Magnetocaloric Research Articles

Negative magnetization and magnetic ordering of rare earth and transition metal sublattices in NdFe0.5Cr0.5O3

We investigate the effect of alloying at the 3d transition metal site of a rare-earth-transition metal oxide, by considering NdFe0.5Cr0.5O3 mixed perovskite with two equal and random distribution of 3d ions, Cr and Fe, interacting with an early 4f rare earth ion, Nd. Employing temperature- and field- dependent magnetization measurements, temperature-dependent x-ray diffraction, neutron powder diffraction, and Raman spectroscopy, we characterize its structural and magnetic properties. Our study reveals bipolar magnetic switching (arising from negative magnetization) and magnetocaloric effect which underline the potential of the studied mixed perovskite in device application. The neutron diffraction study shows the absence of spin reorientation transition over the entire temperature range of 1.5–320 K, although both parent compounds exhibit spin orientation transition. We discuss the microscopic origin of this curious behavior. The neutron diffraction results also reveal the ordering of Nd spins at an unusually high temperature of about 40 K, which is corroborated by Raman measurements.

Magnetic properties and magnetocaloric performances in the (Dy0.25Ho0.25Er0.25Tm0.25)2Cu2In high-entropy compound

We herein fabricated the (Dy0.25Ho0.25Er0.25Tm0.25)2Cu2In high-entropy (HE) compounds and systematically determined its structural, magnetic, and magnetocaloric properties. The (Dy0.25Ho0.25Er0.25Tm0.25)2Cu2In HE compound was found to crystalize in a tetragonal Mo2B2Fe type structure (P4/mbm space group) and undergoes typical second order type magnetic transition. Large MCE and prominent cryogenic magnetocaloric performances were observed in (Dy0.25Ho0.25Er0.25Tm0.25)2Cu2In HE compound. The evaluated values of magnetic entropy change and refrigerant capacity of (Dy0.25Ho0.25Er0.25Tm0.25)2Cu2In HE compound under magnetic field change of 0–7 T are 17.1 J/kgK and 398.0 J/kg which are comparable with the reported candidate materials for cryogenic magnetic cooling, making the present (Dy0.25Ho0.25Er0.25Tm0.25)2Cu2In HE compound also considerable for practical applications.

Interplay between the reversibility of the inverse magnetocaloric effect and kinetic arrest in Ni-Co-Mn-Sn Heusler alloys

The nature of martensitic phase transitions and its modification as a function of composition and application of magnetic field have been studied in detail for Ni40Co10Mn40Sn10-xGax (x=0, 0.3, 0.4 and 0.5). The phase transition temperature (TM) increases with increasing x. The kinetic arrest (KA) of the austenitic phase has been observed for x=0 and 0.3, which disappeared for x>0.3. The KA results in a decrease in the change of magnetization (ΔM) across TM. However, the isothermal entropy change ΔS varies almost linearly with [dTM/d(μ0H)]−1 (field-induced shift in TM) irrespective of the composition variation and thermal cycling. This behavior indicates that the variation of dTM/d(μ0H) is the dominant factor determining the magnitude of the ΔS rather than ΔM. Consequently, the effect of KA on ∆M has a negligible influence on ΔS in the studied Heusler alloys. The reduced field-sensitivity in TM associated with the temperature-induced decrease of magnetization in the ferromagnetic austenitic phase leads to a decrease of the thermal hysteresis and an increase of ΔS. As a result, a large reversible (|ΔSrev|=21 J/kg K for Δμ0H=5 T) has been observed for x=0.5, which exceeds previously reported values for Sn-based Heusler alloys.

