Magnetic and magnetocaloric properties of the intermetallic compound TbNiAl

Magnetization measurements have been carried out on the intermetallic compound TbNiAl in applied fields up to 120 kOe. Temperature dependence of magnetization under zero-field-cooled and field-cooled conditions shows thermomagnetic irreversibility, which is attributed to magnetic frustration. With the increase of field, the irreversibility decreases and vanishes completely at high fields. Magnetocaloric effect has been calculated in terms of isothermal magnetic entropy change using magnetization isotherms obtained at various temperatures. The maximum entropy change is 13.8 J kg⁻¹ K⁻¹ near the ordering temperature for a field change of 50 kOe. The refrigerant capacity is found to be 494 J kg⁻¹ for the same field change and for a temperature difference of 52 K between the cold and the hot sinks.     

Magnetocaloric effect in ferromagnetic and ferrimagnetic systems under first and second order phase transition

In this work we present a model to describe the magnetocaloric effect (MCE) in ferrimagnetic arrangements. Our model takes into account the magnetoelastic interactions in the two coupled magnetic sublattices, which can lead to the onset of the first order magnetic phase transition and the giant-MCE. Several profiles of the MCE, such as: the inverse- and giant-MCE were systematically studied. Application of the model to the ferromagnetic compounds GdAl₂, Gd₅(Ge_1.72Si_2.28), Gd₅(Ge₂Si₂), and to the ferrimagnetic compound Y₃Fe₅O₁₂ was performed, showing a good agreement with the experimental data.     

Magnetocaloric effects in (Gd1−xTbx)Co2

The structures and magnetocaloric effects of (Gd_1−xTb_x)Co₂ (x=0, 0.25, 0.4, 0.5, 0.6, 0.7, 0.8, and 1) pseudobinary compounds were investigated by X-ray powder diffraction and magnetic properties measurement. The results show that the T_c of the alloy is near room temperature when X=0.6. The magnetic entropy changes of the compounds increase from 1.7 to 3.6 J/kg K with increasing the content of Tb under an applied field up to 2 T. All the compounds exhibit second order magnetic change. As a result, the values of their ΔS_M are lower than that of some large magnetocaloric effect materials.     

On the magnetocaloric effect in Gd(Zn1−xCdx)

In this work, we calculate the magnetocaloric effect in the compounds Gd(Zn_1−xCd_x). We use a model Hamiltonian of interacting spins in which the indirect exchange interaction parameter between localized spins was calculated as a function of Cd concentration. The calculated isothermal entropy changes and the adiabatic temperature changes upon magnetic field variations are in good agreement with the available experimental data.     

Magnetism, magnetocaloric effect and positive magnetoresistance in Fe-doped antipervoskite compounds SnCMn3−xFex (x=0.05-0.20)

The effects of Fe substitution on the structure, magnetic properties, magnetocaloric effect and positive magnetoresistance (MR) effect in antipervoskite compounds SnCMn_3−xFe_x (x=0.05-0.20) have been investigated systematically. Partial substitution of Fe for Mn leads to the monotonic reduction in both the Curie temperature T_C and saturated magnetization (M_S). It can be attributed to the reduction of electronic density of state at the Fermi energy by Fe-doping. The maximum values of magnetic entropy change (−ΔS_M) and positive MR gradually decrease as x increases, due to the broadening of magnetic phase transition. The refrigerant capacity increases initially with x≤0.05, then decreases gradually as x increases further, which is suggested to originate from the competition between the decreasing −ΔS_M and broadening temperature span. Our result indicates that the chemical doping on Mn site is an effective method for manipulating the properties of antiperovskite compounds AXMn₃.     

