Magnetically Hard Research Articles

Boosting Coercivity of 3D Printed Hard Magnets through Nano-Modification of the Powder Feedstock.

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 1wt.%Ag nanoparticles boost the coercivity of the magnets to a record value of 935±6kAm-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 Nd2Fe14B 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.

Strategy of magnetic hardening region regulation enables a record enhanced energy product and high coercivity in Nd-Fe-B magnets

Strategy of magnetic hardening region regulation enables a record enhanced energy product and high coercivity in Nd-Fe-B magnets

Topological magnetic defects in a strong permanent magnet Nd2Fe14B

Skyrmions, highly mobile and manipulable magnetic objects, have garnered significant interest for their potential applications in modern magnetic device technology. However, their formation has been limited to a small number of materials due to the delicate balance of magnetic energies involved. In this study, we report the irreversible formation of skyrmions in Nd2Fe14B, a rare-earth permanent magnet characterized by large magnetic anisotropy. Remarkably, these magnetic topological defects exist over a wide range of temperatures and magnetic fields (295–565 K and 0–0.1 T) due to the high Curie temperature and significant magnetic anisotropy of Nd2Fe14B. Our findings not only unveil a new material where skyrmions can form but also open up possibilities for exploring topological defects in various magnetic systems, including strong hard magnets.

A Pressure Sensor Based on the Interaction between a Hard Magnet Magnetorheological Elastomer and a Hall Effect Structure

In this article, we report a novel pressure sensing method based on the Hall effect and a hard magnet magnetorheological elastomer (hmMRE). The elastic property of the MRE under pressure was used to generate spatial variation in the magnetic flux density around the MRE, and the variation was detected by the Hall effect device underneath. As the first development in this kind of pressure sensing mechanism, we conducted research for the following three purposes: (1) to verify the Hall effect on the output signal, (2) to understand the sensor output variations under different modes of operation, and (3) to utilize the mechanism as a pressure sensor. We characterized the sensor with its operation parameters, such as signal polarity switching depending on wiring directions, signal amplitude, and offset shift depending on the input voltage. Based on the analyses, we concluded that the Hall voltage represents the pressure applied on the hmMRE, and the new pressure sensing mechanism was devised successfully.

The energy of 180° domain walls of uniaxial crystals with the different magnetocrystalline anisotropy type

The main aim of the present work is to analyze the magnetocrystalline anisotropy (MCA) energy function of uniaxial crystals and to derive analytical expressions for the domain wall (DW) energy taking into account two MCA constants. Thus, the article presents a detailed analysis of the magnetocrystalline anisotropy energy function of uniaxial crystals taking into account two MCA constants (K1, K2). The values of the MCA energy extremes and the position of the easy magnetization directions (EMD) and hard magnetization directions (HMD) were determined. The MCA diagram was plotted in “K1”-“K2” coordinates. Six types of MCA have been found for uniaxial crystals. Two of them are simple with one maximum and one minimum of the EA(θ) function, and four are complex with two absolute and one local extreme for each. It is shown that EA(K1, K2) function has the smallest difference between the maximum and minimum values equal to |K1|/4 and the smallest angle between EMD and HMD equal to π/4 when the K1 + K2 = 0 condition is met. Analytical expressions for the 180° Bloch domain wall energy surface density (γ) were derived for uniaxial crystals with each MCA type. It is found that the γ(K1, K2) function has a minimum, equal to γ=2A|K1| when the relation K1 + K2 = 0 between MCA constants is satisfied. The derived analytical expressions are useful for a detailed spin-reorientation transition analysis. To illustrate this, examples of the application of the obtained results to MCA analyses of real crystals and DW energy calculations are given.

