Field-induced structural transition and the related magnetic entropy change in Ni43Mn43Co3Sn11 alloy

Magnetic properties and magnetic entropy change ΔS were investigated in Heusler alloy Ni₄₃Mn₄₃Co₃Sn₁₁. With decreasing temperature this alloy undergoes a martensitic structural transition at T_M=188 K. The incorporation of Co atoms enhances ferromagnetic exchange for parent phases. Austenitic phase with cubic structure shows strong ferromagnetic behaviors with Curie temperature T_C^A at 346 K, while martensitic phase shows weak ferromagnetic properties. An external magnetic field can shift T_M to a lower temperature at a rate of 4.4 K/T, and a field-induced structural transition from martensitic to austenitic state takes place at temperatures near but below T_M. As a result, a great magnetic entropy change with positive sign appears. The size of ΔS reaches 33 J/kg K under 5 T magnetic field. More important is that the ΔS displays a table-like peak under 5 T, which is favorable for Ericsson-type refrigerators.     

Effect of Mn incorporation for Ni on the properties of melt spun off-stoichiometric compositions of NiMnGa alloys

The investigation addresses the effect of Mn incorporation for Ni on the properties of a series of Ni_77−xMn_xGa₂₃ (x=22-29; at%) ferromagnetic shape memory alloys prepared in the form of ribbons by a melt spinning technique. Phase transformation studies in these ribbons by differential scanning calorimetry revealed that austenitic start and martensitic start temperatures decreased with the increase in Mn content. The Curie temperature (T_C) of these alloys determined from thermal variation of magnetisations was found to rise with increasing Mn content. The martensitic transformation temperatures were above T_C in low Mn containing (x=22 and 23) alloys. Morphology observed through transmission electron microscopy manifested complex martensitic features in the alloy with x=22 while x=29 had an austenitic phase. The alloys with intermediate Mn content (x=24, 25) had overlapping magnetic and martensitic transformations close to room temperature. The thermal lag between austenitic and martensitic characteristic temperatures in these alloys has been corroborated to their structural state. X-ray diffraction indicated a predominant martensite phase and austenite phase in low and high Mn containing alloys respectively. In-situ diffraction studies during thermal cycle indicate martensite-austenite transformations.     

Magnetocaloric properties of as-quenched Ni50.4Mn34.9In14.7 ferromagnetic shape memory alloy ribbons

The temperature dependences of magnetic entropy change and refrigerant capacity have been calculated for a maximum field change of Δ H=30 kOe in as-quenched ribbons of the ferromagnetic shape memory alloy Ni_50.4Mn_34.9In_14.7 around the structural reverse martensitic transformation and magnetic transition of austenite. The ribbons crystallize into a single-phase austenite with the L2₁-type crystal structure and Curie point of 284 K. At 262 K austenite starts its transformation into a 10-layered structurally modulated monoclinic martensite. The first- and second-order character of the structural and magnetic transitions was confirmed by the Arrott plot method. Despite the superior absolute value of the maximum magnetic entropy change obtained in the temperature interval where the reverse martensitic transformation occurs (|\varDelta S_M^max|=7.2 J kg^-1 K^-1)(|\varDelta S_{\mathrm{M}}^{\max}|=7.2\mbox{ J}\,\mbox{kg}^{-1}\,\mbox{K}^{-1}) with respect to that obtained around the ferromagnetic transition of austenite (|\varDelta S_M^max|=2.6 J kg^-1 K^-1)(|\varDelta S_{\mathrm{M}}^{\max}|=2.6\mbox{ J}\,\mbox{kg}^{-1}\,\mbox{K}^{-1}), the large average hysteretic losses due to the effect of the magnetic field on the phase transformation as well as the narrow thermal dependence of the magnetic entropy change make the temperature interval around the ferromagnetic transition of austenite of a higher effective refrigerant capacity (RC^magn_eff=95J kg^-1\mathrm{RC}^{\mathrm{magn}}_{\mathrm{eff}}=95\mbox{J}\,\mbox{kg}^{-1} versus RC^struct_eff=60J kg^-1)\mathrm{RC}^{\mathrm{struct}}_{\mathrm{eff}}=60\mbox{J}\,\mbox{kg}^{-1}).     

