Physical nature of "giant" magnetocaloric and electrocaloric effects, MCE and ECE, is explained in terms of the new fundamentals of phase transitions, ferromagnetism and ferroelectricity. It is the latent heat of structural (nucleation-and-growth) phase transitions from a normal crystal state to the orientation-disordered crystal (ODC) state where the constituent particles are engaged in thermal rotation. The ferromagnetism or ferroelectricity of the material provides the capability to trigger the structural phase transition by application, accordingly, of magnetic or electric field.
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…
Molecular dynamics simulations predict a giant electrocaloric effect at the ferroelectric-antiferroelectric phase boundary in PZT (PbTiO$_3$-PbZrO$_3$). These large-scale simulations also give insights into the atomistic mechanisms of the electrocaloric effect in PZT materials. Studying a range of ferroelectric (FE) and antiferroelectric (AFE) PZT materials we found positive electrocaloric effect in FE composites, but AFE ones exhibit a positive-to-negative crossover. At the AFE-FE phase boundary we find complex domain patterns. We demonstrate that the origin of giant electrocaloric change of …
We have recently observed a giant electrocaloric effect (12 K in 25 V) in 350 nm sol-gel Pb Zr_0.95 Ti_0.05 O_3 films near the ferroelectric Curie temperature of 242oC. Here we demonstrate a giant electrocaloric effect (5 K in 25 V) in 260 nm sol-gel films of the relaxor ferroelectric 0.9 PbMg_(1/3)Nb_(2/3)O_3 - 0.1 PbTiO_3 near the Curie temperature of 60oC. This reduction in operating temperature widens the potential for applications in novel cooling systems.
Giant electrocaloric (EC) effect is observed in BaTiO3 multilayer thick film structure. The temperature change is as high as 4.0 oC under an applied electric field of 352 kV/cm. Most importantly, the EC effect is found to depend on the varying rate of the applied field. Based on the giant net cooling (~0.37 J/g) resulting from the difference in the varying rates of rising and falling fields, the kinetic EC effect provides an effective solution for the design of refrigeration cycle in ferroelectric micro-refrigerator.
An applied electric field can reversibly change the temperature of an electrocaloric material under adiabatic conditions, and the effect is strongest near phase transitions. This phenomenon has been largely ignored because only small effects (0.003 K V^-1) have been seen in bulk samples such as Pb0.99Nb0.02(Zr0.75Sn0.20Ti0.05)0.98O3 and there is no consensus on macroscopic models. Here we demonstrate a giant electrocaloric effect (0.48 K V^-1) in 300 nm sol-gel PbZr0.95Ti0.05O3 films near the ferroelectric Curie temperature of 222oC. We also discuss a solid state device concept for electrical …
Refrigeration systems based on compression of greenhouse gases are environmentally threatening and cannot be scaled down to on-chip dimensions. In the vicinity of a phase transition caloric materials present large thermal responses to external fields, which makes them promising for developing alternative solid-state cooling devices. Electrocaloric effects are particularly well-suited for portable refrigeration applications; however, most electrocaloric materials operate best at non-ambient temperatures or require the application of large electric fields. Here, we predict that modest electric f…
The electrocaloric effect of BaTiO3 multilayer thick film structure was investigated by direct measurement and theoretical calculation. The samples were prepared by the tape-casting method, which had 180 dielectric layers with an average thickness of 1.4μm. The thermodynamic calculation based on the polarization- temperature curves predicted a peak heat adsorption of 0.32J/g at 80^\circC under 176kV/cm electric field. The direct measurement via differential scanning calorimeter showed a much higher electrocaloric effect of 0.91J/g at 80^\circC under same electric field. The difference could re…
We use molecular dynamics with a first-principles-based shell model potential to study the electrocaloric effect (ECE) in lithium niobate, LiNbO$_3$, and find a giant electrocaloric effect along a line passing through the ferroelectric transition. With applied electric field, a line of maximum ECE passes through the zero field ferroelectric transition, continuing along a Widom line at high temperatures with increasing field, and along the instability that leads to homogeneous ferroelectric switching below $T_c$ with an applied field antiparallel to the spontaneous polarization. This line is de…