GeGra: Approaching a generic model for quantitative grain size analysis from materials microscopy data using deep learning

Grain size has a significant impact on the properties of materials, and is crucial for predicting material properties. Traditional grain size measurement relies heavily on human operators, leading to subjective results, and existing machine learning methods are typically material-specific, requiring significant labeling and training efforts for each new material. This paper provides insight into developing a deep learning-based generic grain boundary detection model (GeGra) from different material micrographs. The model is trained on 1006 images from various microscopy techniques such as light optical, Kerr, and scanning electron microscopy, acquired at different magnifications for different materials such as copper, austenite, brass, sintered hard magnet, hard metal, bronze, nickel silver, and aluminum. The developed GeGra model effectively handles visual artifacts and substructures such as twin grains, which often pose challenges for material-specific, state-of-the-art grain boundary segmentation models. The developed model achieved an IoU score of 69 % on a diverse test set and enables accurate grain size analysis using external image analysis software in less than one minute, according to ASTM standards, which is more than 5 times faster than the manual method. The developed model prioritizes generality with objective that it can have broader applicability for various materials instead of high-precision grain boundary detection. Additionally, the model has the potential to be a foundational tool for generalized grain size analysis in material microscopy, reducing the effort required for such analysis and assisting both material science experts and machine learning users.

Improvement of magnetic properties and hardness by alloying Mo to a FeCrCo alloy

In most of the technologies used for improving material properties, the enhancement of some properties usually leads to the degradation of others. In this study, we demonstrated that we were able to simultaneously improve hardness, coercivity, and remanence by alloying an FeCrCo alloy with Mo by engineering its α → α1 + α2 spinodal decomposition. We prepared six Mo-alloyed samples and subjected them to the appropriate aging protocols. As aging progressed, hardness increased from 272 to 447 HV and coercivity increased from 47 to 592 Oe in the alloyed samples. Remanence gradually increased from 52 to 98 Am2/kg, and then decreased to 82 Am2/kg in the final stage of the aging process. By adding Mo to six individual FeCrCo samples aged to different stages, we increased the hardness of these samples by 3 %, 8 %, 7 %, 8 %, 5 %, and 10 %, respectively. At the same time, we increased their coercivity by 74 %, 13 %, 19 %, 4 %, 14 %, and 9 % respectively and their remanence by 82 %, 63 %, 4 %, 4 %, 9 %, and 13 %, respectively. We used data drawn from scanning transmission electron microscopy, first-principles calculations, and magnetic force microscopy in order to elucidate the reasons behind the observed enhancements of magnetic properties in the FeCrCoMo alloy.

Thermodynamic stabilities of NdFe3Al2, Nd5Fe17 and μ compounds and evolutions of microstructures and magnetic properties of Nd-Fe-Al alloys with nanocrystallites

In the Nd-Fe-Al ternary system, thermodynamic stabilities of three compounds, NdFe3Al2, Nd5Fe17 and μ, were determined by the equilibrated alloys, indicating that both NdFe3Al2 and μ ternary compounds are metastable phases, while Nd5Fe17 compound is a stable phase. Meantime, the microstructures of five representative as-cast alloy buttons are illustrated, which are consisted of crystalline phases and the complex of nanocrystallites + amorphous matrix (NCAM). The crystalline phases including Nd, Nd3Al, Nd2Fe17-xAlx and Nd6Fe13-xAl1+x as well as the nanocrystallites such as dhcp-Nd, fcc-Nd and Nd6Fe13-xAl1+x embedded in the amorphous matrix were observed. Particularly, it is concluded that the fcc-Nd nanocrystallites may be transformed from the fcc dense packing clusters of the amorphous matrix and/or dhcp-Nd nanocrystallites. The hard magnetic properties of these as-cast alloys can be attributed to NCAM and present a non-strict proportionate effect. The alloy composed of Nd + NCAM, with curie temperature (Tc) 515 K, displays the highest intrinsic coercivity Hci 305 kA/m and remanent magnetization Br 10.8 emu/g. Its good glass-forming ability is presented by the high ratio (Tx/Tm) 0.88 and the small interval (Tm-Tx) 105 K of the crystallization temperature (Tx) with the melting temperature (Tm). Since the present investigation focuses on phase stabilities, microstructural characterizations, magnetic properties and glass-forming ability of the Nd-Fe-Al alloys, the obtained results can provide a better understanding for advancing the design of the Nd-Fe-Al based hard magnets and amorphous materials.

