We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La0.7Sr0.3Mn1-xFexO3 (x = 0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T = 10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (Tc) and saturation magnetization up to x = 0.15 but a dramatic change occurs for x = 0.2. The x = 0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (DSm) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J/KgK at 343 K (x = 0.05) to 1.3 J/KgK at 105 K (x = 0.2), under H = 5 T. The La0.7Sr0.3Mn0.93Fe0.07O3 sample shows negligible hysteresis loss, operating temperature over 60 K range around room temperature with refrigerant capacity of 225 J/Kg, and magnetic entropy of 4 J/kgK which will be an interesting compound for application in room temperature refrigeration.
Role of Fe substitution on the anomalous magnetocaloric and magnetoresistance behavior in Tb(Ni1-xFex)2 compounds
我们报告的磁性，磁热和磁电阻的结果在Tb（Ni 1-xFex）2化合物与x=0，0.025和0.05。Fe取代导致的有序温度从36 K x=0到124 K x=0.05的增加。与TbNi 2中看到的单个尖锐MCE峰相反，Fe取代的化合物的MCE峰相当宽。我们把这种反常的MCE行为归因于Fe取代引起的Tb矩的随机化。磁性和磁阻的结果似乎证实了这一命题。本研究还表明，在本化合物中观察到的异常磁热和磁电阻行为类似于Ho（Ni，Fe）2化合物。
A detailed study on the crystal structure and bulk magnetic properties of Cr substituted Ising type lanthanide gallium garnets $Ln_3\text{CrGa}_4\text{O}_{12}$ ($Ln$ = Tb, Dy, Ho) has been carried out using room temperature powder X-Ray and neutron diffraction, magnetic susceptibility, isothermal magnetisation and heat capacity measurements. The magnetocaloric effect (MCE) in $Ln_3\text{CrGa}_4\text{O}_{12}$ is compared to that of $Ln_3\text{Ga}_5\text{O}_{12}$. In lower magnetic fields attainable by a permanent magnet ($\leq$ 2 T), Cr substitution greatly enhances the MCE by 20% for $Ln$ = Dy…
Recently, a massive magnetocaloric effect near the liquefaction temperature of hydrogen has been reported in the ferromagnetic material HoB$_{2}$. Here we investigate the effects of Dy substitution in the magnetocaloric properties of Ho$_{1-x}$Dy$_{x}$B$_{2}$ alloys ($\textit{x}$ = 0, 0.3, 0.5, 0.7, 1.0). We find that the Curie temperature ($\textit{T}$$_{C}$) gradually increases upon Dy substitution, while the magnitude of the magnetic entropy change |$Δ\textit{S}_{M}$| at $\textit{T}$ = $\textit{T}_{C}$ decreases from 0.35 to 0.15 J cm$^{-3}$ K$^{-1}$ for a field change of 5 T. Due to the pr…
We report the effect of partial substitution of Dy-site by rare-earths (R=Gd, Er and La)on the magnetic and magnetocaloric behavior of a mixed metal oxide DyFe0.5Cr0.5O3.Structural studies reveal that substitution of Dy by R has a minimal influence on the crystal structure. Magnetic and heat capacity studies show that the magnetic transition around 121 K observed for DyFe0.5Cr0.5O3 remains unchanged with rare-earth substitution, whereas the lower magnetic transition temperature is suppressed/enhanced by magnetic/non-magnetic substitution. In all these compounds, the second order nature of magn…
Influence of Ni substitution on the phase transitions and magnetocaloric effect of NdCo2 at cryogenic temperatures
Institute for Energy Technology (IFE)（能源技术研究所）；Technical University of Darmstadt（达姆施塔特工业大学）；Helmholtz-Zentrum Dresden-Rossendorf（亥姆霍兹德累斯顿-罗斯多夫中心）；Technische Universität Dresden（德累斯顿工业大学）；Paul Scherrer Institute (PSI)（保罗谢勒研究所）
Giant magnetocaloric (GMC) materials constitute a requirement for near room temperature magnetic refrigeration. (Fe,Mn)$_2$(P,Si) is a GMC compound with strong magnetoelastic coupling. The main hindrance towards application of this material is a comparably large temperature hysteresis, which can be reduced by metal site substitution with a nonmagnetic element. However, the (Fe,Mn)$_2$(P,Si) compound has two equally populated metal sites, the tetrahedrally coordinated $3f$ and the pyramidally coordinated $3g$ sites. The magnetic and magnetocaloric properties of such compounds are highly sensiti…
In this work, we investigate the magnetic structures of $(Fe_{1-x}Mn_x)_2AlB_2$ solid-solution quaternaries in the $x = 0$ to $1$ range using x-ray and neutron diffraction, magnetization measurements, and mean-field theory calculations. While $Fe_2AlB_2$ and $Mn_2AlB_2$ are known to be ferromagnetic (FM) and antiferromagnetic (AFM), respectively, herein we focused on the magnetic structure of their solid solutions, which is not well understood. The FM ground state of $Fe_2AlB_2$ becomes a canted AFM at $x \approx 0.2$, with a monotonically diminishing FM component until $x \approx 0.5$. The FM…