Crystal Structure and Properties of Heusler Alloys: A Comprehensive Review

Heusler alloys, which were unintentionally discovered at the start of the 20th century, have become intriguing materials for many extraordinary functional applications in the 21st century, including smart devices, spintronics, magnetic refrigeration and the shape memory effect. With this review article, we would like to provide a comprehensive review on the recent progress in the development of Heusler alloys, especially Ni-Mn based ones, focusing on their structural crystallinity, order-disorder atoms, phase changes and magnetic ordering atoms. The characterization of the different structures of these types of materials is needed, where a detailed exploration of the crystal structure is presented, encompassing the influence of temperature and compositional variations on the exhibited phases. Hence, this class of materials, present at high temperatures, consist of an ordered austenite with a face-centered cubic (FCC) superlattice as an L21 structure, or body-centered cubic (BCC) unit cell as a B2 structure. However, a low-temperature martensite structure can be produced as an L10, 10M or 14M martensite structures. The crystal lattice structure is highly dependent on the specific elements comprising the alloy. Additionally, special emphasis is placed on phase transitions within Heusler alloys, including martensitic transformations ranging above, near or below room temperature and magnetic transitions. Therefore, divers’ crystallographic defects can be presented in such types of materials affecting their structural and magnetic properties. Moreover, an important property of Heusler compounds, which is the ability to regulate the valence electron concentration through element substitution, is discussed. The possible challenges and remaining issues are briefly discussed.

Structure, magnetism and magnetocaloric properties in performance GdClWO4 compound

Rare earth elements possessing a diverse range of optical, electrical, and magnetic properties has attracted more attention. In the present work, GdClWO4 compound with monoclinic structure was prepared, the structure, magnetism and magnetocaloric effect (MCE) were investigated. The magnetic phase transition temperature (TN), magnetic ground state and maximum magnetic entropy change (−ΔSMmax) were derived from magnetization measurements. Both first principles calculation and experimental results suggest that the compound displays antiferromagnetic (AFM) interactions, with a magnetic transition occurring at 0.6 K, shifting from a paramagnetic (PM) state to an AFM state. The −ΔSMmax is up to 35.2 J kg−1 K−1 (205.9 mJ cm−3 K−1) for GdClWO4 at T = 1.3 K under a magnetic field change of 0–50 kOe. In particular, the volumetric magnetic entropy change still remains 83.1 mJ cm−3 K−1 at 0.5 K and μ0ΔH = 20 kOe, which is almost twice as much as that of commercial refrigerant Gd3Ga5O12 (GGG) under μ0ΔH = 20 kOe, establishing GdClWO4 compound as a potential candidate for cryogenic refrigeration applications.

Large magnetocaloric effect and giant magnetoresistance in rare earth based intermetallic compound ErAl3: construction of magnetic phase diagram

This study explores the magnetic and magnetotransport behavior of polycrystalline ErAl3 compound. The polycrystalline compound adopts HoAl3-type structures with the R-3m space group, No. 166-2 and hR60 configurations. Multiple magnetic orderings and two field-induced metamagnetic transitions are observed. ErAl3 exhibits a significant magnetocaloric effect (MCE), −ΔSM = 15.25 J kg−1 K−1 and high relative cooling power of 383 J kg−1 with applied magnetic field change (ΔH) of 70 kOe near the paramagnetic to ferromagnetic transition, showcasing its potential for magnetic refrigeration technology. The compound also demonstrates metallic behavior, with a notable magnetoresistance of 48.5 % at 2 K due to the suppression of antiferromagnetism. The magnetic phase diagram reveals four distinct phases influenced by temperature and magnetic field, identified through the study of the MCE.

Characterization of magnetic properties, including magnetocaloric effect, of RE5Pt2In4 (RE = Gd-Tm) compounds

