Magnetic properties of a series of (La0.7Sr0.3MnO3/SrRuO3) superlattices, where the SrRuO3 layer thickness is varying, are examined. A room-temperature magnetocaloric effect is obtained owing to the finite size effect which reduces the TC of La0.7Sr0.3MnO3 layers. While the working temperature ranges are enlarged,, -DeltaSmax values remains similar to the values in polycrystalline La0.7Sr0.3MnO3. Consequently, the relative cooling powers are significantly improved, the microscopic mechanism of which is related to the effect of the interfaces at La0.7Sr0.3MnO3/SrRuO3 and higher nanostructural disorder. This study indicates that artificial oxide superlattices/multilayers might provide an alternative pathway in searching for efficient room-temperature magnetic refrigerators for (nano)microscale systems.
We exploit the magnetic interlayer coupling in La0.7Sr0.3MnO3/SrRuO3 superlattices to realize a crossover between inverse and conventional magnetic entropy changes. Our data reveal a strong anisotropic nature of the magnetocaloric effect due to the magnetic anisotropy of the superlattice. Therefore, artificial superlattices built from ferromagnetic materials that can be used to alter the magnetic structure as well as the magnetic anisotropy, could also be utilized for tuning the magnetocaloric properties, which may open a constructive approach for magnetic refrigeration applications.
We investigate the magnetocaloric properties of certain antiferromagnetic spin systems that have already been or very likely can be synthesized as magnetic molecules. It turns out that the special geometric frustration which is present in antiferromagnets that consist of corner-sharing triangles leads to an enhanced magnetocaloric effect with high cooling rates in the vicinity of the saturation field. These findings are compared with the behavior of a simple unfrustrated spin ring as well as with the properties of the icosahedron. To our surprise, also for the icosahedron large cooling rates c…
The magnetocaloric effect (MCE) in the A-site ordered manganite NdBaMn2O6 is studied. The MCE in this compound has an anomalous behavior. In low magnetic fields, the abrupt transitions between direct and inverse magnetocaloric effect are observed. In a relatively strong magnetic field H=11 kOe the direct and inverse effects are observed only at cooling, while the heating mode reveals only an inverse MCE. The value of the MCE (-ΔS=0.7 J/kg K and ΔS= 1.02 J/kg K for ΔH=11 kOe) does not reach high values, but the proximity of the effects occurring at room temperatures expects the use of both effe…
Over the last two decades, the research activities on magnetocalorics have been exponentially increased leading to the discovery of a wide category of materials including intermetallics and oxides. Even though the reported materials were found to show excellent magnetocaloric properties on laboratory scale, only a restricted family among them could be upscaled toward industrial levels and implemented as refrigerants in magnetic cooling devices. On the other hand, in the most of reported reviews, the magnetocaloric materials are usually discussed in terms of their adiabatic temperature and entr…
$La_{0.7}Ca_{0.3}MnO_3$ samples were prepared in nano- and polycrystalline forms by sol-gel and solid state reaction methods, respectively, and structurally characterized by synchrotron X-ray diffraction. The magnetic properties determined by ac susceptibility and dc magnetization measurements are discussed. The magnetocaloric effect in this nanocrystalline manganite is spread over a broader temperature interval than in the polycrystalline case. The relative cooling power of the poly- and nanocrystalline manganites is used to evaluate a possible application for magnetic cooling below room temp…