Large thermal hysteresis in the MnFe(P, Si, B) system hinders the heat exchange rate and thus limits the magnetocaloric applications at high frequencies. Substitution of Mn by V in Mn1-xVxFe0.95P0.593Si0.33B0.077 and Mn1-xVxFe0.95P0.563Si0.36B0.077 alloys was found to reduce the thermal hysteresis due to a decrease in the latent heat. Introducing V increases both the field-induced transition temperature shift and the magnetic moment per formula unit. Thus, a decease in the thermal hysteresis is obtained without losing the giant magnetocaloric effect. In consequence, an ultralow hysteresis (0.7…
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…
The nature of the magnetic transition, critical scaling of magnetization, and magnetocaloric effect in Mn$_{1+x}$Fe$_{4-x}$Si$_{3}$ ($ x =$ 0 to 1) are studied in detail. Our measurements show no thermal hysteresis across the magnetic transition for the parent compound which is in contrast with the previous report and corroborate the second order nature of the transition. The magnetic transition could be tuned continuously with Mn substitution at the Fe site. The Mn substitution leads to a linear increase in the unit cell volume and a slight reduction in the effective moment. A detailed critic…
Using Density Functional Theory and a thermodynamic model [Physical Review B 86, 134418 (2012)], in this paper, we provide an approach to systematically screen compounds of a given Heusler family to predict ones that can yield giant magnetocaloric effect driven by a first-order magneto-structural transition. We apply this approach to two Heusler series Ni$_{2-x}$Fe$_{x}$Mn$_{1+z-y}$Cu$_{y}$Sb$_{1-z}$ and Ni$_{2-x}$Co$_{x}$Mn$_{1+z-y}$Cu$_{y}$Sb$_{1-z}$, obtained by cosubstitution at Ni and Mn sites. We predict four new compounds with potentials to achieve the target properties. Our computation…
We report a systematic investigation of the magnetic and magnetocaloric properties of Dy5Pd2 and Dy5PdNi. Our study on these compounds gave evidence that they exhibit complex magnetic behaviour along with the presence of glass-like magnetic phase. Furthermore, in these compounds both second order and first order phase transitions were present, which were validated through Arrott plots and Landau parameter analysis. AC susceptibility along with time dependent magnetisation study has confirmed the presence of double cluster glass-like freezing in both Dy5Pd2 and Dy5PdNi. These compounds show sig…
A study investigating the effect of Sn substitution on the magnetocaloric properties of Mn$ _{3} $Ga$ _{(1-x)} $Sn$ _{x} $C compounds reveals that nature of the MCE has a strong dependence on the nature of the magnetic ordering. For small amounts of Sn ($ x\leq0.2 $) the MCE is of the inverse type wherein an increase in the applied field beyond 5T gives rise to a table like temperature dependence of the entropy due to a coupling between the first order FM - AFM transition and the field induced AFM - FM transition. Replacement of Ga by larger concentrations of Sn ($ x\geq0.71 $) $(ΔS_M)$ result…
Derivation of a non-stoichiometric 1/1 quasicrystal approximant from a stoichiometric 2/1 quasicrystal approximant and maximization of magnetocaloric effect
In previous studies, we have reported that double perovskite La2NiMnO6 presents a non-negligible potential for room temperature magnetocaloric tasks. With the aim of improving even further the cooling performances and the working temperature range of double perovskites, we report the magnetic and magnetocaloric properties of La2MnFeO6 and ALaMnFeO6 (A = Sr, Ba, Ca) compounds. X-ray diffraction (XRD) and Rietveld refinement show that La2MnFeO6 (LMFO) and CaLaMnFeO6 (CLMFO) samples crystallize in an orthorhombic structure with the Pnma space group. However, a rhombohedral structure with the R3C …
