A magnetocaloric effect (MCE) with sizable isothermal entropy change (ΔS) maintained over a broad range of temperatures above the blocking temperature is reported for a rare earth-free superparamagnetic nanoparticle system comprising of Fe–TiN heterostructure. Superparamagnetic iron (Fe) particles were embedded in a titanium nitride (TiN) thin film matrix in a TiN/Fe/TiN multilayered pattern using a pulsed laser deposition method. High angle annular dark-field images in conjunction with dispersive energy analysis, recorded using scanning transmission electron microscopy, show a clear presence of alternating layers of Fe and TiN with a distinct atomic number contrast between Fe particles and TiN. Quantitative information about the isothermal entropy change (ΔS) and the magnetocaloric effect in the multilayer Fe–TiN system has been obtained by applying Maxwell relation to the magnetization vs temperature data at various fields. With the absence of a dynamic magnetic hysteresis above the blocking temperature, the negative ΔS as high as 4.18 × 10 3 J/Km 3 (normal or forward MCE) is obtained at 3 T at 300 K.
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Enhanced Magnetic Cooling through Tailoring the Size-Dependent Magnetocaloric Effect of Iron Nanoparticles Embedded in Titanium Nitride Thin Films
The magnetocaloric effect (MCE) in iron (Fe) nanoparticles incorporated within a titanium nitride (TiN) thin-film matrix grown using pulsed laser deposition (PLD) is investigated in this study. The study demonstrates the ability to control the entropy change across the magnetic phase transition by varying the size of the Fe nanoparticles. The structural characterization carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning transmission electron (TEM) showed that TiN films are (111) textured, while the Fe-particles are mostly spherical in shapes, are single-crystalline, and have a coherent structure with the surrounding TiN thin-film matrix. The TiN thin-film matrix was chosen as a spacer layer since it is nonmagnetic, is highly corrosion-resistive, and can serve as an excellent conduit for extracting heat due to its high thermal conductivity (11 W/m K). The magnetic properties of Fe–TiN systems were investigated using a superconducting quantum interference device (SQUID) magnetometer. In-plane magnetic fields were applied to record magnetization versus field (M–H) and magnetization versus temperature (M–T) curves. The results showed that the Fe–TiN heterostructure system exhibits a substantial isothermal entropy change (ΔS) over a wide temperature range, encompassing room temperature to the blocking temperature of the Fe nanoparticles. Using Maxwell’s relation and analyzing magnetization–temperature data under different magnetic fields, quantitative insights into the isothermal entropy change (ΔS) and magnetocaloric effect (MCE) were obtained for the Fe–TiN heterostructure system. The study points out a considerable negative change in ΔS that reaches up to 0.2 J/kg K at 0.2 T and 300 K for the samples with a nanoparticle size on the order of 7 nm. Comparative analysis revealed that Fe nanoparticle samples demonstrate higher refrigeration capacity (RC) in comparison to Fe thin-film multilayer samples, with the RC increasing as the Fe particle size decreases. These findings provide valuable insights into the potential application of Fe–TiN heterostructures in solid-state cooling technologies, highlighting their enhanced magnetocaloric properties.
more » « less- Award ID(s):
- 1719875
- PAR ID:
- 10549412
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Magnetochemistry
- Volume:
- 9
- Issue:
- 7
- ISSN:
- 2312-7481
- Page Range / eLocation ID:
- 188
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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High-entropy alloys (HEAs) with significant magnetocaloric effects (MCEs) have attracted widespread attention due to their potential magnetic refrigeration applications over a much more comprehensive temperature range with large refrigerant capacity (RC). However, most of them are metallic glasses (MGs) with problems of limited size, resulting in the difficulty of further applications. Therefore, research on HEAs with crystalline structures and giant MCE is urgently needed. In this paper, GdErHoCoM (M = Cr and Mn) rare-earth HEA ingots with orthorhombic structures are developed, and their magnetic behavior and MCE are studied in detail. Phase investigations find that the main phase of GdErHoCoM ingots is probably (GdErHo)Co with an orthorhombic Ho3Co-type structure of a space group of Pnma. The secondary phases in GdErHoCoCr and GdErHoCoMn are body-center-cubic Cr and Mn-rich HoCo2-type phases, respectively. Magnetic investigations reveal that both ingots undergo a first-order magnetic phase transition below their respective Neel temperatures. Above their respective Neel temperatures, a second-order transition is observed. The Neel temperatures are 40 and 56 K for GdErHoCoCr and GdErHoCoMn, respectively. Additionally, the GdErHoCoCr and GdErHoCoMn ingots exhibit maximum magnetic entropy changes and RC values of 12.29 J/kg/K and 746 J/kg and 10.13 J/kg/K and 606 J/kg, respectively, under a magnetic field of 5 T. The ingots GdErHoCoM (M = Cr and Mn) show excellent MEC properties and can be manufactured easily, making them promising for magnetic refrigerant applications.
