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Nearly single-phase samples of compound TbCo5 + δ (where δ = 0) are obtained and certified in the poly-and monocrystalline state. The latent heat is measured on these samples for the first time in the region of the spin-reorientation phase transition using differential scanning calorimetry. The latent heat of the transition is found to be 1.3 ± 0.2 kJ/kg. The experimental data are compared with the theoretical results obtained in the framework of the single-ion theory ( Q L = 1.1 kJ/kg). It is found that the discrepancy is insignificant to within the experimental error. [ABSTRACT FROM AUTHOR]

Abstract: The effect of hydrogen on structural and magnetic properties of the Dy2Fe17H x single crystal was investigated. The host alloys symmetry is retained upon hydrogenation. It was found that the magnetic characteristics (such as the Curie temperature and magnetocrystalline anisotropy) are highly sensitive to the presence of hydrogen and exhibit dramatic changes with changing of H content. The results are discussed in terms of a model considering the interaction of the quadrupole and 4f electron magnetic moments of the rare-earth ion with the interstitial hydrogen atoms. [Copyright &y& Elsevier]

The investigations of magnetization processes for Er3Ni and Er3Co single crystal compounds are presented. The magnetization processes are discussed on the basis of magnetic structures determined previously by neutron diffraction for both compounds. It is shown that both ferromagnetic and antiferromagnetic exchange interactions as well as strong local ionic anisotropy of erbium atoms play a significant role in the magnetization processes forming. [Copyright &y& Elsevier]

Magnetization and dc-susceptibility measurements of a Gd3Ni single crystal and polycrystalline material were performed. The Gd3Ni compound crystallizes in the orthorhombic Fe3C-type structure. Below the ordering temperature, TN=100 K, the field dependence of magnetization, measured along three basic symmetry axes, exhibit one or two field induced transitions. This behavior is discussed in terms of a model that includes the influence of the magnetic field on the exchange and anisotropy energies. We also discussed the anomalous behavior of the magnetization in the paramagnetic temperature range appearing as an inflection of the field dependence of the magnetization. [Copyright &y& Elsevier]

The demand for strong, compact permanent magnets essential for the energy transition drives innovation in magnet manufacturing. Additive manufacturing, particularly Powder Bed Fusion of metals using a laser beam (PBF-LB/M), offers potential for near-net-shaped Nd-Fe-B permanent magnets but often falls short compared to conventional methods. A less explored strategy to enhance these magnets is feedstock modification with nanoparticles. It is demonstrated that modifying a Nd-Fe-B-based feedstock with 1 wt.% Ag nanoparticles boost the coercivity of the magnets to a record value of 935 ± 6 kA m -1 without further post-processing or heat treatments. Suitable volumetric energy densities for the PBF-LB/M process are determined using finite element simulations predicting melt pool behavior and part density. Microstructural analyses reveal finer grain sizes and more equiaxed nanocrystalline structures due to the modification. Atom probe tomography identifies three phases in the Ag-modified samples, with Ag forming nanophase regions with rare-earth elements near the amorphous Zr-Ti-B-rich intergranular phase, potentially decoupling the Nd 2 Fe 14 B primary phase. The study shows that superior magnetic properties primarily result from microstructure modification rather than part density. These findings highlight inventive material design approaches via feedstock surface modification to achieve superior magnetic performance in additively manufactured Nd-Fe-B magnets., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Among the magnetocaloric materials featuring first-order phase transitions (FOPT), FeRh is considered as a reference system to study the FOPT because it is a "simple" binary system with a CsCl structure exhibiting a large adiabatic temperature change. Recently, ab initio theory predicted that changes in the Fe/Rh stoichiometry in the vicinity of equiatomic composition strongly influence the FOPT characteristics. However, this theoretical prediction was not clearly verified experimentally. Here, we investigated the composition dependence of the transitional hysteresis in FeRh. It is shown that a Fe excess of only 1 at. % induces a ferromagnetic state in the whole temperature range (from 5 K up to T c ) for a minor portion of the sample (≈10%), while 5 at. % is enough to completely eliminate the FOPT. Element-specific X-ray magnetic circular dichroism (XMCD) measurements suggest that this ferromagnetic contribution arises from residual FeRh ferromagnetic regions. We attribute the formation of such domains to Fe antisite defects, as Mössbauer spectroscopy demonstrates the presence of Fe atoms located at the 1b (Rh) sites in the CsCl-type structure. As a consequence, compared with the equiatomic composition, the slightly Fe-rich sample exhibits completely different FOPT properties, influencing the magnetocaloric performances. Thus, our study sheds light on the origin of the remarkable stoichiometric sensitivity of the FOPT behavior in FeRh. These insights have broader implications for understanding FOPT dynamics and the role of residual ferromagnetic domains.