Cementite-type carbides are of interest for magnetocaloric applications owing to their temperature- or pressure-induced magnetic phase transition. Here, using first-principles calculations, we investigate the magnetism and the magnetic phase transition in iron carbide (Fe3C) with the substitution of Cr atoms at Fe sites with the strain effect. The presence of Cr atoms is found to give rise to a second-order magnetic phase transition from a ferromagnetic phase for Fe3C to a nonmagnetic phase in chromium carbide (Cr3C).While the ternary Fe2CrC and Cr2FeC compounds prefer the ferrimagnetic ground…
In an effort to produce Giant Magnetocaloric effect (GMCE) near room temperature, in a first ever such study, the austenite transformation temperature (As) was fine tuned to ferromagnetic Curie temperature (TC) in Ferromagnetic Shape Memory Alloys (FSMA) and a large GMCE of delta-SM = - 81.75 J/Kg-K was achieved in Ni50Mn18.5Cu6.5Ga25 alloy during reverse martensitic transformation (heating cycle) for a magnetic field change of 9 T at 302.5 K. Fine tuning of As with TC was achieved by Cu substitution in Ni50Mn25-xCuxGa25 (0< x < 7.0)-based FSMAs. Characterizations of these alloys were carried …
The magnetocaloric effect in the metamagnetic Ni43Mn37.9In12.1Co7 Heusler alloy is directly studied experimentally under the adiabatic and quasi-isothermal conditions in a magnetic field with induction of up to 14 T.
The present Letter describes the magnetocaloric effect of a diamagnetic material with a magnetic field $B_\parallel$ along the $z$ axis and a transversal and oscillating field $B_\perp (\ll B_\parallel)$ parallel to the $x-y$ plane. We show that the magnetocaloric potentials due to a change in $B_\parallel$ is the same as those due to a change in the frequency of $B_\perp$. These results raise the possibility of building magnetocaloric devices without moving parts, since changing frequency is a simple electronic issue, while changing the field from permanent magnets depends on mechanical aspec…
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.
It is known that orthorhombic RMnO3 multiferroics (R = magnetic rare earth) with low symmetry exhibit a large rotating magnetocaloric effect because of their strong magnetocrystalline anisotropy. In this paper, we demonstrate that the hexagonal ErMnO3 single crystals also unveils a giant rotating magnetocaloric effect that can be obtained by spinning them in constant magnetic fields around their a or b axes. When the ErMnO3 crystal is rotated with the magnetic field initially parallel to the c-axis, the resulting entropy change reaches maximum values of 7, 17 and 20 J/kg K under a constant mag…
This chapter reviews the basic physics and thermodynamics that govern magnetocaloric materials. The thermodynamics of magnetic materials is discussed by introducing relevant free energy terms together with their microscopic origin leading to a discussion of the sources of entropy that can change in an applied magnetic field. Such entropies account for measurable magnetocaloric effects, especially in the vicinity of magnetic phase transitions. Particular attention is devoted to first order magnetic transitions that involve the coupling of spin, lattice, electronic and anisotropic magneto-crysta…
We study the magnetocaloric effect and critical behavior of Co$_2$Cr$_{1-x}$Mn$_x$Al ($x=$ 0.25, 0.5, 0.75) Heusler alloys across the ferromagnetic (FM) transition (T$_{\rm C}$). The Rietveld refinement of x-ray diffraction patterns exhibit single phase cubic structure for all the samples. The temperature dependent magnetic susceptibility $χ$(T) data show a systematic enhancement in the Curie temperature and effective magnetic moment with Mn concentration, which is consistent with the Slater-Pauling behavior. The M(H) isotherms also exhibit the FM ordering and the analysis of $χ$(T) data indic…
In this paper, we report on the magnetocaloric properties of some selected multiferroic oxides, namely HoMn2O5 and La2(Ni,Co)MnO6 compounds which exhibit transition points from 10K up to almost room temperature. In order to avoid grain boundary effects and structural inhomogeneity observed frequently in polycrystalline samples, only single crystals were considered for this study.