Electrical,magnetic and magnetocaloric properties of polycrystalline Pr0.63A0.07Sr0.3MnO3 (A=Pr,Sm and Bi)

We studied the effects of the partial substitution (10%) of praseodymium by samarium and bismuth, on the structural, magnetic, magnetocaloric and electrical properties of the Pr_0.63A_0.07Sr_0.3MnO₃ (A=Pr, Sm and Bi) manganites prepared using the solid state reaction. Refinement of the X-ray diffraction patterns shows that all our samples are single phase and crystallize in the orthorhombic structure with Pnma space group. Magnetic studies indicate that all the samples exhibit a ferromagnetic–paramagnetic transition with increasing temperature. Curie temperature T_C decreases by substitution. M(H) curves indicate the presence of some antiferromagnetic domains in the substituted samples testifying the phase-separated nature of these samples. The magnetic entropy curves –ΔS(T) show a maximum in vicinity of T_C. Important values of maximum of −ΔS are recorded for our compounds. For the parent compound, we found 4.59 J/kg K for an applied magnetic field of 2 T at T_C=266 K which raises the possibility of using this compound as a magnetic refrigerant. The temperature dependence of the electrical resistivity ρ(T) indicates that all compounds exhibit a metal-insulator transition with increasing temperature. Electrical study suggests the presence of a correlation between electrical and magnetic properties.     

Magnetic properties and magnetic entropy change in Heusler alloys Ni50Mn35?xCuxSn15

The influence of Cu substitution for Mn on magnetic properties and magnetic entropy change has been investigated in Heusler alloys, Ni₅₀Mn_35−x Cu _x Sn₁₅ (x=2,5 and 10). With increasing Cu content from x=2 to x=5, the martensitic transition temperature, T _M , decreases from 220 K to 120 K. Further increasing Cu up to x=10 results in the disappearance of T _M . For samples Ni₅₀Mn₃₃Cu₂Sn₁₅ and Ni₅₀Mn₃₀Cu₅Sn₁₅, both martensitic and austenitic states exhibit ferromagnetic characteristics, but the magnetization of martensitic phase is notably lower than that of austenitic phase. The magnetization difference, ΔM, across the martensitic transition leads to a considerably large Zeeman energy, μ ₀ΔM⋅H, which drives a field-induced metamagnetic transition. Associated with the metamagnetic behavior, a large positive magnetic entropy change ΔS takes place around T _M . For the sample Ni₅₀Mn₃₃Cu₂Sn₁₅,ΔS reaches 13.5 J/kg⋅K under a magnetic field change from 0 to 5 T.     

Enhanced magnetocaloric effect in Eu-doped La0.7Ca0.3MnO3 compounds

Orthorhombic La_0.7-xEu_xCa_0.3MnO₃ samples (x = 0.04–0.12) with apparent density of ρ = 3.9–4.1 g/cm³ prepared by solid-state reactions have been studied. The analysis of temperature-dependent magnetization for an applied field H = 500 Oe indicated a decrease of the Curie temperature (T_C) from about 225 K for x = 0.04 through 189 K for x = 0.08–146 K for x = 0.12. The magnetocaloric (MC) study upon analyzing M(H, T) data has revealed that the magnetic entropy change around T_C reaches the maximum (|ΔS_max|), which is dependent on both x and H. For an applied field interval of ΔH = 60 kOe, |ΔS_max| values are about 5.88, 4.93, and 4.71 J/kg⋅K for x = 0.04, 0.08, and 0.12, respectively. Though |ΔS_max| decreases with increasing x, relative cooling power (RCP) increases remarkably from 383 J/kg for x = 0.04 to about 428 J/kg for x = 0.08 and 0.12. This is related to the widening of the ferromagnetic-paramagnetic transition region when x increases. Particularly, if combining two compounds with x = 0.04 and 0.08 (or 0.12) as refrigerant blocks for MC applications, a cooling device can work in a large temperature range of 145–270 K, corresponding to RCP ≈ 640 J/kg for H = 60 kOe. M(H) analyses around T_C have proved x = 0.04 exhibiting the mixture of first- and second-order phase transitions while x = 0.08 and 0.12 exhibit a second-order nature. The obtained results show potential applications of Eu-doped La_0.7Ca_0.3MnO₃ materials for magnetic refrigeration below room temperature.     