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Magnetocaloric properties of TbCrO3 and TmCrO3 are reported and compared with those of the previously reported rare-earth chromites RCrO3 (R = Gd, Dy, Ho, and Er) and other perovskite-type oxides. The samples of TbCrO3 and TmCrO3 in this work were synthesized using a citrate gel combustion technique, and their magnetic properties were investigated and compared with those reported previously on RCrO3 (R = Gd, Dy, Ho, and Er). The Cr3+–Cr3+ ordering temperatures were found to strongly depend on the ionic radii of the rare-earth. By fitting the dc magnetization data with modified Curie–Weiss law including the Dzyaloshinsky–Moriya antisymmetric exchange interaction (D) and the symmetric exchange constant Je, spin canting angles (α) were obtained. In general, α was found to increase with the decreasing ionic radii of R3+ in RCrO3. The magnetocaloric properties investigated included the magnetic entropy change (−ΔS) for a given change in magnetic field (ΔH), the corresponding adiabatic temperature change (ΔTad), and their relative variations (ΔTad/ΔH) and (−ΔS/ΔH). It is observed that for RCrO3, (−ΔS) measured in the vicinity of the ordering temperature of R3+–R3+, varies almost as G2/3 where G is the de Gennes factor. Among RCrO3, GdCrO3 shows the largest value of (−ΔS/ΔH), because of its largest G factor and its magnitudes of (ΔTad/ΔH) and (−ΔS/ΔH) compare well with the reported values for the perovskites GdFeO3 and EuTiO3. These comparisons presented here provide useful information on the potential use of these materials in magneto-refrigeration technology.more » « less
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Abstract Martensitic transformation (MT), magnetic properties, and magnetocaloric effect (MCE) in Heusler-type Ni 47 Mn 40 Sn 13− x Cd x ( x = 0, 0.75, 1, 1.25 at. %) metamagnetic shape memory alloys (MetaMSMAs) are investigated, both experimentally and theoretically, as a function of doping with Cd. Ab-initio computations reveal that the ferromagnetic (FM) configuration is energetically more favorable in the cubic phase than the antiferromagnetic (AFM) state in undoped and doped alloys as well. Moreover, it is revealed that the alloys in the ground state exhibit a tetragonal structure confirming the existence of MT, in agreement with the experiments. It was indicated, both in theory and practice, that a reduction of the unit cell volume and an increase of the MT temperature as a function of the Cd doping. Indirect estimations of MCE in the vicinity of MT were carried out by using thermomagnetization curves measured under different magnetic fields up to 5 T. The results demonstrated that the doped alloys exhibit enhanced values of the inverse MCE comparable with those of Ni-Mn-based MetaMSMAs. Maximum magnetic entropy change in a field change of 2 T increases from 3.0 J .k g − 1 K − 1 for the undoped alloy to 3.4 and 5.0 J .k g − 1 K − 1 for the alloys doped with 0.75 and 1 at.% of Cd, respectively. The inverse and conventional MCE were explored by direct measurements of the adiabatic temperature change under the magnetic field change of 1.96 T. The Cd doping increased the maximum of inverse MCE by nearly 78% from 0.9 K to 1.6 K for the undoped and doped alloys, respectively. The results depicted that Cd doping can effectively tailor the structural, magnetic, and MCE properties of the Ni–Mn–Sn MetaMSMAs.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/magnetochemistry9070188