Investigation on the magnetocaloric effect in DyNi2, DyAl2 and Tb1−nGdnAl2 (n=0, 0.4, 0.6) compounds

The magnetocaloric effect (MCE) in the DyNi₂, DyAl₂ and Tb_1−nGd_nAl₂ (n=0, 0.4, 0.6) was theoretically investigated in this work. The DyNi₂ and DyAl₂ compounds are described considering a model Hamiltonian which includes the crystalline electrical field anisotropy. The anisotropic MCE was calculated changing the magnetic field direction from 〈1 1 1〉 to 〈0 0 1〉 in DyNi₂ and from 〈1 0 0〉 to 〈0 1 1〉 in DyAl₂. The influence of the second- and first-order spin-reorientation phase transitions on the MCE that occurs in these systems is discussed. For the calculations of the MCE thermodynamic quantities in the Tb_1−nGd_nAl₂ systems we take into account a two sites magnetic model, and good agreement with the available experimental data was obtained.     

Magnetocaloric effects in Ni-Mn-X based Heusler alloys with X=Ga, Sb, In

The Mn-based Heusler alloys encompass a rich collection of useful materials from highly spin-polarized systems to shape memory alloys to magnetocaloric materials. In this work we have summarized our studies of magnetostructural transitions from paramagnetic austenite to ferromagnetic martesite phases at TMC in Ni₂MnGa-based alloys (Ni₂Mn_0.75Cu_0.25-xCo_xGa, Ni₂Mn_0.70Cu_0.30Ga_0.95Ge_0.05, Ni₂Mn_1-xCu_xGa, Ni_2+xMn_1-xGa, and Ni₂Mn_0.75-xCu_xGa), and martensitic transitions from the ferromagnetic austenite to the martesite state in off-stoichiometric Ni-Mn-(In/Sb) Heusler alloys. The phase transition temperatures and respective magnetic entropy changes (ΔS) depend on composition in these systems and have been determined from magnetization measurements in the temperature interval 5-400 K, and in magnetic fields up to 5 T. It is shown that, depending on the composition and doping scheme the “giant” ΔS=40-60 J/(kgK) (for a field change of 5 T) can be observed in the temperature range (300-360 K) for the Ga-based alloys. The interplay between or coupling of the various transitions in Ni₂Mn(Mn,X) systems with X=Sb and In leads to exchange bias effects, giant magnetoresistance, and both inverse and “normal” magnetocaloric effects.     

Itinerant electron metamagnetism and magnetocaloric effect in Dy(Co,Si)2

Itinerant electron metamagnetism in Dy(Co_1-xSi_x)₂ compounds was studied in the light of a recent theoretical model based on magnetovolume effect and spin fluctuations. The nature of the magnetic transition in these compounds was analyzed within the framework of this model. The magnetocaloric effect in these compounds has been calculated and correlated with the strength of itinerant electron metamagnetism. The domain wall pinning effect was found to be dominant at low temperatures.     

Magnetocaloric effect in DyCu2

The magnetocaloric effect of the rare-earth intermetallic compound DyCu₂ is explored through magnetization measurements. DyCu₂ is paramagnetic at the room temperature but becomes antiferromagnetic below 27 K (Neel temperature). Strong temperature and field dependence of magnetization in DyCu₂ at and around the Neel temperature lead to a large magnetocaloric effect. An appreciable magnetocaloric effect persists well above the Neel temperature probably because of the presence of short-range ferromagnetic correlations in the paramagnetic state of DyCu₂. This along with the absence of magnetic hysteresis lead to a large effective refrigerant capacity of 194 J/kg below 44 K, which makes the material important as a potential magnetic refrigerant for the cryogenic liquefier cycles.     

First observation of ferromagnetism and ferromagnetic domains in a liquid metal

80 Pd₂₀ alloy below the Curie temperature T_C(l)=1257 K of the liquid state. The magnetization of the undercooled liquid sample has been measured as a function of temperature using a modified Faraday balance. Below T_C(l), the magnetization of the liquid metal shows a plateau in the weak external field of μ₀H_z=5.6 mT. The effect is comparable to the behaviour of the corresponding solid phase, indicating the onset of spontaneous magnetization with ferromagnetic domains. T_C(l) is about 20 K lower than the Curie temperature of the solid phase T_C(s). Received: 24 February 1997/Accepted: 16 May 1997     