Thermal stability,magnetic and magnetocaloric properties of Gd55Co35M10 (M = Si,Zr and Nb) melt-spun ribbons

The thermal stability, magnetic and magnetocaloric properties of Gd₅₅Co₃₅M₁₀ (M = Si, Zr and Nb) melts-pun ribbons were studied. The relatively high reduced glass transition temperature (T_x1/T_m > 0.60) and low melting point (T_m) resulted in excellent glass forming ability (GFA). The Curie temperatures (T_C) of melt-spun amorphous ribbons Gd₅₅Co₃₅M₁₀ for M = Si, Zr and Nb were 166, 148 and 173 K, respectively. For a magnetic field change of 2 T, the values of maximum magnetic entropy change (−ΔS_M)^max for Gd₅₅Co₃₅Si₁₀, Gd₅₅Co₃₅Zr₁₀ and Gd₅₅Co₃₅Nb₁₀ were found to be 2.86, 4.28 and 4.05 J kg⁻¹K⁻¹, while the refrigeration capacity (RC) values were 154, 274 and 174 J kg^–1, respectively. The RC_FWHM values of amorphous alloys Gd₅₅Co₃₅M₁₀ (M = Si, Zr and Nb) are comparable to or larger than that of LaFe_11.6Si_1.4 crystalline alloy. Large values of (−ΔS_M)^max and RC along with good thermal stability make Gd₅₅Co₃₅M₁₀ (M = Si, Zr and Nb) amorphous alloys be potential materials for magnetic cooling operating in a wide temperature range from 150 to 175 K, e.g., as part of a gas liquefaction process.     

Effects of divalent alkaline earth ions on the magnetic and transport features of La0.65A0.35Mn0.95Fe0.05O3 (A = Ca, Sr, Pb, Ba) compounds

We have studied the magnetic and transport properties of Fe doped La_0.65A_0.35Mn_0.95Fe_0.05O₃ (A = Ca, Sr, Pb, Ba) manganites. All the compositions show ferromagnetic/metal to paramagnetic/insulator transition (T_C) except the Pb doped sample which is insulating and ferromagnetic (FM) in the entire temperature range. The magnetization and T_C are decreased by decreasing the cation size on La site. The transition temperature and magnetic moment at 77 K is a maximum for Sr doped sample and is decreasing if we increase or decrease the cation size from Sr size. The maximum value of T_C and magnetic moment for Sr based sample is most likely due to the closer ionic sizes of La and Sr as compared to the other dopants (Ca, Pb, and Ba). We observed a spin freezing type effect in the Pb doped sample below 120 K in resistivity, ac susceptibility and in magnetization. This suggests that the AFM interactions introduced by the Fe are most effective in the Pb doped composition leading to increased competition between the FM and AFM interactions. This FM and AFM interaction generates some degree of frustration leading to the appearance of spin glass like phase whose typical magnetic behavior is studied for small ion when the metallic like behavior is lost.     

Magnetic properties and magnetocaloric effects in Gd1−xHoxNiIn intermetallic compounds

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Gd_1?xHo_xNiIn (x=0?1) compounds have been evaluated by magnetization and heat capacity measurements. The Curie temperature T_C can be tuned from near 100 K to 20 K by substituting Ho for Gd atoms. In addition, all the compounds with Ho atoms undergo two successive magnetic transitions with the decrease of temperature: a paramagnetic (PM) to ferromagnetic (FM) transition around T_C and a spin-reorientation (SR) transition around 7?9 K. It is found that both transitions contribute to the magnetic entropy change (ΔS_M). For a field change of 5 T, the maximum values of ?ΔS_M for Gd_0.4Ho_0.6NiIn are 6 J/kg K at T_t=9 K and 10 J/kg K at T_C=52 K, respectively. These two ?ΔS_M peaks overlap partly and result in a wide working temperature range of MCE, and thus leading to the largest RC value of 443 J/kg in the Gd_1?xHo_xNiIn system.     