The production of bulk nanostructured silicide thermoelectric materials by a reversible hydrogen absorption-desorption process is demonstrated. Here, high-pressure reactive milling under 100 bar hydrogen is used to decompose the Ca 2 Si phase into CaH 2 and Si. Subsequent vacuum heat treatment results in hydrogen desorption and recombination of the constituents into the original phase. By changing the heat treatment temperature, recombination into Ca 2 Si or Ca 5 Si 3 can be achieved. Most importantly, the advanced synthesis process enables drastic and simple microstructure refinement by more than two orders of magnitude, from a grain size of around 50 µm in the initial ingot to 100-200 nm after the hydrogen absorption-desorption process. Fine precipitates with sizes ranging from 10-50 nm are forming coherently inside the grains. Thus, the route is promising and can be used for reducing thermal conductivity due to phonon scattering from grain boundaries as well as through nanostructuring with second-phase precipitates. Moreover, the process is environmentally friendly since hydrogen is reversibly absorbed, desorbed, and can be fully recovered., (© 2023 The Authors. Small published by Wiley‐VCH GmbH.)

Currently, magnetocaloric refrigeration technologies are emerging as ecofriendly and more energy-efficient alternatives to conventional expansion-compression systems. However, major challenges remain. A particular concern is the mechanical properties of magnetocaloric materials, namely, their fatigue under cycling and difficulty in processing and shaping. Nevertheless, in the past few years, using multistimuli thermodynamic cycles with multicaloric refrigerants has led to higher heat-pumping efficiencies. To address simultaneously the challenges and develop a multicaloric material, in this work, we have prepared magnetocaloric-based flexible composite mats composed of micrometric electroactive (EA) polyvinylidene fluoride (PVDF) fibers with embedded magnetocaloric/strictive La(Fe,Si) 13 particles by the simple and cost-effective electrospinning technique. The composite's structural characterization, using X-ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, and measurements of the local-scale piezoresponse, revealed a cubic NaZn 13 -type structure of the La(Fe,Si) 13 phase and the formation of the dominant polar β-phase of the PVDF polymer. The PVDF-La(Fe,Si) 13 composite showed an enhancement of the longitudinal piezoelectric coefficient (effective d 33 ) (-11.01 pm/V) compared with the single PVDF fiber matrix (-9.36 pm/V). The main magnetic properties of La(Fe,Si) 13 powder were retained in the PVDF-La(Fe,Si) 13 composite, including its giant magnetocaloric effect. By retaining the unique magnetic properties of La(Fe,Si) 13 embedded in the electroactive piezoelectric polymer fiber mats, we have designed a flexible, easily shapeable, and multifunctional composite enabling its potential application in multicaloric heat-pumping devices and other sensing and actuating devices.

Zero thermal expansion (ZTE) composites are typically designed by combining positive thermal expansion (PTE) with negative thermal expansion (NTE) materials acting as compensators and have many diverse applications, including in high-precision instrumentation and biomedical devices. La(Fe 1- x ,Si x )13-based compounds display several remarkable properties, such as giant magnetocaloric effect and very large NTE at room temperature. Both are linked via strong magnetovolume coupling, which leads to sharp magnetic and volume changes occurring simultaneously across first-order phase transitions; the abrupt nature of these changes makes them unsuitable as thermal expansion compensators. To make these materials more useful practically, the mechanisms controlling the temperature over which this transition occurs and the magnitude of contraction need to be controlled. In this work, ball-milling was used to decrease particles and crystallite sizes and increase the strain in LaFe 11.9 Mn 0.27 Si 1.29 H x alloys. Such size and strain tuning effectively broadened the temperature over which this transition occurs. The material's NTE operational temperature window was expanded, and its peak was suppressed by up to 85%. This work demonstrates that induced strain is the key mechanism controlling these materials' phase transitions. This allows the optimization of their thermal expansion toward room-temperature ZTE applications.