The RE5Pt2In4 (RE = Gd-Tm) rare earth compounds have been investigated by means of X-ray diffraction (XRD) as well as by DC and AC magnetometric measurements. The compounds crystallize in an orthorhombic crystal structure of the Lu5Ni2In4-type (Pbam space group, No. 55). With decreasing temperature, the intermetallics undergo a transition from para- to ferro-/ferri- (RE = Gd, Tb, Ho, Er) or antiferromagnetic state (RE = Tm). In case of Dy5Pt2In4, the ferromagnetic state is reached through an intermediate antiferromagnetic order present in a limited temperature range. The critical temperatures of magnetic ordering range from 4.1 K (RE = Tm) up to 108 K (RE = Tb). For the majority of investigated compounds, a cascade of additional magnetic transitions is found below the respective critical temperatures of magnetic ordering. The magnetic moments are found solely on the rare earth atoms, while the moments of the remaining Pt and In atoms are absent or are too small to be detected while accompanied by the strong rare earth’s moments. The magnetocaloric (MCE) performance of RE5T2In4 (RE = Gd-Tm) is found quite good, especially while taking into account the compounds with RE = Ho and Er. Maximum magnetic entropy change (−ΔSMmax) reaches 11.8 (RE = Ho) or 11.4 J ⋅ kg−1 ⋅ K−1 (RE = Er) under magnetic flux density change of 0–9 T. Under the same conditions, the relative cooling power (RCP) and refrigerant capacity (RC) equal 607 and 495 J ⋅ kg−1 (RE = Ho) or 434 and 341 J ⋅ kg−1 (RE = Er).

Magnetic properties and cryogenic magnetocaloric effect in α-Gd2(MoO4)3 compound

Magnetic refrigeration technology has received extensive attention due to its application prospects in various fields. The research of magnetocaloric materials is the basis for the development of magnetic refrigeration technology. In this study, the α-Gd2(MoO4)3 was prepared by the high temperature solid state reaction. By X-ray diffraction characterization, α-Gd2(MoO4)3 crystallizes in monoclinic structure (space group C12/c1). Furthermore, its magnetism and magnetocaloric effect are investigated. The magnetic ordering temperature of α-Gd2(MoO4)3 is less than 1.8 K and there is a second-order phase transition. The maximum magnetic entropy changes are 20.8 and 32.7 J kg−1 K−1 under the field changes of 0–2 T and 0–5 T, respectively. Besides, the refrigeration capacity and relative cooling power are 142.0 and 190 J kg−1 under field change of 0–5 T. These properties indicate that α-Gd2(MoO4)3 is an excellent candidate for low temperature magnetic refrigeration.

Structural and magnetic properties of Gd4Ga2O9 oxide with a large cryogenic magnetocaloric effect

The magnetocaloric effect has been extensively investigated in various types of magnetic solids to not only develop practical magnetic cooling applications but also deepen the understanding of these materials’ underlying inherent properties. Through experimental determination and theoretical calculation, we conducted a systematic investigation of Gd4Ga2O9 oxide in terms of its structural, magnetic, and magnetocaloric properties and found it to crystallize in a monoclinic structure belonging to the space group P21/c and to possess an antiferromagnetic semiconducting ground state. The consistent elements were uniformly distributed up to the nanoscale and presented as Gd3+, Ga3+, and O2 states, respectively. The magnetocaloric performances of Gd4Ga2O9 oxide were checked according to the parameters of maximum magnetic entropy change, refrigerant capacity, and temperature-averaged entropy changes (lift of 5 K), which were determined to be 25.77 J/kgK, 218.27 J/kg, and 23.43 J/kgK under 0–7 T magnetic field change. These parameters of Gd4Ga2O9 oxide are comparable to those of some recently reported materials with prominent performances, which means that it can be considered for cryogenic magnetic cooling applications.

Optimization and development of a new rotary magnetic refrigerator

AbstractMagnetic refrigeration is becoming increasingly relevant as a means to achieve sustainability in refrigeration, thanks to its durability, efficiency, and low environmental impact. This paper regards the design of a new rotary magnetic refrigerator feasible for domestic use at room temperature. An interdisciplinary approach was necessary to perform the design, construction, and optimization of the device through mechanical design, thermo-hydraulic design, and integration into a proper test rig. Optimization of critical parts, such as the regenerator, the magnet structure, and the external heat exchangers, was performed using numerical models. The optimal values of control parameters were determined using a parametric sweep study. The results of all these steps of the study resulted in significant progress in designing and constructing an efficient rotary magnetic refrigerator. This work presents the insights obtained from the project implementation, including the design and construction aspects, presented in a practical way that can guide future projects in the field of magnetic refrigeration. Graphical abstract

Designing Advanced Amorphous/Nanocrystalline Alloys by Controlling the Energy State.