Enhanced dipole-interaction in Nd-Dy-Fe-Co-B/Fe composite thick stacked trilayer

It is crucial to better understand the magnetization reversal process between soft and hard magnets and to achieve a high maximum energy product in thick composite multilayers. In this study, we find that the exchange interactions dominate in soft–hard-magnetic composite bilayers, while dipole interactions are predominant in soft–hard-magnetic composite trilayers. Based on the first-order reversal curve, magnetization reversal models are developed for both the thick composite bilayer and trilayer. Dipole interactions play an important role in the long range, resulting in higher coercivity and remanence in the thick trilayer. A multilayer in a stacked trilayer structure is achieved, which is composed of thick films with a perpendicular magnetic anisotropy at a thickness of up to 16 μm. The enhanced dipole interactions lead to a remanent polarization of 1 T and a maximum energy product of 22.5 MGOe. This work contributes to the preparation of thick films with a high maximum energy product for applications in magnetic microelectromechanical systems.

Magnetic properties of hard-soft MnBi/FeNi@C exchange coupled nanostructures via cryo-milling

The extremely important permanent magnets encounter uncertainty and cost variations due to utilization of rare earths as prime components. Hence, the exchange coupled magnets comprised of hard and soft magnets in different proportions are explored to optimize the magnetic properties and cost. In this line, we prepared exchange coupled magnets of MnBi with FeNi@C nanoparticles (varying compositions = 10, 15 and 20 wt %) via cryogenic ball milling route. Out of these, the nanocomposite with MnBi and 15 wt% FeNi@C provided a coercivity value of 7.9 kOe with saturation magnetization and remanance values of 63 and 38 emu/g respectively. This exchange coupled magnet shown improvement in the MS, HC and Mr values by 53, 18 and 90 % respectively as compared to MnBi alone. The carbon layer over FeNi@C phase (MS = 147 emu/g) as well as cryomilling facilitated the formation of its exchange coupled magnet with MnBi.

Preparation of hard magnetic Co2C nanospheres as electrocatalysts for hydrogen evolution reaction

Cobalt carbide as a new type of transition metal carbides (TMACs) has received extensive attention in the field of magnetism and electrocatalysis. As one of the cobalt carbide materials, Co2C shows good hard magnetism. In this paper, we have designed a simple and efficient method to successfully prepare single-phase Co2C nanospheres. Co2C is synthesized by using Co3O4 as precursor and small molecule amino ethylenediamine as carbon source. The material exhibits excellent hard magnetic properties, with saturation magnetization up (Ms) to 32.19 emu/g and coercivity up to 1111 Oe at room temperature. Co2C also demonstrats excellent hydrogen evolution reaction performance in 1 M KOH solution. Using nickel foam as the working electrode, the overpotential of only 92 mV can reach the current density of 10 mA cm−2, and the Tafel slope is 104 mV dec−1. This provides a new idea for the further development of synthetic cobalt carbide and its composite materials.

Inkjet-Assisted Lithography of Templates for the Electroforming of Micromagnets for MEMS Applications