An atomistic effective Hamiltonian is used to investigate electrocaloric (EC) effects of Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$ (PMN) relaxor ferroelectrics in its ergodic regime, and subject to electric fields applied along the pseudocubic [111] direction. Such Hamiltonian qualitatively reproduces (i) the electric field-versus-temperature phase diagram, including the existence of a critical point where first-order and second-order transitions meet each other; and (ii) a giant EC response near such critical point. It also reveals that such giant response around this critical point is microscopically …
There is a surge of interest in developing environmentally friendly cooling technology based on the solid--state electrocaloric effect (ECE). Here, we point out that negative ECE with a fast cooling rate ($\approx$10$^{11}$ K/s) can be achieved by driving solid crystals to a high--temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a negative ECE up to 35 K in PbTiO$_3$ occurring on few picosecond time scales. We acquire and analyze these results by clarifying the mechanism of ECE during an adiabatic irrever…
We report on the existence of acoustic emission during the paramagnetic-monoclinic to ferromagnetic-orthorhombic magnetostructural phase transition in the giant magnetocaloric Gd5Si2Ge2 compound. The transition kinetics have been analyzed from the detected acoustic signals. It is shown that this transition proceeds by avalanches between metastable states.
Large thermal changes driven by a magnetic field have been proposed for environmentally friendly energy efficient refrigeration, but only a few materials which suffer hysteresis show these giant magnetocaloric effects. Here we create giant and reversible extrinsic magnetocaloric effects in epitaxial films of the ferromagnetic manganite La0.7Ca0.3MnO3 using strain mediated feedback from BaTiO3 substrates near a first-order structural phase transition. Our findings should inspire the discovery of giant magnetocaloric effects in a wide range of magnetic materials, and the parallel development of …
Structural, magnetic and magnetocaloric properties of Mn2-xCrxSb compounds have been studied. In these compounds a first order magnetic phase transition from the ferrimagnetic to the antiferromagnetic state occurs with decreasing temperature, giving rise to giant inverse magnetocaloric effects that can be tuned over a wide temperature interval through changes in substitution concentration. Entropy changes as high as 7.5 J/kgK have been observed, and a composition independent entropy change is obtained for several different concentrations/working temperatures, making these compounds suitable ca…
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…
Off-stoichiometric alloys based on Ni 2 MnIn have drawn attention due to the coupled first order magnetic and structural transformations, and the large magnetocaloric entropy associated with the transformations. Here we describe calorimetric and magnetic studies of four compositions. The results provide a direct measure of entropy changes contributions including at the first-order phase transitions, and thereby a determination of the maximum field-induced entropy change corresponding to the giant magnetocaloric effect. We find a large excess entropy change, attributed to magneto-elastic coupli…
We report a giant magnetocaloric effect near room temperature in an off-stoichiometric Mn-Co-Ge alloy, across the magnetostructural transition. The isothermal entropy change accompanying this transition has a peak value of nearly 40 J/kg-K near 297 K and a refrigerant capacity of 270 J/kg with the hot end at 302.5 K and cold end at 293.5 K. We also present an experimental protocol to avoid spurious peaks in the magnetocaloric effect across a sharp first order magnetostructural transition, not confined to Mn-Co-Ge alone, where metastability during the transition could influence the measured mag…
The processing of promising magnetocaloric materials into spheres is one of the important issues on developing high-performance magnetic refrigeration systems. In the present study, we achieved in producing spherical particles of a giant magnetocaloric compound HoB2 by a crucible-free gas atomization process, despite its high melting point of 2350 C. The particle size distribution ranges from 100 to 710 micrometers centered at 212-355 micrometers with the highest yield of 14-20wt% of total melted electrode, which is suitable for magnetic refrigeration systems. The majority of the resulting par…