Amorphous alloys, also known as metallic glasses, exhibit many advanced mechanical, physical, and chemical properties. Owing to the nonequilibrium nature, their energy states can vary over a wide range. However, the energy relaxation kinetics are very complex and composed of various types that are coupled with each other. This makes it challenging to control the energy state precisely and to study the energy-properties relationship. This brief review introduces the recent progresses on studying the enthalpy relaxation kinetics during isothermal annealing, for example, the observation of two-step relaxation phenomenon, the detection of relaxation unit (relaxun), the key role of large activation entropy in triggering memory effect, the influence of glass energy state on nanocrystallization. Based on the above knowledge, a new strategy is proposed to design a series of amorphous alloys and their composites consisting of nanocrystals and glass matrix with superior functional properties by precisely controlling the nonequilibrium energy states. As the typical examples, Fe-based amorphous alloys with both advanced soft magnetism and good plasticity, Gd-based amorphous/nanocrystalline composites with large magnetocaloric effect, and Fe-based amorphous alloys with high catalytic performance are specifically described.

Giant magnetocaloric effect and hysteresis loss in MnxFe2-xP0.5Si0.5 (0.7 ≤ x ≤ 1.2) microwires at ambient temperatures

Magnetocaloric microwires are very promising for energy-efficient magnetic refrigeration in micro electromechanical systems (MEMS) and nano electromechanical systems (NEMS). Creating microwires that exhibit large magnetocaloric effects around room temperature represents an important but challenging task. Here, we report a tunable giant magnetocaloric effect around room temperature in MnxFe2-xP0.5Si0.5 (0.7≤x ≤ 1.2) microwires by utilizing a melt-extraction technique paired with thermal treatment and chemical engineering. The isothermal magnetic entropy change (ΔSiso) and Curie temperature (TC) can be tuned by adjusting the Mn/Fe ratio. The TC varies from 351 to 190 K as x increases from 0.8 to 1.2. Among the compositions investigated, the x = 0.9 sample shows the largest value of ΔSiso = 18.3 J kg−1 K−1 for a field change of 5 T around 300 K. After subtracting magnetic hysteresis loss, a large refrigerant capacity of ∼284.6 J kg−1 is achieved. Our study paves a new pathway for the design of novel magnetocaloric microwires for active magnetic refrigeration at ambient temperatures.

Mechanisms of rapid magnetocaloric enhancement of La–Fe–Co–Si alloy by high-temperature hot compression with large deformation

In this study, the microstructure, phase composition, magnetic transition, and magnetocaloric effect of the LaFe10.6Co0.9Si1.5 alloy hot compressed at high temperatures over 1173 K with a strain rate 0.005 s−1 and reduction ratio 50%–70 % are studied. No La(Fe, Si, Co)13 phase is formed until the hot-compression temperature is elevated to 1273 K and the reduction ratio is increased to 70 %. As a result, 86.8 ± 2 wt% 1:13 phases are rapidly obtained in the LaFe10.6Co0.9Si1.5 ingot. The whole process can be completed within only 10 min and no post-annealing process is needed. This fast formation of the La(Fe, Si, Co)13 phases is possibly induced by the directional atomic diffusion, accelerated atomic diffusion, and the stability of the La(Fe, Si, Co)13 phase and structural relaxation caused by the sufficiently restored elastic energy during the hot compression. The LaFe10.6Co0.9Si1.5 ingot hot compressed at 1273 K with a reduction ratio 70 % at a strain rate 0.005/s exhibits a second-order phase transition and negligible magnetic hysteresis. A large magnetic entropy change of 4.4 J/kg.K and a wide working temperature range of 57 K under 2 T are acquired near room temperature. This study proposes a new efficient hot compression route for processing the La–Fe–Co–Si alloy and enhancing the magnetocaloric effect.