The integration of hard magnetic alloys in the form of patterned layers is one of the most interesting challenges for the manufacturing of energy efficient magnetic microelectromechanical systems (MEMS) [1]. With respect to current state of the art devices, whose working principle mostly relies on the exploitation of Lorentzian forces, MEMS based on permanent magnets can potentially present lower power consumption, larger displacements and stronger actuation forces. However, despite these attractive advantages, it is generally difficult to integrate thick hard magnetic layers with currently employed MEMS fabrication techniques.Electrodeposition is a technique that can be exploited to accomplish this task and that is characterized by many significant advantages: high deposition rates, no necessity of a vacuum system, low cost, possibility to deposit both alloys and composites. In addition, Reverse Pulse Plating (RPP) [2] can be used to mitigate the challenges connected to the deposition of hard magnetic alloys: high residual stress, presence of cracks and inadequate surface finishing. It can also simplify electrolyte formulation, eliminating the need of excessive amounts of additives.Regardless of the material selected, electrodeposition needs a template in order to confer a specific shape to the magnetic layer. Such template is normally manufactured using state-of-the-art technologies like standard lithography. This technique, however, is characterized by the necessity to use photomasks, which are costly and poorly adaptable to geometrical variations. Furthermore, the initial investment for the lithography equipment is typically high. A possible alternative is represented by the use of inkjet printing (IJP). This technology is characterized by low costs, high flexibility and optimal productivity. It can be applied to the micrometric patterning of electroformed layers by following a novel approach described in the present work for the first time: inkjet-assisted lithography (IAL). Briefly, droplets of a dispersion of silver nanoparticles are printed on the surface of a spin coated layer of negative photoresist. Silver is opaque for the UV radiation and it constitutes a mask for the resist. The resist is exposed and developed, forming thus templates usable for electroforming.The present work investigates the application of this approach to the production of thick and crack-free CoNiP micromagnets, which are RPP deposited inside IAL templates. CoNiP was selected due to its low-cost and good magnetic properties (with HC up to 2000 Oe). The alloy is electrodeposited from a chloride based acidic electrolyte [3], using ultra-fast RPP, in micrometric circular pores created via IAL. The diameter of the pores, and consequently the diameter of the finished magnets, can be efficiently tuned by changing the speed of the jetted droplets of silver ink. Conversely, the thickness of the magnets can be tuned by varying the deposition time. The resulting micromagnets, characterized by diameters in the 20-50 µm range and thickness up to 10 µm, are characterized to assess their morphology, phase composition and magnetic properties. The micrometric magnets here described may potentially find application for the realization of powerless MEMS, energy harvesting systems or microelectronic components.[1] N. M. Dempsey, “Hard Magnetic Materials for MEMS Applications” in: Nanoscale Magnetic Materials and Applications, Springer, Boston, MA (2009)[2] S. Pané et al., Electrochim. Acta 56, 8979-8988 (2011)[3] D. Y. Park et al., Electrochim. Acta 47, 2893-2900 (2002)

Aridity record of the Arabian Peninsula for the last 200 kyr: Environmental magnetic evidence from the western equatorial Indian ocean

The evolution of aridity and its forcing mechanisms in the Arabian Peninsula are of significance for better understanding the environmental response of the region to global change and the impact of past climate shifts in human evolution. Paleoclimatic reconstructions for the region are predominantly derived from fragmentary terrestrial records. Here, we present a detailed environmental magnetic record for marine sediments from the western equatorial Indian Ocean, which constitute the terminal sink for eolian material originated from the Arabian Peninsula. The dominant magnetic minerals identified in the studied sediments include magnetite, maghemite, and hematite. The hard isothermal remanent magnetization (HIRM), widely used as a proxy for the abundances of the high coercivity mineral hematite, has been used to track variations in the concentration of Arabian dust over the last 200 kyr. Dust concentrations are lowest during interglacial periods of maximum boreal summer isolation, and coincide with intervals during which lake and fluvial systems developed and speleothems formed across most of southern and central Arabia. Our results point to a sharp decrease in the production of dust due to the expansion of vegetation cover up to 30°N during these periods. West African Monsoon appears to be the major source of increased rainfall across Arabia, while the Indian Summer monsoon likely contributed to enhance rainfall in the south and southeastern parts of the peninsula. Variation in the supply of Arabian dust were also driven by changes in high-latitude ice volume and atmospheric CO2, as indicated by highest dust concentration found during glacial periods. We interpret that the expansion of high-latitude ice sheets increased the global meridional temperature gradient, weakened the monsoon system, and resulted in a more southerly, colder and descending subtropical westerly jet, leading to the retreat of vegetation cover and the enhanced production of dust from the Arabian deserts. Our results highlight a link between the production of Arabian dust and orbital-scale climate variability, including both monsoon and northern hemisphere ice sheets dynamics.

SmCo/Fe and SmCo/Co magnetic heterostructures: Micromagnetic simulation using the MuMax3 package

The magnetic SmCo/Fe and SmCo/Co heterostructures were numerically investigated in an external magnetic field using the micromagnetic simulation package MuMax3. The magnetization reversal curves and magnetic phase diagrams for these structures were plotted for different thicknesses of the magnetic layers and directions of the external magnetic field. The SmCo(20 nm)/Fe(20 nm) heterostructure reached saturation along the hard magnetization axis at an external magnetic field of 18 T, while a single SmCo(20 nm) layer achieved saturation at 18.2 T. The highest values of (BH)max were found to be 29.2MG∙Oe for the SmCo(20 nm)/Fe(10 nm) and 35.5MG∙Oe for the SmCo(20 nm)/Co(20 nm) heterostructures.