Utilizing the molecular beam epitaxy technique, a nanoscale thin-film magnet of c -axis-oriented Sm 2 Co 17 and SmCo 5 phases is stabilized. While typically in the prototype Sm(Co, Fe, Cu, Zr) 7.5-8 pinning-type magnets, an ordered nanocomposite is formed by complex thermal treatments, here, a one-step approach to induce controlled phase separation in a binary Sm-Co system is shown. A detailed analysis of the extended X-ray absorption fine structure confirmed the coexistence of Sm 2 Co 17 and SmCo 5 phases with 65% Sm 2 Co 17 and 35% SmCo 5 . The SmCo 5 phase is stabilized directly on an Al 2 O 3 substrate up to a thickness of 4 nm followed by a matrix of Sm 2 Co 17 intermixed with SmCo 5 . This structural transition takes place through coherent atomic layers, as revealed by scanning transmission electron microscopy. Highly crystalline growth of well-aligned Sm 2 Co 17 and SmCo 5 phases with coherent interfaces result in strong exchange interaction, leading to enhanced magnetization and magnetic coupling. The arrangement of Sm 2 Co 17 and SmCo 5 phases at the nanoscale is reflected in the observed magnetocrystalline anisotropy and coercivity. As next-generation permanent magnets require designing of materials at an atomic level, this work enhances our understanding of self-assembling and functioning of nanophased magnets and contributes to establishing new concepts to engineer the microstructure for beyond state-of-the-art magnets.

Pinning-type magnets with high coercivity at high temperatures are at the core of thriving clean-energy technologies. Among these, Sm 2 Co 17 -based magnets are excellent candidates owing to their high-temperature stability. However, despite intensive efforts to optimize the intragranular microstructure, the coercivity currently only reaches 20-30% of the theoretical limits. Here, the roles of the grain-interior nanostructure and the grain boundaries in controlling coercivity are disentangled by an emerging magnetoelectric approach. Through hydrogen charging/discharging by applying voltages of only ≈1 V, the coercivity is reversibly tuned by an unprecedented value of ≈1.3 T. In situ magneto-structural characterization and atomic-scale tracking of hydrogen atoms reveal that the segregation of hydrogen atoms at the grain boundaries, rather than the change of the crystal structure, dominates the reversible and substantial change of coercivity. Hydrogen reduces the local magnetocrystalline anisotropy and facilitates the magnetization reversal starting from the grain boundaries. This study opens a way to achieve the giant magnetoelectric effect in permanent magnets by engineering grain boundaries with hydrogen atoms. Furthermore, it reveals the so far neglected critical role of grain boundaries in the conventional magnetization-switching paradigm of pinning-type magnets, suggesting a critical reconsideration of engineering strategies to overcome the coercivity limits., (© 2020 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Due to economic, environmental and geopolitical issues, the development of permanent magnets with a composition free of rare earth elements and with acceptable magnetic properties has been considered a priority by the international community, being MnAl based alloys amongst the most promising candidates. The aim of this work was to evaluate the toxicity of powders of two forms of newly developed MnAl(C) permanent magnets through exposure experiments applying three model organisms, using as a benchmark powders of a commercial rare-earth-containing magnet (Nd 2 Fe 14 B). For this purpose, the direct exposure to the different particles suspensions as well as to magnets leachates was evaluated. Both viability and oxidative stress assays were applied in an adenocarcinomic human alveolar basal epithelial cell line (A549) and in the yeast Saccharomyces cerevisiae, together with the bioluminescent inhibition assay in the Gram negative bacterium Vibrio fischeri. The obtained results indicate that MnAl(C) permanent magnets, in general terms, presented similar toxicity than the Nd magnet for the selected biological models under the studied conditions. Overall, the presented data provide, for the first time, an in vitro toxicity analysis of MnAl based magnets., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Owing to electric-field screening, the modification of magnetic properties in ferromagnetic metals by applying small voltages is restricted to a few atomic layers at the surface of metals. Bulk metallic systems usually do not exhibit any magneto-electric effect. Here, we report that the magnetic properties of micron-scale ferromagnetic metals can be modulated substantially through electrochemically-controlled insertion and extraction of hydrogen atoms in metal structure. By applying voltages of only ~ 1 V, we show that the coercivity of micrometer-sized SmCo 5 , as a bulk model material, can be reversibly adjusted by ~ 1 T, two orders of magnitudes larger than previously reported. Moreover, voltage-assisted magnetization reversal is demonstrated at room temperature. Our study opens up a way to control the magnetic properties in ferromagnetic metals beyond the electric-field screening length, paving its way towards practical use in magneto-electric actuation and voltage-assisted magnetic storage.