Spin switching and magnetocaloric effect of high-entropy orthoferrite single crystal

The concept of high-entropy oxides/alloys was introduced into the rare-earth orthoferrite (RFeO3, R represents a rare-earth ion) system. Doping five different rare-earth ions with equal molar ratios at the R-site, a single crystal of high-entropy orthoferrite (Y0.2Sm0.2Eu0.2Gd0.2Er0.2)FeO3 (HERFO) was synthesized using optical floating zone method. At high temperatures, the weak ferromagnetic (wFM) moments induced by the distortion of the Fe sublattices align along the c axis, with a spin configuration of Γ4. As the temperature decreases, a spin reorientation transition (SRT) occurs from Γ4 to Γ2 due to the Fe3+-R3+ super-exchange interactions, with an immediate state Γ24. The wFM moments gradually rotate from the c axis to the a axis within the ac plane. In the zero-field-cooling (ZFC) mode, both the type-I and type-II spin switching (SSW) are observable along the a axis. Under low magnetic fields, the type-II SSW is magnetically controlled. The trigger temperature and variation in net moment of the type-II SSW exhibit systematic changes concerning the applied magnetic field. The rich magnetic phase transitions in HERFO make it a promising candidate for spintronic applications aimed at spin manipulation. Additionally, HERFO single crystal exhibits a large magnetocaloric effect (MCE) and magnetic entropy anisotropy, with the negative magnetic entropy change (‐ΔSm) along the c axis (14.45 J/(kg·K)) being greater than that along the a and b axes (9.57 J/(kg·K) and 10.32 J/(kg·K)). Consequently, HERFO holds great promise as a novel material for magnetic refrigeration applications aimed at achieving rotational magnetic cooling.

Role of Griffiths phase on magnetocaloric properties and critical behavior of half-doped manganites [La0.5Sr0.5-xCaxMnO3(x = 0, 0.25, 0.5)

In this article, a comprehensive study of the effect of calcium substitution on structural magnetic, magnetocaloric properties, and role of Griffiths phase on magnetocaloric properties of half-doped manganites La0.5Sr0.5-xCaxMnO3(x=0,0.25,0.5)] have been presented. A structural phase transition I4/mcm - Pbnm is observed in the whole series. The system exhibits two magnetic transitions for Ca-00 and Ca-25, whereas only one phase transition is observed for Ca-50. Paramagnetic (PM)-ferromagnetic (FM) transition is observed in the whole series and ferromagnetic (FM) - antiferromagnetic (AFM) phase transition is only observed in Ca-25. Interestingly, short range FM clusters exist in the PM matrix of Ca-50, which is a signature of Griffiths phase (GP). The confirmation of GP has been carried out by performing iso-field magnetization measurements at 200 Oe, 500 Oe, and 1 kOe, respectively. Further magnetocaloric properties have been discussed on the basis of isothermal magnetization curves recorded at certain temperature intervals. Calcium substitution favors the enhancement of magnetic entropy change in the series, especially for Ca-50, a magnetic entropy change of 4.5J/(kgK) with relative cooling power of 180J/kg under 5T magnetic field was observed. Iso-field magnetization and magnetocaloric effect along with critical behavior analysis have been carried out to probe the GP and other inhomogeneities present in the respective series.

Revealing contrary contributions of the magnetic and lattice entropy to the inverse magnetocaloric effect in magnetic shape memory alloy

In this work, we studied the nature and dilemma of the inverse magnetocaloric effect using Ni50Mn36In14 magnetic shape memory alloy. In this context, the inverse magnetocaloric effects of Ni50Mn36In14 magnetic shape memory alloy polycrystalline samples were investigated as a function of annealing heat treatments by the thermo-magnetometry method. Two forms of Ni49TiMn36In14 magnetic shape memory alloy were studied: one that predominantly undergoes a magnetic phase transition and the other that exhibits both a magnetic and martensitic phase transition. The magnetic behaviors and magnetocaloric properties of these alloys were analyzed to investigate the competition between magnetic and lattice contributions to the total entropy change. Finally, the mutually contradictory role of magnetic and lattice contributions was demonstrated.