The rotating magnetocaloric effect (RMCE) is a recent interest in magnetic refrigeration technique in which the cooling effect is attained by rotating the anisotropic magnetocaloric material from one orientation to the other in a fixed magnetic field. In this work, we report the anisotropic magnetocaloric properties of single crystals of the ferromagnetic Weyl semimetal Co$_{3}$Sn$_{2}$S$_{2}$ for magnetic field $H\parallel c$ axis and $H\parallel ab$ plane. We observed a significant (factor of $2$) difference between the magnetocaloric effect measured in both orientations. The rotating magnet…
We report the characteristic magnetic properties of several members of the rare-earth garnet family, Gd$_3$Ga$_5$O$_{12}$ (GGG), Dy$_3$Ga$_5$O$_{12}$ (DGG), Tb$_3$Ga$_5$O$_{12}$ (TGG), and Nd$_3$Ga$_5$O$_{12}$ (NGG), and compare their relative potential utility for magnetocaloric cooling, including their minimal adiabatic demagnetization refrigeration (ADR) temperatures and relative cooling parameters. A main objective of this work concerns the identification of potential improvements over the magnetocaloric properties of GGG for use in low temperature ADR cryostats. Using Tb$^{+3}$ and Dy$^{+…
The non-stoichiometric Heusler alloy Ni$_{50}$Mn$_{36}$In$_{14}$ undergoes a martensitic phase transformation in the vicinity of 345 K, with the high temperature austenite phase exhibiting paramagnetic rather than ferromagnetic behavior, as shown in similar alloys with lower-temperature transformations. Suitably prepared samples are shown to exhibit a sharp transformation, a relatively small thermal hysteresis, and a large field-induced entropy change. We analyzed the magnetocaloric behavior both through magnetization and direct field-dependent calorimetry measurements. For measurements passin…
We have measured and calculated the magnetocaloric effect in macroscopic samples of oriented high-spin molecular clusters like Mn12 and Fe8 as a function of the temperature and both the intensity and the sweeping rate of the applied magnetic field. We have observed a high magnetic entropy variation around the blocking temperature of the magnetic moment of molecules and calculated the shift of the entropy variation and cooling temperature, with the sweeping rate of the magnetic field.
Here we report magneto-thermal properties of Gd3Ir compounds using magnetic and heat capacity data. We observed large isothermal entropy change, adiabatic temperature change and relative cooling power are 4.1J/Kg, 4K and 437J/Kg on 50KOe respectively.
We investigate the magnetocaloric effect (MCE), relative cooling power (RCP) and crystalline structure in Sb substituted CrTe_{1-x}Sb_{x} (0 \leq x \leq 0.2) alloy. The Rietveld refinement of the XRD pattern of CrTe1-xSbx showed the emerging of pure hexagonal NiAs structure with P63/mmc (194) space group with increasing Sb substitution. We detect a slight increase in the basal plane a-lattice parameter, with a much larger reduction in the c-axis. Magnetic isotherms were measured in the temperature range of 50-400K. The results revealed an increase in the maximum entropy change |S_{M}(T,H)| wit…
We discuss the magnetocaloric properties of gadolinium containing magnetic molecules which potentially could be used for sub-Kelvin cooling. We show that a degeneracy of a singlet ground state could be advantageous in order to support adiabatic processes to low temperatures and simultaneously minimize disturbing dipolar interactions. Since the Hilbert spaces of such spin systems assume very large dimensions we evaluate the necessary thermodynamic observables by means of the Finite-Temperature Lanczos Method.
The prospect of efficient solid state refrigeration at room temperature is driving research into magnetic cooling engine design and magnetic phase transition-based refrigerants. In this Viewpoint an Ashby-style map of magnetic refrigerant properties is constructed, comparing popular materials with limits derived from an idealised first order transition model. This comparison demonstrates the potential for new magnetocaloric material systems to be established through structural control and optimisation at the atomic-, nano- and micro-scale.