We have investigated magnetocaloric effect in double perovskite Gd2NiMnO6 (GNMO) and Gd2CoMnO6 (GCMO) samples by magnetic and heat capacity measurements. Ferromagnetic ordering is observed at ~130 K (~112 K) in GNMO (GCMO), while the Gd exchange interactions seem to dominate for T < 20 K. In GCMO, below 50 K, an antiferromagnetic behaviour due to 3d-4f exchnage interaction is observed. A maximum entropy (-ΔSM) and adiabatic temperature change of ~35.5 J Kg-1 K-1 (~24 J Kg-1 K-1) and 10.5 K (6.5 K) is observed in GNMO (GCMO) for a magnetic field change of 7 T at low temperatures. Absence of mag…
An effective scheme of isostructural alloying was applied to establish a Curie-temperature window in isostructural MnNiGe-CoNiGe system. With the simultaneous accomplishment of decreasing structural-transition temperature and converting antiferromagnetic martensite to ferromagnetic state, a 200 K Curie-temperature window was established between Curie temperatures of austenite and martensite phases. In the window, a first-order magnetostructural transition between paramagnetic austenite and ferromagnetic martensite occurs with a sharp jump in magnetization, showing a magnetic entropy change as …
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…
Magnetic and magnetocaloric properties of high-purity, giant magnetocaloric polycrystalline and single-crystalline Fe2P are investigated. Fe2P displays a moderate magnetic entropy change which spans over 70 K and the presence of strong magnetization anisotropy proves this system is not fully itinerant but displays a mix of itinerant and localized magnetism. The properties of pure Fe2P are compared to those of giant magnetocaloric (Fe,Mn)2(P,A) compounds helping understand the exceptional characteristics shown by the latter which are so promising for heat pump and energy conversion applications…
A remarkable decrease of the structural transition temperature of MnNiSi from 1200 K to <300 K by chemically alloying it with MnFeGe results in a coupling of the magnetic and structural transitions, leading to a large magnetocaloric effect near room temperature. It was found that the magnetostructural transition is highly sensitive to external (hydrostatic) pressure: relatively low hydrostatic pressures (~2.4 kbar) lead to an extraordinary enhancement of the isothermal entropy change from $-$Δ$S$ = 44 to 89 J/kg K at ambient (atmospheric) and 2.4 kbar applied pressures, respectively, for a fie…
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 …
Three first order magnetic phase transitions (FOMT) have been detected at TCPr, TNinter and TCinter over the temperature range from 5 K to 340 K at fields up to 9 T in PrMn1.4Fe0.6Ge2, and the magnetocaloric effect (MCE) around these transitions evaluated. The MCE of two FOMT from planar antiferromagnetism (AFl) to c-axis ferromagnetism (Fmc) around 168 K, and from the Fmc state to the c-axis AFmc state around 157 K have acceptable values compared with those of existing MCE systems. A giant magnetocaloric effect (GMCE) has been observed around 25.5 K associated with the field-induced FOMT from…
We report the magnetic entropy change (Delta Sm) in magnetoelectric Eu1-xBaxTiO3 for x = 0.1- 0.9. We find - delta Sm = 11 (40) J/kg.K in x = 0.1 for a field change of 1 (5) Tesla respectively, which is the largest value among all Eu-based oxides. Delta Sm arises from the field-induced suppression of the spin entropy of Eu2+:4f7 localized moments. While -delta Sm decreases with increasing x, -DeltaSm = 6.58 J/kg.K observed in the high spin diluted composition x = 0.9 is larger than that in many manganites. Our results indicate that these magnetoelectrics are potential candidates for cryogenic …
The structural and magnetic properties of functional Ni-Mn-Z (Z = Ga, In, Sn) Heusler alloys are studied by first-principles and Monte Carlo methods. The \textit{ab initio} calculations give a basic understanding of the underlying physics which is associated with the strong competition of ferro- and antiferromagnetic interactions with increasing chemical disorder. The resulting $d$-electron orbital dependent magnetic ordering is the driving mechanism of magnetostructural instability which is accompanied by a drop of magnetization governing the size of the magnetocaloric effect. The thermodynam…
A strong electronic reconstruction resulting in a quenching of the Fe magnetic moments has recently been predicted to be at the origin of the giant magnetocaloric effect displayed by Fe2Pbased materials. To verify this scenario, X-ray Magnetic Circular Dichroism experiments have been carried out at the L edges of Mn and Fe for two typical compositions of the (Mn,Fe)2(P,Si,B) system. The dichroic absorption spectra of Mn and Fe have been measured element specific in the vicinity of the first-order ferromagnetic transition. The experimental spectra are compared with first-principle calculations …
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$_3…