Discerning the magnetization reversal mechanism and magnetic interactions in arrays of FeNi nanowires

FeNi nanowires (NWs), 40 nm in diameter, were grown by electrodeposition. Compositional analysis showed Fe anomalous co-deposition, with different trends across the different potentials and electrolytes used. Those trends were explained within a modified Bocris-Drazic-Despic chemical reactions model, highlighting the importance of the electrochemical theory in understanding Fe-Ni electrodeposited systems. Structural characterization showed a change from a body-centred cubic structure for Fe-rich NWs to face-centred cubic at mid and low Fe content. Magnetic hysteresis measurements showed a range of coercivities from 20 mT for Fe-rich to 100 mT for Ni-rich NWs. Angular measurements allowed to determine that the magnetization reversal mechanism was dominated by transverse domain wall reversal. The analysis also hinted at the non-shape anisotropy acting as a demagnetizing force. First-order reversal curves (FORCs) showed that arrays with a high absolute value for the non-shape anisotropy had higher magnetic interactions, and vice versa. The non-shape anisotropy is dominated by the magnetostatic interactions between NWs, causing a weakening of the magnetic hardness. In combination with the coercivity angular measurements, the FORC analysis explained the shift in easy axis preference depending on NW chemical composition observed in the hysteresis loops of the samples.

Influence of calcination temperature and particle size distribution on the physical properties of SrFe12O19 and BaFe12O19 hexaferrite powders

The paper deals with the economic optimisation of ferrite powder preparation during producing hard ferrite magnets. The magnetic properties of ferrites are investigated by replacing feedstock and reducing calcination temperature and particles in the order of tens of microns. The granulates about 8–10 mm in size were calcined for 2 h in the temperature range from 1100 °C to 1300 °C and additionally crushed and milled to an average particle size of about 80–90 µm. The scanning electron microscopy images confirmed the agglomerates of particles with different shapes and sizes in tens of µm. The X-ray diffraction measurements revealed that, besides the SrFe12O19 and BaFe12O19 phases, there was also the presence of 2–39% hematite. The highest values of maximum energy product (BH)max = 930 J/m3 and remanent magnetic induction Br = 72.8 mT were obtained at a calcination temperature of 1300 °C. The Henkel plots confirmed the presence of exchange-coupling and dipolar magnetic interactions at lower and higher magnetic fields, respectively. The strength of interactions was also dependent on the calcination temperature. Replacing strontium with barium led to a deterioration of the magnetic parameters, which were optimal at a lower calcination temperature (1100 °C). This phenomenon was partly overcome by reducing the mean particle size of Ba-based hexaferrites to 45–50 µm.

Magnetic Hardening: Unveiling Magnetization Dynamics in Soft Magnetic Fe-Ni-B-Nb Thin Films at Cryogenic Temperatures.

Recent advancements in amorphous materials have opened new avenues for exploring unusual magnetic phenomena at the sub-nanometer scale. We investigate the phenomenon of low-temperature "magnetic hardening" in heterogeneous amorphous Fe-Ni-B-Nb thin films, revealing a complex interplay between microstructure and magnetism. Magnetization hysteresis measurements at cryogenic temperatures show a significant increase in coercivity (HC) below 25 K, challenging the conventional Random Anisotropy Model (RAM) in predicting magnetic responses at cryogenic temperatures. Heterogeneous films demonstrate a distinct behavior in field-cooled and zero-field-cooled temperature-dependent magnetizations at low temperatures, characterized by strong irreversibility. This suggests spin-glass-like features at low temperatures, which are attributed to exchange frustration in disordered interfacial regions. These regions hinder direct exchange coupling between magnetic entities, leading to magnetic hardening. This study enhances the understanding of how microstructural intricacies impact magnetic dynamics in heterogeneous amorphous thin films at cryogenic temperatures.

