP_1-xB_x and Fe_2-zCo_zP_1-ySi_y quaternaries, we found it is possible to increase the Curie temperature up to at least 640 K while maintaining a c axis uniaxial magnetocrystalline anisotropy, leading to an appreciable magnetic anisotropy at room temperature. In Fe_2-zCo_zP_1-xB_x, though boron is appropriate to increase the Curie temperature, its amount is limited as it also favors the formation of secondary phases. Contrary to what could be anticipated from the phase diagrams of Fe_2-zCo_zP or Fe₂P_1-ySi_y ternaries, simultaneous Co for Fe and Si for P substitutions in Fe_2-zCo_zP_1-ySi_y are found to significantly expand the range of stability of the Fe₂P-type crystal structure. X-ray diffraction patterns on powders oriented in magnetic field indicate a c axis uniaxial magnetic anisotropy. Appropriate heat-treatments and slight metal deficiency are found suitable to limit the formation of unwanted secondary phase with 3:1 metal:metalloid ratio. As a result, nearly single-phase Fe_1.95-zCo_zP_1-ySi_y materials are prepared and exhibit an appreciable magnetic anisotropy with K₁ up to approximately 0.93 MJm⁻³ at room temperature. This study experimentally demonstrates that Fe₂P-type transition metal quaternaries can present an interest not only for their first-order magnetic transition, but also for their magnetic anisotropy making them potential candidates for magnetostatic applications.

After almost 20 years of intensive research on magnetocaloric effects near room temperature, magnetic refrigeration with first-order magnetocaloric materials has come close to real-life applications. Many materials have been discussed as potential candidates to be used in multicaloric devices. However, phase transitions in ferroic materials are often hysteretic and a metric is needed to estimate the detrimental effects of this hysteresis. We propose the coefficient of refrigerant performance, which compares the net work in a reversible cycle with the positive work on the refrigerant, as a universal metric for ferroic materials. Here, we concentrate on examples from magnetocaloric materials and only consider one barocaloric experiment. This is mainly due to lack of data on electrocaloric materials. It appears that adjusting the field-induced transitions and the hysteresis effects can minimize the losses in first-order materials. This article is part of the themed issue 'Taking the temperature of phase transitions in cool materials'.

Magnetic cooling is a highly efficient refrigeration technique with the potential to replace the traditional vapor compression cycle. It is based on the magnetocaloric effect, which is associated with the temperature change of a material when placed in a magnetic field. We present experimental evidence for the origin of the giant entropy change found in the most promising materials, in the form of an electronic reconstruction caused by the competition between magnetism and bonding. The effect manifests itself as a redistribution of the electron density, which was measured by X-ray absorption and diffraction on MnFe(P,Si,B). The electronic redistribution is consistent with the formation of a covalent bond, resulting in a large drop in the Fe magnetic moments. The simultaneous change in bond length and strength, magnetism, and electron density provides the basis of the giant magnetocaloric effect. This new understanding of the mechanism of first order magneto-elastic phase transitions provides an essential step for new and improved magnetic refrigerants.

The field dependence of the magnetocaloric effect (MCE) in Mn_1.22Fe_0.73P_0.47Si_0.53 is studied in terms of the entropy change (Δ S) and the temperature change (Δ T) for applied magnetic fields up to 5 and 14 T, respectively. The magnetic fields required to saturate the MCE in this system are ∼ 1.7 and 4-5 T for Δ S and Δ T, respectively. The MCE field dependence is compared with the two approaches of the literature: 1) latent heat model and 2) the power law evolution predicted from the universal analysis of the MCE. It turns out that both of these methods are unsuitable to describe the MCE field evolution in MnFe(P,Si) materials.