Magnetic entropy and adiabatic temperature changes in and above the room-temperature region has been measured for La0.7Sr0.3Mn1-xM'xO3 (M' = Al, Ti) by means of magnetization and heat capacity measurements in magnetic fields up to 6 T. The magnetocaloric effect becomes largest at the ferromagnetic ordering temperature Tc that is tuned to ~300 K by the substitution of Al or Ti for Mn. While the substitution of Al for Mn drastically reduces the entropy change, it extends considerably the working temperature span and improves the relative cooling power. The magnetocaloric effect seems to be only …
As materials with suppressed ordering temperatures and enhanced ground state entropies, frustrated magnetic oxides are ideal candidates for cryogenic magnetocaloric refrigeration. While previous materials design has focused on tuning the magnetic moments, their interactions, and density of moments on the lattice, there has been relatively little attention to frustrated lattices. Prior theoretical work has shown that the magnetocaloric cooling rate at the saturation field is proportional to a macroscopic number of soft mode excitations that arise due to the classical ground state degeneracy. Th…
A perspective magneto-thermo-electric cooling device (MTECD) comprising a central magnetocaloric (MC) material (e.g., Gd) sandwiched by two thermoelectric (TE) materials (e.g., MnP) is proposed. The presence of the TE materials in the MTECD guides the heat flow direction and enhances heat pulsation. In this case, the usage of a ferromagnetic TE material that combines large TE with small MC properties within a similar temperature region can enhance the magnetic flux density and heat exchange efficiency. Here, we show that MnP nanorod-structured films with desired magnetic, MC and TE properties …
The magnetocaloric effect (MCE) of A-site ordered PrBaMn2O6 manganite has been studied by direct methods and by the specific heat measurements. Direct measurements of the MCE in low magnetic fields were performed using recently proposed modulation technique and by classic direct method in high fields. Direct and inverse MCE are observed at Curie and Neel points correspondingly. A value of the inverse MCE in the heating run is less than in the cooling regime. This effect can be attributing to competition between ferromagnetic and antiferromagnetic interactions. Indirectly estimated and direct M…
Hysteresis is more than just an interesting oddity, which occurs in materials with a first-order transition. It is a real obstacle on the path from existing lab-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 how to minimize losses associated with thermal hysteresis in order…
We report the \QTR{it}{pinned/biased} \QTR{it}{moment} in the superlattices consisting of ferromagnetic (FM) SrRuO$_3$ and antiferromgnetic (AFM) SrMnO$_3$. This superlattice system shows anisotropy and oriented pinning/biasing in the field-cooled (FC) hysteresis loop. The in-plane cooling-field provides antiferromagnetic orientations while out-of-plane cooling-field provides ferromagnetic orientations to the pinned/biased moments. The spacer layer thickness, strength and orientation of magnetic field, cooling field, and driving current influence the pinning strength. We propose that the magne…
Two-dimensional magnets could potentially revolutionize information technology, but their potential application to cooling technology and magnetocaloric effect (MCE) in a material down to the monolayer limit remain unexplored. Herein, we reveal through multiscale calculations the existence of giant MCE and its strain tunability in monolayer magnets such as CrX$_3$ (X=F, Cl, Br, I), CrAX (A=O, S, Se; X=F, Cl, Br, I), and Fe$_3$GeTe$_2$. The maximum adiabatic temperature change ($ΔT_\text{ad}^\text{max}$), maximum isothermal magnetic entropy change, and specific cooling power in monolayer CrF$_3…
Structural, magnetic and magnetocaloric properties of Fe2P-based Mn-Fe-P-Si compounds were investigated. The study reveals a large magneto-elastic coupling that starts to develop in the paramagnetic state and grows when the ferromagnetic transition temperature is approached. Based on the behavior of the magneto-elastic coupling, we show the thermal evolution of the magnetic moments. On cooling, magnetic moments on the tetrahedral site form and gradually increase in the paramagnetic state. At the magnetic ordering temperature the moments attain a much larger value in a discontinuous step. We al…