Magnetic refrigeration is an upcoming technology that could be an alternative to the more than 100-year-old conventional gas-vapor compression cooling. Magnetic refrigeration might answer some of the global challenges linked with the increasing demands for readily available cooling in almost every region of the world and the global-warming potential of conventional refrigerants. Important issues to be solved are, for example, the required mass and the ecological footprint of the rare-earth permanent magnets and the magnetocaloric material, which are key parts of the magnetic cooling device. The majority of existing demonstrators use Nd-Fe-B permanent magnets, which account for more than 50% of the ecological footprint, and Gd, which is a critical raw material. This work shows a solution to these problems by demonstrating the world's first magnetocaloric demonstrator that uses recycled Nd-Fe-B magnets as the magnetic field source, and, as a Gd replacement material, La-Fe-Mn-Si for the magnetocaloric heat exchanger. These solutions show that it is possible to reduce the ecological footprint of magnetic cooling devices and provides magnetic cooling as a green solid-state technology that has the potential to satisfy the rapidly growing global demands., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

The search for tunable, size-dependent properties and unique processability has triggered the development of new synthetic routes for transition metal borides. MnB is a soft to semi-hard ferromagnetic material. This boride is now available by bottom-up, low-temperature solution chemistry. It is obtained as an unexpected metastable α'-variant that crystallises with a stacking-fault dominated CrB-type structure, as shown by transmission electron microscopy and X-ray powder diffraction (space group Cmcm, a = 300.5(8), b = 768.6(2), and c = 295.3(4) pm). The nanostructured powder consists of agglomerates of small particles (mean diameter of 85(41) nm) and transforms into well-known β-MnB with FeB-type structure at 1523 K. The room temperature ferromagnetic behavior (T C = 545 K) is attributed to the positive exchange-correlation between the manganese atoms, that have many unpaired d electrons.

Hysteresis is more than just an interesting oddity that occurs in materials with a first-order transition. It is a real obstacle on the path from existing laboratory-scale prototypes of magnetic refrigerators towards commercialization of this potentially disruptive cooling technology. Indeed, the reversibility of the magnetocaloric effect, being essential for magnetic heat pumps, strongly depends on the width of the thermal hysteresis and, therefore, it is necessary to understand the mechanisms causing hysteresis and to find solutions to minimize losses associated with thermal hysteresis in order to maximize the efficiency of magnetic cooling devices. In this work, we discuss the fundamental aspects that can contribute to thermal hysteresis and the strategies that we are developing to at least partially overcome the hysteresis problem in some selected classes of magnetocaloric materials with large application potential. In doing so, we refer to the most relevant classes of magnetic refrigerants La-Fe-Si-, Heusler- and Fe2P-type compounds.This article is part of the themed issue 'Taking the temperature of phase transitions in cool materials'., (© 2016 The Author(s).)

Achieving a very strong magnetic anisotropy in a 3d material is a difficult, but not an impossible task. It is difficult because there is no general recipe (necessary condition) for a strong anisotropy in a band magnet. Several strategies can be pursued in this situation. One of them is to re-examine the less studied 3d compounds, somewhat neglected since the discovery of the Nd-Fe-B magnets 30 years ago. As an example, a single crystal of (Fe0.7Co0.3)2B has been investigated in this work.

We have investigated the anisotropy of the magnetocaloric effect in a NdCo₅ single crystal in a wide range of temperatures, including the spin-reorientation temperature region. In the field μ(0)H =1.3 T in the spin-reorientation region 250-310 K, we discovered a giant rotating magnetocaloric effect of ~ 1.6 K, caused by rotation of the magnetization vector. The calculations of the anisotropy magnetocaloric effect for the field μ(0)H =1.3 T have been carried out.