Magnetocaloric effect of Gd5SixSn4−x Alloys

The crystal structure and magnetocaloric effect of Gd₅Si_xSn_4−x   (with x=2.4$x=2.4$, 2.6 and 2.8) alloys were studied by means of X-ray power diffraction (XRD) and magnetic measurements. From the XRD results, these alloys adopt a Gd₅Si₄-type structure for x=2.8$x=2.8$, Gd₅Si₄-type and Gd₅Si₂Ge₂-type mixed structures for x=2.4$x=2.4$ and 2.6, while some minor phases can also be found. The Curie temperatures of the Gd₅Si_xSn_4−x increases gradually when x increases from 276 K for x=2.4$x=2.4$, to 301.5 K for x=2.8$x=2.8$. Magnetic entropy changes of these alloys at a magnetic field change of 0–1.8 T are 1.88, 2.26 and 1.69 J/kg K for x=2.4$x=2.4$, 2.6 and 2.8, respectively. The temperature-dependent XRD analysis shows that there is no crystallographic transition for these alloys, which can explain their low magnetic entropy changes.     

Magnetocaloric effect in R2Fe17 (R=Sm,Gd, Tb,Dy, Er)

A series of R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) have been synthesized. The magnetocaloric effect (MCE) of these compounds has been investigated by means of magnetic measurements in the vicinity of their Curie temperature. The Curie temperature of Er₂Fe₁₇ is 294 K. The maximum magnetic entropy change of Er₂Fe₁₇ under 5 T magnetic field is ∼3.68 J/kg K. In the R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) system, the maximum magnetic entropy change under 1.5 T magnetic field is 1.72, 0.89, 1.32, 1.59, 1.68 J/kg K corresponding to their Curie temperature (400, 472, 415, 364, 294 K), respectively.     

Fine structure of the field-induced magnetic transition in Nd0.1La0.9Fe11.5Al1.5

For the Nd_0.1La_0.9Fe_11.5Al_1.5 compound, the fine structure of the magnetic transition from the ferromagnetic (FM) to the antiferromagnetic (AFM) states has been studied carefully by means of magnetization (M) and heat capacity (C_p) measurements. Although a single phase with the cubic NaZn₁₃-type structure (Fm3c) has been proved by the room temperature X-ray diffraction pattern, the phase transition has been clearly found to be a stepwise process in M(T) and C_p(T) curves under proper fields. Due to the strong competition between the FM order and AFM order, the characteristic is especially evident under low fields, weakens gradually with the increasing applied field and finally vanishes when the field is higher than 2 T. This multi-step magnetic transition results from the inhomogeneity of the sample, probably due to the inhomogeneous distribution of Nd atoms.     

Magnetocaloric effect: Overcoming the magnetic limit

We have studied anomalous peaks observed in magnetocaloric −ΔS(T) curves for systems that undergo first-order magnetostructural transitions. The origin of those peaks, which can exceed the conventional magnetic limit, R ln(2J+1), is discussed on thermodynamic bases by introducing an additional-exchange contribution (due to exchange constant variation arising from magnetostructural transition). We also applied a semiphenomenological model to include this additional-exchange contribution in Gd₅Si₂Ge₂- and MnAs-based systems, obtaining excellent results for the observed magnetocaloric effect.     

Metamagnetic transition and magnetocaloric effect in charge-ordered Pr0.68Ca0.32−xSrxMnO3 (x=0, 0.1, 0.18, 0.26 and 0.32) compounds

In this study, magnetic and magnetocaloric properties of Pr_0.68Ca_0.32−xSr_xMnO₃ (x=0, 0.1, 0.18, 0.26 and 0.32) compounds were investigated. X-ray results indicated that all the samples have a single phase of orthorhombic symmetry. The orthorhombic unit cell parameters increase with the increase in Sr content. Large negative magnetic entropy changes (−26.2 J/kg K at 38 K and 5 T for x=0 and −6.5 J/kg K at 83 K and 6 T for x=0.1) were attributed to ultrasharp metamagnetic transitions. The peak value of ΔS_m decreased from −4.1 J/kg K for x=0.18 sample to −2.4 J/kg K for x=0.32 at 1 T magnetic field.     