Polycrystalline CrTe1-xSex samples were prepared using the conventional solid-state reaction technique and characterized by x-rad diffraction, temperature- and field- dependent magnetization for possible use in magnetocaloric cooling. Rietveld refinement revealed two phases in all prepared samples; a minor monoclinic phase that decreases with Se concentration until it vanishes near 10% of Se, and a major hexagonal one. At high temperature, CrTe1-xSex is paramagnetic, with ferromagnetic phase transition occurs at Tc ~332, 320, 318, 310, 299, and 295 K for x= 0.00, 0.02, 0.04, 0.06, 0.08, and 0.…
The magnetic and magnetocaloric properties of Ga1-xCMn3+x have been investigated. Reversible magnetocaloric effect (MCE) occurs near the Curie temperature TC. The magnetic entropy change decreases with increasing x, though TC and magnetization increases. Meanwhile, the temperature span of vs. T plot becomes well broadened with x. Due to the competition between the broadening temperature span and decreasing, the relative cooling power (RCP) increases initially, and then decreases with increasing x. The largest RCP (2.1 J/cm3, under 45 kOe) observed when x=0.07 (TC = 296.5 K) is comparable to th…
Inelastic neutron scattering measurements were performed on single crystals of the antiferromagnetic compound Mn5Si3 in order to investigate the relation between the spin dynamics and the magneto-thermodynamic properties. It is shown that among the two stable antiferromagnetic phases of this compound, the high temperature one has an unusual magnetic excitation spectrum where propagative spin-waves and diffuse spin-fluctuations coexist. Moreover, it is evidenced that the inverse magnetocaloric effect of Mn5Si3, the cooling by adiabatic magnetization, is associated with field induced spin-fluctu…
We have studied the magnetocaloric effect (MCE) in the shape-memory Heusler alloy Ni$_{50}$Mn$_{35}$In$_{15}$ by direct measurements in pulsed magnetic fields up to 6 and 20 T. The results in 6 T are compared with data obtained from heat-capacity experiments. We find a saturation of the inverse MCE, related to the first-order martensitic transition, with a maximum adiabatic temperature change of $ΔT_{ad} = -7$ K at 250 K and a conventional field-dependent MCE near the second-order ferromagnetic transition in the austenitic phase. The pulsed magnetic field data allow for an analysis of the temp…
We report on measurements of the adiabatic temperature change in the inverse magnetocaloric Ni$_{50}$Mn$_{34}$In$_{16}$ alloy. It is shown that this alloy heats up with the application of a magnetic field around the Curie point due to the conventional magnetocaloric effect. In contrast, the inverse magnetocaloric effect associated with the martensitic transition results in the unusual decrease of temperature by adiabatic magnetization. We also provide magnetization and specific heat data which enable to compare the measured temperature changes to the values indirectly computed from thermodynam…
Recent research dealing with magnetocaloric effect (MCE) study of antiferromagnetic (AFM) low dimensional spin systems have revealed a number of fascinating ground-state crossover characteristics upon application of external magnetic field. Herein, through MCE investigation we have explored field-induced quantum level-crossing characteristics of one such spin system: NH4CuPO4.H2O (NCP), an AFM spin 1/2 dimer. Experimental magnetization and specific heat data are presented and the data have been employed to evaluate entropy, magnetic energy and magnetocaloric properties. We witness a sign chang…
The existence and feasibility of the multicaloric, polycrystalline material 0.8Pb(Fe1/2Nb1/2)O3-0.2Pb(Mg1/2W1/2)O3, exhibiting magnetocaloric and electrocaloric properties, are demonstrated. Both the electrocaloric and magnetocaloric effects are observed over a broad temperature range below room temperature. The maximum magnetocaloric temperature change of ~0.26 K is obtained with a magnetic-field amplitude of 70 kOe at a temperature of 5 K, while the maximum electrocaloric temperature change of ~0.25 K is obtained with an electric-field amplitude of 60 kV/cm at a temperature of 180 K. The mat…