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…
This work investigates the magnetic properties and the magnetocaloric effect in the spin-1 Blume-Capel model. The study was carried out using the mean-field theory from the Bogoliubov inequality to obtain the expressions of free energy, magnetization and entropy. The magnetocaloric effect was calculated from the variation of the entropy obtained by the mean-field theory. Due to the dependence on the external magnetic field and the anisotropy included in the model, the results for the magnetocaloric effect provided the system with first-order and continuous phase transitions. To ensure the resu…
We present the results of a comparative analysis of the magnetocaloric effect (MCE) in Pr0.7Sr0.2Ca0.1MnO3, through direct and indirect measurements, using experimentally measured magnetization, specific heat, magnetostriction, resistivity, thermal diffusivity and thermal conductivity parameters. We have demonstrated that the change in each parameter in response to a magnetic field near the ferromagnetic-paramagnetic phase transition temperature of the material correlates with the change in magnetic entropy. These findings allow us to interrelate these parameters and provide an alternative, ef…
As one of magnetic refrigerants with giant magnetocaloric effect (GMCE), MnFePGe-based compounds had drawn tremendous attention due to their many advantages for practical applications. In this paper, correlations among preparation conditions, magnetic and crystal structures, and magnetocaloric effects (MCE) of the MnFePGe-based compounds are reviewed. Structure evolution and phase transformation in the compounds as a function of temperature, pressure, and magnetic field were reported. Influences of preparation conditions to the chemical composition and microstructure homogeneity of the compoun…
The effect of the short milling times on R5(Si,Ge)4 R =Gd, Tb magnetocaloric material properties was investigated. In particular, the effect of milling on atomic structure, particles size and morphology, magnetic, and magnetocaloric effect was studied. With short milling times (< 2.5h), a reduction of the Gd5Si1.3Ge2.7 and Tb5Si2Ge2 particles size was achieved down to approximately 3.5 DSm. For both compositions the main differences are a consequence of the milling effect on the coupling of the structural and magnetic transitions. In the Gd5Si1.3Ge2.7 case, a second-order phase transition emer…
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…
Among the magnetic materials, those with ferromagnetic character are, by far, the most studied in what concerns applications of the magnetocaloric effect. However, recently, diamagnetic materials received due attention never received before, and an oscillatory behavior, analogous to the de Haas-van Alphen effect, has been found. The present effort describes in details the magnetocaloric properties of a 2D non-relativistic material (a Gold thin film, for instance), where oscillations, depending on the reciprocal magnetic field $1/B$, are found. A comparison of the magnetic entropy change per el…
Barocaloric and Magnetocaloric Effects in Fe49Rh51
本文报道了在外加静水压和磁场作用下Fe $_{49}$ Rh $_{51}$的反铁磁（AFM）-铁磁（FM）相变的量热研究。结果表明，存在一个巨大的压热效应，在这种合金，一个新的功能特性，增加了磁热和弹性热效应，以前报道的这种合金。所有的热效应都源于AFM/FM转变，其中包括体积、磁化强度和熵的变化。转变温度对流体静压和磁场的强烈敏感性赋予该合金优异的压热和磁热强度值（$|ΔS|$/$Δp$ $\sim$ 12 J kg $^{-1}$ K $^{-1}$ kbar $^{-1}$ and $|ΔS|$/$μ_0ΔH$ $\sim$ 12 J kg $^{-1}$ K $^{-1}$ T $^{-1}$）。已经发现压热和磁热效应两者在压力和磁场循环时是可再现的。这种良好的再现性和大的热强度使得Fe-Rh合金在弱外部刺激下特别适合固态冷却技术。
A coupling of the first-order paramagnetic-to-induced-ferromagnetic martensitic and the second-order antiferromagnetic-to-ferromagnetic metamagnetic transitions was found in MnNi0.8Fe0.2Ge alloy. Based on the coupling, a magneto-volume effect driven by the martensitic transition and a table-like magnetocaloric effect generated by the successive magnetic phase transitions arise collectively. By using the magneto-volume effect, the internal pressure stress in the volume-expansion martensitic transition was determined at 350 MPa. The magnetocaloric effect, with a wide working temperature range of…