Investigation of magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by magnetic,differential scanning calorimetry and thermal analysis

We investigated magnetocaloric effect in La_0.45Pr_0.25Ca_0.3MnO₃ by direct methods (changes in temperature and latent heat) and indirect method (magnetization isotherms). This compound undergoes a first-order paramagnetic to ferromagnetic transition with T_C=200 K upon cooling. The paramagnetic phase becomes unstable and it transforms into a ferromagnetic phase under the application of magnetic field, which results in a field-induced metamagnetic transition (FIMMT). The FIMMT is accompanied by release of latent heat and temperature of the sample as evidenced from differential scanning calorimetry and thermal analysis experiments. A large magnetic entropy change of ΔS_m=−7.2 J kg⁻¹ K⁻¹ at T=212.5 K and refrigeration capacity of 228 J kg⁻¹ are found for a field change of ΔH=5 T. It is suggested that destruction of magnetic polarons and growth of ferromagnetic phase accompanied by a lattice volume change with increasing magnetic field is responsible for the large magnetocaloric effect in this compound.     

Large magnetic entropy change and refrigerant capacity in rare-earth intermetallic RCuAl (R=Ho and Er) compounds

The magnetic properties and the magnetocaloric effects of RCuAl (R=Ho and Er) compounds have been investigated. Both HoCuAl and ErCuAl just undergo a second-order ferromagnetic–paramagnetic phase transition at T_C. Large reversible magnetic entropy changes (ΔS_M) are observed around their respective Curie temperatures due to the ferromagnetic–paramagnetic phase transition. For a field change of 0–5 T, the peak values of −ΔS_M of RCuAl (R=Ho and Er) compounds are 23.9 and 22.9 J kg⁻¹ K⁻¹ at T_C, with the values of refrigerant capacity of 393 and 321 J kg⁻¹, respectively. These properties suggest that RCuAl (R=Ho and Er) compounds could be considered as attractive magnetic refrigerants working in low temperature range.     

Magnetic and structural phase transitions in the shape-memory ferromagnetic alloys Ni2+x Mn1−x Ga

The results of an experimental investigation of the temperature dependences of the magnetic susceptibility and resistivity in the shape-memory ferromagnetic alloys Ni_2+x Mn_1−x Ga (x=0–0.20) are reported. A T−x phase diagram is constructed on the basis of these data. It is shown that partial substitution of Ni for Mn causes the temperatures of the structural (martensitic) T _M and magnetic T _C (Curie point) phase transitions to converge. In the region where T _C =T _M the transition temperature increases linearly with magnetic field in the range from 0 to 10 kOe. The kinetics of a magnetic-field-induced martensitic phase transition is investigated, and the velocities of the martensite-austenite interphase boundary during direct and reverse transitions are measured. A theoretical model is proposed and the T−x phase diagram is calculated. It is shown that there exist concentration ranges where the magnetic and martensitic transitions merge into a first-order phase transition. The theoretical results are in qualitative agreement with experiment. Zh. éksp. Teor. Fiz. 115, 1740–1755 (May 1999)     

Giant magneto-caloric effect around room temperature at moderate low field variation in La0.7(Ca1−xSrx)0.3MnO3 perovskites

Among the perovskite manganites, a series of La_1?xCa_xMnO₃ has the largest magneto-caloric effect (MCE) (|ΔS_m|_max=3.2–6.7 J/kg K at ΔH=13.5 kOe), but the Curie temperatures, T_C, are quite low (165–270 K). The system of LaSrMnO₃ has quite high T_C but its MCE is not so large. The manganites La_0.7(Ca_1?xSr_x)_0.3MnO₃ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25) have been prepared by solid state reaction technique with an expectation of large MCE at room temperature region. The samples are of single phase with orthorhombic structure. The lattice parameters as well as the volume of unit cell are continuously increased with the increase of x due to large Sr²⁺ ions substituted for smaller Ca²⁺ ions. The field-cooled (FC) and zero-field-cooled (ZFC) thermomagnetic measurements at low field and low temperatures indicate that there is a spin-glass like (or cluster glass) state occurred. The Curie temperature T_C increases continuously from 258 K (for x=0) to 293 K (for x=0.25). A large MCE of 5 J/kg K has been observed around 293 K at the magnetic field change ΔH=13.5 kOe for the sample x=0.25. The studied samples can be considered as giant magneto-caloric materials, which is an excellent candidate for magnetic refrigeration at room temperature region.     