Magnetocaloric cooling offers the potential to improve the efficiency of refrigeration devices and hence cut the significant CO2 emissions associated with cooling processes. A critical issue in deployment of this technology is the mechanical degradation of the magnetocaloric material during processing and operation, leading to limited service-life. The mechanical properties of hydrogenated La(Fe,Mn,Si)13-based magnetocaloric material are studied using macroscale bending tests of polycrystalline specimens and in situ micropillar compression tests of single crystal specimens. The impact of hydro…
The advent of caloric materials for magnetocaloric, elastocaloric, and electrocaloric cooling is changing the landscape of solid state cooling technologies with potentials for high-efficiency and environmentally-friendly residential and commercial cooling as well as heating applications. Given that caloric materials are ferroic materials which undergo first (or second) order transitions near room temperature, they open up intriguing possibilities for novel multiferroic devices with hitherto unexplored functionalities coupling their thermal properties with different fields (magnetic, electric, …
The interplay of charge, spin, orbital and lattice degrees of freedom has recently received great interest due to its potential to improve the magnetocaloric effect (MCE) for the purpose of magnetic cooling applications. Here we propose a new mechanism for a giant inverse MCE in rare-earth tetraborides, especially for Ho1-xDyxB4 (x = 0.0, 0.5, and 1.0). For x = 0.0, 0.5, and 1.0, the maximum entropy changes of the giant inverse MCE are found to be 22.7 J/kgK, 19.6 J/kgK, and 19.0 J/kgK with critical fields of 25 kOe, 40 kOe, and 50 kOe, respectively. It is remarkable that such a giant MCE is r…
We report the structural, magnetic properties, and magnetocaloric effect of a new polycrystalline compound of $\mathrm{Tb_2Rh_3Ge}$. This present compound crystallizes with $\mathrm{Mg_2Ni_3Si}$-type of rhombohedral Laves phases (space group $R\overline{3}m$, hR18). The magnetic properties and magnetocaloric effect of the $\mathrm{Tb_2Rh_3Ge}$ is explored through dc-magnetization measurements. Temperature dependence of magnetization revealed that the compound exhibits ferromagnetic behavior with $T_C$$=$56 K. The field dependence of magnetization indicates that $\mathrm{Tb_2Rh_3Ge}$ is a soft …
Composition-Driven High-Entropy Alloys with Enhanced Magnetocaloric Properties
Indian Institute of Technology Kharagpur（印度理工学院卡拉格普尔分校）；Chalmers University of Technology（查尔姆斯理工大学）；Federal University of ABC（ABC联邦大学）；Southern Illinois University（南伊利诺伊大学）
The first order magneto-structural transition ($T_t\simeq95$ K) and magnetocaloric effect in MnNiGe$_{0.9}$Ga$_{0.1}$ are studied via powder x-ray diffraction and magnetization measurements. Temperature dependent x-ray diffraction measurements reveal that the magneto-structural transition remains incomplete down to 23 K, resulting in a coexistence of antiferromagnetic and ferromagnetic phases at low temperatures. The fraction of the high temperature Ni$_2$In-type hexagonal ferromagnetic and low temperature TiNiSi-type orthorhombic antiferromagnetic phases is estimated to be $\sim 40\%$ and $\s…
High cooling power of magnetocaloric refrigeration can be achieved only at large amounts of heat, which can be transferred in one cycle from cold end to hot end at quasi-isothermal conditions. The simple experimental method for direct measurement of the transferred heat from material with magnetocaloric effect (MCE) to massive nonmagnetic block at quasi-isothermal conditions was proposed. The vacuum calorimeter was designed for the simultaneous measurements of MCE both at adiabatic conditions (deltaT) and quasi-isothermal conditions (deltaQ) in the magnetic fields of Bitter coil magnet. This c…
We report on calorimetry under applied hydrostatic pressure and magnetic field at the antiferromagnetic (AFM)-ferromagnetic (FM) transition of Fe$_{49}$Rh$_{51}$. Results demonstrate the existence of a giant barocaloric effect in this alloy, a new functional property that adds to the magnetocaloric and elastocaloric effects previously reported for this alloy. All caloric effects originate from the AFM/FM transition which encompasses changes in volume, magnetization and entropy. The strong sensitivity of the transition temperatures to both hydrostatic pressure and magnetic field confers to this…