Magneto-structural correlations in Pr0.15Gd0.85Mn2Ge2

Magneto-structural correlations in Pr_0.15Gd_0.85Mn₂Ge₂ have been studied by synchrotron diffraction in the temperature range between 11 and 300 K. This compound crystallizes in the ThCr₂Si₂-type structure (space group ). The unit cell parameters a and c were determined by Rietveld refinements as a function of temperature. Anomalies in the temperature dependence of the unit cell parameters a and c, the c/a ratio and the unit cell volume V at about 240 and 140 K, which is close to the magnetic phase transition temperatures, indicate a pronounced magneto-structural correlation. Spontaneous volume change and linear magnetostrictions are derived as a function of temperature.     

Novel RCo5Ga7 intermetallic compound

The novel RCo₅Ga₇ (R=Y, Tb, Dy, Ho and Er) intermetallic compounds have been synthesized, and their crystallographic and magnetic properties have been studied using X-ray diffraction and magnetic measurement. RCo₅Ga₇ crystallizes in an orthorhombic structure with ScFe₆Ga₆ type. The space group is Immm, and Z=2. According to the structural refinement result, the 2a, 4e, 4f, 4g, 4h, and 8k crystal positions are occupied by 2R, 4Ga^I, 4(Ga^II, Co^I), 4Ga^III, 4(Ga^IV,Co^II), and 8(Co^III,Ga^V), respectively. The RCo₅Ga₇ intermetallic compound can be stabilized in the range of the radius ratio of R_Re/R_(Co,Ga)<1.36. The RCo₅Ga₇ compound exhibits a paramagnetic behavior. The magnetization at 5 K ranges from 28.93 to 40.62 emu/g.     

Magnetic and magnetocaloric results of magnetic field-induced transitions in La1−xCexMn2Si2 (x=0.35 and 0.45) compounds

The La_1−xCe_xMn₂Si₂ compounds (x=0.35 and 0.45) exhibit an antiferromagnetic-ferromagnetic transition caused by the changes in distance between Mn atoms due to temperature changes. A field-induced transition from antiferromagnetic state to ferromagnetic state at a critical field, which decreases with increase in temperature, can also be induced by applying a magnetic field. In this paper our aim is to study the magnetization and magnetocaloric effect, close to transition temperatures. Our subsidiary aim is to examine the temperature dependence of critical field and ferromagnetic fraction of compounds. The variation of magnetocaloric effect with temperature is correlated with the ferromagnetic-antiferromagnetic phase coexistence. Our final aim is to examine the harmony between magnetocaloric effect values calculated both by the Maxwell theory and by the Landau theory.     

Review of the magnetocaloric effect in manganite materials

A thorough understanding of the magnetocaloric properties of existing magnetic refrigerant materials has been an important issue in magnetic refrigeration technology. This paper reviews a new class of magnetocaloric material, that is, the ferromagnetic perovskite manganites (R_1−xM_xMnO₃, where R=La, Nd, Pr and M=Ca, Sr, Ba, etc.). The nature of these materials with respect to their magnetocaloric properties has been analyzed and discussed systematically. A comparison of the magnetocaloric effect of the manganites with other materials is given. The potential manganites are nominated for a variety of large- and small-scale magnetic refrigeration applications in the temperature range of 100–375 K. It is believed that the manganite materials with the superior magnetocaloric properties in addition to cheap materials-processing cost will be the option of future magnetic refrigeration technology.     

Anisotropy of the magnetocaloric effect in DyNiAl

We present study of the anisotropic magnetocaloric effect in DyNiAl. This compound crystallizes in the hexagonal ZrNiAl-type structure, orders magnetically below and undergoes a further magnetic phase transition at . The Dy-moments are aligned ferromagnetically along the hexagonal c-axis below T_C, the additional antiferromagnetic component develops within the basal plane below T₁. The magnetocaloric effect was evaluated from the magnetization measurements with field applied along the c-axis and perpendicular to it. Our data reveal a strong anisotropy of the magnetocaloric effect. The large effect occurs for field applied along the c-axis whereas the entropy change is small for the perpendicular field direction.