Intrinsic and extrinsic relaxation mechanisms for controlling spin current intensity in Fe 100−x Co x /Ta bilayers

Controlling the damping parameter in metallic ferromagnetic thin films is a key step for spintronic applications in which spin currents are generated by spin pumping. The coexistence of two states with low and high damping constant values would allow to obtain states of high and low spin current intensity, respectively. We have fabricated Fe 100−x Co x /Ta (with nominal x = 0, 15, 20, 25, 30 and 35) bilayers in which the Fe 100−x Co x layers grow epitaxially and the Ta layer is polycrystalline. We have found the coexistence of Gilbert damping and two magnon scattering mechanisms linked to a sign change in the magnetocrystalline anisotropy constant that allows the manipulation of low and high intensity states of the measured inverse spin Hall effect voltage. Bilayers with lower Co concentrations ( x⩽ 25%) present different relaxation mechanisms (isotropic Gilbert damping and two magnon scattering) and an extra ferromagnetic resonance linewidth broadening produced due to mosaicity. Bilayers with Co concentration x> 25% present a dominating Gilbert damping for all directions in the film plane. However, in this concentration range the damping constant is anisotropic and when the magnetic field is applied along the hard magnetization direction α increases ∼420% with respect to the value obtained for the easy magnetization direction. Coexistence of isotropic Gilbert damping and two magnon scattering generated spin currents 2.5 times larger when the field is applied along the hard magnetization axis compared to the value observed in the easy magnetization axis. Thesefindings make the Fe 100−x Co x /Ta system an excellent candidate for spintronic device applications.

Optimizing the grain boundary structure of sintered Nd-Fe-Co-B magnets by Dy-Al-Cu alloys grain boundary diffusion

The substitution of Fe by Co can effectively increase the Curie temperature of Nd-Fe-B magnets. However, the enrichment of Co in the grain boundary phase makes the grain boundary phase change from nonmagnetic to ferromagnetic, which has a harmful effect on the coercivity. In this paper, Dy70Al10Cu20 alloy was used as the diffusion source for grain boundary diffusion of sintered Nd-Fe-Co-B magnets. The magnetic properties and microstructure of the magnets were investigated by controlling the coating thickness of the diffusion source (thickness of 0.03 mm, 0.09 mm, and 0.15 mm). The results show that the coercivity of the magnet after diffusion is increased to 17.63 kOe, which is 9.69 kOe higher than that of the undiffused magnet. The phase composition analysis shows that the original magnet contains the soft magnetic 2:17 phase, and the 2:17 phase is significantly reduced after diffusion. The microstructure observation shows that the main phase is connected and the grain boundary phase is absent in the high Co original magnet. After diffusion, the thin grain boundary phase in the magnet increases, which effectively isolates the main phase grains. Dy-rich shell is formed on the surface of the main phase grain, which is beneficial to the improvement of coercivity. Therefore, magnetic hardening of Dy-rich shells and exchange-decoupling strengthening of adjacent 2:14:1 grains isolated by intergranular phases contributed to further coercivity increment Hcj of magnet simultaneously. Studies have shown that grain boundary diffusion is an effective way to improve the microstructure of Nd-Fe-Co-B magnets.

Core and surface structure and magnetic properties of mechano-synthesized LaFeO3 nanoparticles and their Eu3+-doped and Eu3+/Cr3+-co-doped variants

The core and surface structure and magnetic properties of mechano synthesized LaFeO3 nanoparticles (30–40 nm), their Eu3+-doped (La0.70Eu0.30FeO3), and Eu3+/Cr3+ co-doped (La0.70Eu0.30Fe0.95Cr0.05O3) variants are reported. Doping results in a transition from the O′-type to the O-type distorted structure. Traces of reactants, intermediate phases, and a small amount of Eu2+ ions were detected on the surfaces of the nanoparticles. The nanoparticles consist of antiferromagnetic cores flanked by ferromagnetic shells. The Eu3+ dopant ions enhance the magnetization values relative to those of the pristine nanoparticles and result in magnetic susceptibilities compatible with the presence of Eu3+ van Vleck paramagnetism of spin–orbit coupling constant (λ = 363 cm−1) and a low temperature Curie–Weiss like behavior associated with the minority Eu2+ ions. Anomalous temperature-dependent magnetic hardening due to competing magnetic anisotropy and magnetoelectric coupling effects together with a temperature-dependent dopant-sensitive exchange bias, caused by thermally activated spin reversals at the core of the nanoparticles, were observed.