Frustrated lanthanide oxides with dense magnetic lattices are of fundamental interest for their potential in cryogenic refrigeration due to a large ground state entropy and suppressed ordering temperatures, but can often be limited by short-range correlations. Here, we present examples of frustrated fcc oxides, Ba$_2$GdSbO$_6$ and Sr$_2$GdSbO$_6$ and the new site-disordered analog Ca$_2$GdSbO$_6$ ([CaGd]$_A$[CaSb]$_B$O$_6$), in which the magnetocaloric effect is influenced by minimal superexchange ($J_1 \sim 10$ mK). We report on the crystal structures using powder x-ray diffraction and the bu…
We report anisotropic magnetocaloric effect and magnetic critical behavior in van der Waals crystal CrCl$_3$. The maximum magnetic entropy change $-ΔS_M^{max} \sim 14.6$ J kg$^{-1}$ K$^{-1}$ and the relative cooling power $RCP \sim 340.3$ J kg$^{-1}$ near $T_c$ with a magnetic field change of 5 T are much larger when compared to CrI$_{3}$ or CrBr$_{3}$. The rescaled $ΔS_M(T,H)$ curves collapse onto a universal curve, confirming the second order ferromagnetic transition. Further critical behavior analysis around $T_c$ presents a set of critical exponents $β$ = 0.28(1) with $T_c$ = 19.4(2) K, $γ…
We report a detailed study of the magnetocaloric effect in heterostructures of La2NiMnO6 and La2/3Sr1/3MnO3. The shape, width and magnitude of the temperature dependence of the magnetic entropy change ($ΔS_{m}$) for these multilayer samples can be tuned and controlled by changing their layout. A large $ΔS_{m}$ over a wide temperature range which goes beyond room temperature is observed in all samples. We observe a temperature-independent table-top-like $ΔS_{m}$ over a temperature range as large as 100 K in the trilayer samples. La2NiMnO6 double perovskite with multiple magnetic phase transitio…
The isostructural alloying of two compounds with extremely different magnetic and thermo-structural properties has resulted in a new system, (MnNiSi)1-x(FeCoGe)x, that exhibits extraordinary magnetocaloric properties with an acute sensitivity to applied hydrostatic pressure (P). Application of hydrostatic pressure shifts the first-order phase transition to lower temperature ($Δ$ T=-41 K with P=3.43 kbar) but preserves the giant value of isothermal entropy change (-$Δ$S$\max$=143.7 J/kg K for a field change of ΔB=5 T at atmospheric pressure). Together with the magnetic field, this pressure-indu…
This work aims to present an analytical and numerical study of the magnetocaloric effects (MCE) providing realistic proposals about materials that should be chosen in the design of new refrigerator appliances around the room temperature. Starting from a spin Hamiltonian including the exchange interaction, the single-ion anisotropy and the applied magnetic field terms, we have calculated the partition function at a given temperature and derived a set of relevant physical quantities as magnetization, magnetic entropy and specific heat and analyzed their behavior with atomic parameters as spin, e…
We report the effect of exchange frustration on the magnetocaloric properties of GdCrTiO$_5$ compound. Due to the highly exchange-frustrated nature of magnetic interaction, in GdCrTiO$_5$, the long-range antiferromagnetic ordering occurs at much lower temperature $T_N$=0.9 K and the magnetic cooling power enhances dramatically relative to that observed in several geometrically frustrated systems. Below 5 K, isothermal magnetic entropy change (-$ΔS_{\rm m}$) is found to be 36 J kg$^{-1}$ K$^{-1}$, for a field change ($ΔH$) of 7 T. Further, -$ΔS_{\rm m}$ does not decrease from its maximum value …
Anomalous magnetocaloric effects in the quasi-one-dimensional antiferromagnet BaCo$_2$V$_2$O$_8$
Peking University（北京大学）；Huazhong University of Science and Technology（华中科技大学）；Southern University of Science and Technology（南方科技大学）；Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences（中国科学院福建物质结构研究所）
We have investigated magnetization(M), magnetocaloric effect(MCE) and magnetothermopower(MTEP) in polycrystalline Pr0.6Sr0.4MnO3, which shows a second-order paramagnetic to ferromagnetic transition near room temperature (TC = 305 K). However, field-cooled M(T) within the long range ferromagnetic state shows an abrupt decrease at TS = 86 K for H < 3 T. The low temperature transition is first-order in nature as suggested by the hysteresis in M(T) and exothermic/endothermic peaks in differential thermal analysis for cooling and warming cycles. The anomaly at TS is attributed to a structural trans…