Three [Ln2Co2] cluster-based three-dimensional frameworks: Syntheses, structure, and magnetocaloric effect

The heterometallic 3d-4f clusters are being researched, for some time now, as being applicable to molecular magnetism. Especially, the Gd3+-containing multi-nuclear clusters attract wide study attention, on account of the significant magnetocaloric effect (MCE). Herein, three-dimensional (3D) 3d-4f heterometallic clusters are successfully gained via solvothermal conditions, formulated as {[Ln2Co2Na2(L)2(C2O4)2(H2O)4]·(H2O)2}n (abbreviated as Ln2Co2, Ln = Gd for 1; Ln = Tb for 2, and Ln = Dy for 3; L = ethylenediaminetetraacetic acid disodium salt). Structural analysis shows that Ln2Co2 clusters are mainly consistent of the [Ln2Co2Na2(L)2(C2O4)2(H2O)4] metal frames, which are the asymmetric building units. Interestingly, [Ln2Co2Na2(L)2(C2O4)2(H2O)4] metal frames can be constructed by one chain-shaped [Ln2(C2O4)2], one [Na2(H2O)2] dimer, and two [CoL(H2O)] units. Tree building units are connected to constitute 3D structure of Ln2Co2. In addition, the metal ions make Gd2Co2 exhibit the magnetic entropy change (-∆Sm = 31.17 J kg−1 K−1 at 2.0 K and 7.0 T) and ideal -∆Sm value at low-field condition (20.18 J kg−1 K−1 at 2.0 K and 2.0 T).

Structural, magnetic and magnetocaloric properties of the Er2BaCu1-xNixO5 oxides

The solid-state magnetic cooling based on the magnetocaloric (MC) effects was recognized as one of the most prospective alternative cooling methods to the gas compression technology. Exploring suitable candidate materials with prominent MC performances remains an urgent research priority in this field. Thus, we herein investigated fabricated the Er2BaCu1-xNixO5 oxides (x = 1/3, 1/2, and 2/3) and experimentally determined their structural and magnetic properties together with their MC performances. All the present studied Er2BaCu1-xNixO5 oxides are crystallized in the RE-211 type oxide structure (space group: Pnma). Considerable reversible low-temperature MC effects and good MC performances have been observed in present studied Er2BaCu1-xNixO5 oxides which were assessed by determination the parameters including the magnetic entropy changes, temperature-averaged entropy changes, and relative cooling power.

Synthesis and investigating of the impact of the barium substitution on the structural, magnetic, magnetocaloric effect and critical properties of La0.7Ba0.3−xMn0.95Fe0.05O3 (x = 0 and 0.06)

Synthesis and investigating of the impact of the barium substitution on the structural, magnetic, magnetocaloric effect and critical properties of La0.7Ba0.3−xMn0.95Fe0.05O3 (x = 0 and 0.06)

Structural and magnetic properties of RE2O2SO4 (RE = Gd, Tb, Dy and Ho) oxides featuring large direct and inverse magnetocaloric effect

In this work, we fabricated the RE2O2SO4 (RE = Gd, Tb, Dy and Ho) oxides by thermal decomposition and systematically determined regarding their structural and magnetic properties, especially of the magnetic phase transition (MPT) and magnetocaloric effect (MCE). All of these RE2O2SO4 oxides are confirmed to crystallize in an orthogonal structure (space group: pmnb); the constituting elements are all distributed uniformly and presented as the RE3+, S6+, and O2− valence states, respectively. They all exhibit a typical cryogenic MPT from paramagnetic to antiferromagnetic (AFM) state together with a field-induced metamagnetic transition (first-order type MPT) from AFM to ferromagnetic state below their MPT temperatures. All of these RE2O2SO4 oxides exhibit considerable direct and inverse cryogenic MCE. The determined direct magnetocaloric parameters of present RE2O2SO4 oxides, especially of Gd2O2SO4 and Ho2O2SO4 oxides, are comparable with most of recently reported RE-based magnetic solids, making them also considerable for practical cryogenic MR applications.