Spin-glass-like behaviour and magnetic order in Mn[Cr0.5Ga1.5]S4 spinels

Magnetization and susceptibility were investigated as a function of temperature and magnetic field in polycrystalline Mn[Cr_0.5Ga_1.5]S₄ spinel. The dc susceptibility measurements at 919 Oe showed a disordered ferrimagnetic behaviour with a Curie-Weiss temperature θ_CW=−55 K and an effective magnetic moment of 5.96 μ_B close to the spin-only value of 6.52 μ_B for Cr³⁺ and Mn²⁺ ions in the 3d³ and 3d⁵ configurations, respectively. The magnetization measured at 100 Oe revealed the multiple magnetic transitions with a sharp maximum at the Néel temperature T_N=3.9 K, a minimum at the Yafet-Kittel temperature T_YK=5 K, a broad maximum at the freezing temperature T_f=7.9 K, and an inflection point at the Curie temperature T_C=48 K indicating a transition to paramagnetic phase. A large splitting between the zero-field-cooled (ZFC) and field-cooled (FC) magnetizations at a temperature smaller than T_C suggests the presence of spin-glass-like behaviour. This behaviour is considered in a framework of competing interactions between the antiferromagnetic ordering of the A(Mn) sublattice and the ferromagnetic ordering of the B(Cr) sublattice.     

Phase separation, ferromagnetism and magnetic irreversibility in La1−xSrxMn1−yFeyO3

Magnetic susceptibility, χ(T), is investigated in ceramic La_1−xSr_xMn_1−yFe_yO₃ (LSMFO) samples with x=0.3 and y=0.15−0.25. A ferromagnetic (FM) transition observed in LSMFO is accompanied with an appreciable decrease of the transition temperature with increasing y, which is connected to breaking of the FM double-exchange interaction by doping with Fe. Strong magnetic irreversibility, observed in low (B=10 G) field, gives evidence for frustration of the magnetic state of LSMFO. The FM transition, which is expanded with increasing B, is more pronounced in the samples with y=0.15-0.20 and broadens considerably at y=0.25, where the irreversibility is increased. Well above the transition, χ(T) exhibits a Curie-Weiss asymptotic behavior, yielding very large values of the effective Bohr magneton number per magnetic ion, incompatible with those of Mn or Fe single ions. At y=0.15 and 0.20 a critical behavior of χ⁻¹(T)∼(T/T_C−1)^γ in the region of the FM transition is characterized by influence of two different magnetic systems, a 3D percolative one with γ₌γ_p≈1.8 and T_C=T_C^(p), and a non-percolative 3D Heisenberg spin system, with γ=γ_H≈1.4 and T_C=T_C^(H), where T_C^(p)<T_C^(H). At y=0.25 the percolative contribution to the critical behavior of χ(T) is not observed. The dependence of χ on T and y gives evidence for phase separation, with onset already near the room temperature, leading to generation of nanosize FM particles in the paramagnetic host matrix of LSMFO. The ferromagnetism of LSMFO is attributable to percolation over the system of such particles and generation of large FM clusters, whereas the frustration is governed presumably by a system of smaller weakly-correlated magnetic units, which do not enter the percolative FM clusters.     

Charge and lattice dynamics of ordered state in La1/2Ca1/2MnO3: infrared reflection spectroscopy study

We report an infrared reflection spectroscopy study of La_1/2Ca_1/2MnO₃ over a broad frequency range and temperature interval which covers the transitions from the high temperature paramagnetic to ferromagnetic and, upon further cooling, to antiferromagnetic phase. The structural phase transition, accompanied by a ferromagnetic ordering at T_C=234 K, leads to enrichment of the phonon spectrum. A charge ordered antiferromagnetic insulating ground state develops below the Néel transition temperature T_N=163 K. This is evidenced by the formation of charge density waves and opening of a gap with the magnitude of 2Δ₀=(320±15) cm⁻¹ in the excitation spectrum. Several of the infrared active phonons are found to exhibit anomalous frequency softening. The experimental data suggest coexistence of ferromagnetic and antiferromangetic phases at low temperatures.     