We study the magnetoelectric and electrocaloric response of strain-engineered, multiferroic SrMnO$_3$, using a phenomenological Landau theory with all parameters obtained from \emph{first-principles}-based calculations. This allows to make realistic and materials-specific predictions about the magnitude of the corresponding effects. We find that in the vicinity of a tetracritical point, where magnetic and ferroelectric phase boundaries intersect, an electric field has a huge effect on the antiferromagnetic order, corresponding to a magnetoelectric response several orders of magnitude larger th…
Indirect exchange coupling in magnetic multilayers, also known as the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction, is known to be highly effective in controlling the interlayer alignment of the magnetization. This coupling is typically fixed at the stage of the multilayer fabrication and does not allow ex-situ control needed for device applications. It is highly desirable, in addition to the orientational control, to also control the magnitude of the intralayer magnetization, ideally switch it on/off by switching the relevant RKKY coupling. Here we demonstrate a magnetic multilayer materi…
The magnetocaloric effect (MCE) in paramagnetic materials has been widely used for attaining very low temperatures by applying a magnetic field isothermally and removing it adiabatically. The effect can be exploited also for room temperature refrigeration by using recently discovered giant MCE materials. In this letter, we report on an inverse situation in Ni-Mn-Sn alloys, whereby applying a magnetic field adiabatically, rather than removing it, causes the sample to cool. This has been known to occur in some intermetallic compounds, for which a moderate entropy increase can be induced when a f…
Recently, a massive magnetocaloric effect near the liquefaction temperature of hydrogen has been reported in the ferromagnetic material HoB$_{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…
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…
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 …
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.
Electrocaloric (EC) materials show promise in eco-friendly solid-state refrigeration and integrable on-chip thermal management. While direct measurement of EC thin-films still remains challenging, a generic theoretical framework for quantifying the cooling properties of rich EC materials including normal-, relaxor-, organic- and anti-ferroelectrics is imperative for exploiting new flexible and room-temperature cooling alternatives. Here, we present a versatile theory that combines Master equation with Maxwell relations and analytically relates the macroscopic cooling responses in EC materials …
It is known that the Zircon-type orthovanadates RVO4 show promise in many different applications as catalysts and optical materials. In this work, we demonstrate that the TbVO4 compound can be also used as magnetic refrigerant in efficient and ecofriendly cryocoolers due to its strong magnetocaloric effect at low temperature regime. The application of a relatively low magnetic field of 2 T along the easy magnetization axis (a) gives rise to a maximum entropy change of about 20 J/kg K at 4 K. More interestingly, under sufficiently high magnetic fields, the isothermal entropy change -ΔST remains…
The magneto-electrocaloric effect which can be defined as the coupling between magnetocaloric and electrocaloric effects attracts currently considerable attention due to the advantages provided by the caloric effect in designing solid-state refrigeration technologies. The magneto-electrocaloric effect of a multiferroic antiferromagnetic spin system with the Dzyaloshinskii Moriya (DM) interaction is investigated in this paper. The DM interaction is assimilated to a coupling between an external site-dependent electric field and a local electric polarization. The external magnetic is also conside…
The structural, magnetic, and magnetocaloric properties of epitaxial Ni-Co-Mn-Al thin films with different compositions have been studied. The films were deposited on MgO(001) substrates by co-sputtering on heated substrates. All films show a martensitic transformation, where the transformation temperatures are strongly dependent on the composition. The structure of the martensite phase is shown to be 14M. The metamagnetic martensitic transformation occurs from strongly ferromagnetic austenite to weakly magnetic martensite. The structural properties of the films were investigated by atomic for…