Second-order phase transition with coexistence of short-range and long-range ferromagnetic interactions in Ba1.7La0.3FeMoO6 compound

In this work, the magnetic properties and critical behavior around ferromagnetic–paramagnetic (FM–PM) phase transition in Ba_1.7La_0.3FeMoO₆ compound have been investigated in detail. This compound exhibits a second-order magnetic phase transition with Curie temperature T_C = 345 K. The critical exponents β, γ, and δ that are determined by using the modified Arrott plots (MAP), the Kouvel–Fisher (KF) and the critical isotherm analysis agree very well. Our results indicate a coexistence of short-range and long-range ferromagnetic (FM) interactions in Ba_1.7La_0.3FeMoO₆ compound. The existence of long-range FM interactions in this compound can be associated with the crystal structure of materials with long-range Fe/Mo ordering parameter and strength of double-exchange interaction, whereas the existence of the short-range FM interactions can be explained by magnetic inhomogeneity and FM clusters.     

Giant magnetic refrigerant capacity in Ho3Al2 compound

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Ho₃Al₂ compound are investigated by magnetization and heat capacity measurements. Two successive magnetic transitions, a spin-reorientation (SR) transition at T_SR=31 K followed by a ferromagnetic (FM) to paramagnetic (PM) transition at T_C=40 K, are observed. Both magnetic transitions contribute to the MCE and result in a large magnetic entropy change (ΔS_M) in a wide temperature range. The maximum values of ?ΔS_M and adiabatic temperature change (ΔT_ad) reach 18.7 J/kg K and 4.8 K for the field changes of 0–5 T, respectively. In particular, a giant value of refrigerant capacity (RC) is estimated to be 704 J/kg for a field change of 5 T, which is much higher than those of many potential refrigerant materials with similar transition temperatures.     

Electronic transport properties of stuffed compositions of ferromagnetic copper chromium telluride: Cu1+xCr2Te4 (x=0-1)

We present here a detailed study of electronic transport properties of the metallic-ferromagnetic compounds Cu_1+xCr₂Te₄, having excess Cu atoms with x=0-1, from 2 to 400 K. The stuffing of the copper atoms in the parent structure reduces the ferromagnetic ordering temperature T_C from 325 to 156 K, while for the entire range the dependence of the electrical resistance and the thermopower with temperature and the anomalies in them on the magnetic ordering remain similar. All the compounds show a magnon-drag contribution in thermopower as a positive maximum around T_C/3, and a T² - dependence of resistivity at low temperatures. The increasing effects of the short range magnetic ordering in the paramagnetic resistivity are seen with the increase in the stuffing of atoms in these compounds. The transport properties are explained by the current carriers —the holes in a wide energy band dominated by the p-state of Te-atoms, which are scattered by the spindisorder in the paramagnetic phase and from the magnons in the ferromagnetic phase.     

Magnetocaloric effect in Y-doped La0.6Ca0.4MnO3 enhanced by Griffiths phase and re-entrance of first-order phase transition

It has been known that bulk La_0.6Ca_0.4MnO₃ is an intermediate material of the first- and second-order characters with the tricritical-point exponents, and the doping of a metal ion in it usually causes a continuous second-order transition. The present work reports the re-entrance of a discontinuous first-order transition in orthorhombic La_0.6-xY_xCa_0.4MnO₃ (x = 0.03–0.09) compounds. This enhances the magnetocaloric effect. For the field H = 30 kOe, the maximum magnetic-entropy change (|ΔS_max|) and relative cooling power (RCP) have been evaluated being about 5.45–6.3 J/kg·K and 130–185 J/kg, respectively. If combining these compounds as refrigerant blocks in a rotary ring model, a magnetic cooling device can operate at temperatures T = 85–280 K, with |ΔS_max| ≈ 5.5 J/kg⋅K and RCP ≈ 1073 J/kg. Aside from the re-entranced first-order phase transition, the magnetization and structural analyses have proved the enhanced magnetocaloric effect in La_0.6-xY_xCa_0.4MnO₃ related to a Griffiths singularity, and local Jahn-Teller distortions of the perovskite structure (since the Mn³⁺/Mn⁴⁺ ratio and orthorhombic structural phase are unchanged vs. x).