In the lifetime of a magnetic refrigerator the materials are subjected to millions of thermal magnetic cycles, so it is of the utmost importance to predict the behavior of such materials when subjected to related work conditions. Thus, in this work we investigated the influence of thermal cycling in the microstructure, magnetic phase transition and magnetic entropy change of a Gd5Si1.3Ge2.7 thin film up to 1000 cycles. In a first stage, till 450 cycles, the hysteresis area of the magnetization curves as a function of temperature was found to decrease 16% with thermal cycling, due to an arresti…
Giant Magnetocaloric Effect in a High-Spin Shastry-Sutherland Dipolar Magnet
Ganjiang Innovation Academy, Chinese Academy of Sciences（中国科学院赣江创新研究院）；University of Science and Technology of China（中国科学技术大学）；High Magnetic Field Laboratory, Chinese Academy of Sciences（中国科学院合肥物质科学研究院高磁场实验室）；Institute of Theoretical Physics, Chinese Academy of Sciences（中国科学院理论物理研究所）；Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所）；Anhui University（安徽大学）；Beijing Institute of Technology（北京理工大学）
Mechanical control of magnetic properties in magnetostrictive thin films offers the unexplored opportunity to employ surface wave acoustics in such a way that acoustic triggers dynamic magnetic effects. The strain-induced modulation of the magnetic anisotropy can play the role of a high frequency varying effective magnetic field leading to ultrasonic tuning of electronic and magnetic properties of nanostructured materials, eventually integrated in semiconductor technology. Here, we report about the opportunity to employ surface acoustic waves to trigger magnetocaloric effect in MnAs(100nm)/GaA…
Electric field control of magnetism is the key to many next generation spintronics applications1. Ferroelectric control of spin polarization2,3 followed by the electrically driven repeatable magnetization reversal in the absence of applied magnetic field4 have proven to be the milestones in this direction. This article propose how these phenomena could be utilized in a reverse manner to gain control over magnetization even in the absence of electric field. In turn, coexistence of positive5 as well as negative6 magnetocaloric effect (MCE) is attained in tri-layered PbZr0.53Ti0.47O3-CoFe2O4-PbZr…
We have investigated the magnetocaloric effect in single and polycrystalline samples of quantum paraelectric EuTiO3 by magnetization and heat capacity measurements. Single crystalline EuTiO3 shows antiferromagnetic ordering due to Eu2+ magnetic moments below TN = 5.6 K. This compound shows a giant magnetocaloric effect around its Neel temperature. The isothermal magnetic entropy change is 49 Jkg-1K-1, the adiabatic temperature change is 21 K and the refrigeration capacity is 500 JKg-1 for a field change of 7 T at TN. The single crystal and polycrystalline samples show similar values of the mag…
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…
Solid state-refrigerants have generated worldwide interest owing to their growing potential for use in efficient and green cooling devices. Caloric effects could be obtained by manipulating their degrees of freedom such as magnetization, electric polarization and volume using a variable external field. In conventional magnetocaloric refrigeration systems, the magnetocaloric effect is exploited by moving the active material in and out of the magnetic field source. Here we demonstrate that a giant and reversible magnetocaloric effect can be generated simply by rotating the multiferroic TbMn2O5 s…
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…
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…
The three primary ferroics, namely ferromagnets, ferroelectrics and ferroelastics exhibit corresponding large (or even giant) magnetocaloric,electrocaloric and elastocaloric effects when a phase transition is induced by the application of an appropriate external field. Recently the suite of primary ferroics has been extended to include ferrotoroidic materials in which there is an ordering of toroidic moments in the form of magnetic vortex-like structures, examples being LiCo(PO_4)_3 and Ba_2CoGe_2O_7. In the present work we formulate the thermodynamics of ferrotoroidic materials. Within a Land…
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…
There is currently great interest in replacing the harmful volatile hydrofluorocarbon fluids used in refrigeration and air-conditioning with solid materials that display magnetocaloric, electrocaloric or mechanocaloric effects. However, the field-driven thermal changes in all of these caloric materials fall short with respect to their fluid counterparts. Here we show that plastic crystals of neopentylglycol (CH3)2C(CH2OH)2 display unprecedentedly large pressure-driven thermal changes near room temperature due to molecular reconfiguration, and that these changes are comparable with those exploi…
