13 research outputs found
Study of the magnetocaloric effect in intermetallics RTX (R = Nd, Gd; T = Sc, Ti ; X = Si, Ge)
A detailed study of the magnetocaloric properties of six compounds of the intermetallic family RTX (R = Nd, Gd; T = Sc, Ti ; X = Si, Ge) has been undertaken: NdScSi, NdScGe, GdScSi, GdScGe, GdSc(Si0.5Ge0.5) and Gd(Sc0.5Ti0.5)Ge. The magnetic entropy changes at the Curie temperature TC and the refrigerant capacities signal that they are competitive magnetocaloric materials, showing that an improvement can be obtained by tuning the composition, as Gd(Sc0.5Ti0.5)Ge presents the best properties. These magnetocaloric variables fulfill the scaling equations with the critical parameters corresponding to the universality classes to which the ferromagnetic transitions belong (3D-XY, 3D-Heisenberg, Mean field). For each compound, a universal curve has been found for the rescaled magnetic entropy changes obtained at different applied fields, whose behavior at temperatures below TC indicate the relevance of taking into account the demagnetization field. Finally, it has been demonstrated that the rescaled magnetic entropy changes for the compounds which share the same universality class collapse onto a single universal curve.This work has been supported by Universidad del País Vasco UPV/EHU (GIU16/93)
Critical behavior of the ferromagnetic transition in GdSc(Si,Ge) intermetallic compounds
A complete study on the critical behavior of the paramagnetic to ferromagnetic transition in intermetallics GdScSi, GdScGe, GdSc(Si0.5Ge0.5) and Gd(Sc0.5Ti0.5)Ge has been carried out by means of magnetic as well as calorimetric measurements, using a high resolution ac photopyroelectric technique. The critical exponents alfa, beta, gamma, delta and the ratio of the critical coefficients A+/A- have been independently obtained for the four samples. It has been proved that the magnetic interactions are short range as the values of the critical parameters correspond to the 3D-Heisenberg class, stating an isotropic ordering of the Gd spins. In some cases, there are small deviations of some of the critical parameters from the theoretical values which have been discussed on the basis of the variation of the d states hybridization between the rare earth and the transition metal, as well as the presence of small magnetocrystalline anisotropies arising from spin-orbit coupling effects.This work has been supported by Universidad del País Vasco UPV/EHU (GIU16/93)
Retrieving the thermal diffusivity and effusivity of solids from the same frequency scan using the front photopyroelectric technique
The photopyroelectric (PPE) technique in the front configuration consists in illuminating one
surface of a pyroelectric slab while the other surface is in contact with the test sample. This
method has been widely used to measure the thermal effusivity of liquids. Recently, it has
been extended to measure the thermal effusivity of solids, by taking into account the influence
of the coupling fluid layer used to guarantee the thermal contact. In both cases, the sample
(liquid or solid) must be very thick. In this work, we propose a classical frequency scan of a
thin sample slab to retrieve the thermal diffusivity and effusivity simultaneously. We use the
amplitude and the phase of the front PPE signal, which depend on four parameters: the sample
diffusivity and effusivity, the coupling fluid thickness and the coefficient of heat losses. It is
demonstrated that the four quantities are not correlated. PPE measurements performed on a
set of calibrated solids confirm the ability of the method to obtain the thermal diffusivity and
effusivity of solids accurately.This work has been supported by Ministerio de Economía y Competitividad, (DPI2016-77719-R, AEI/FEDER, UE), by Gobierno Vasco (KK-2016/00027) and by Universidad del País Vasco UPV/EHU (GIU16/33)
Critical behavior study of magnetic transitions in Dy3Co single crystals
An ac photopyroelectric calorimeter has been used to study the critical behaviour of the magnetic transitions in Dy3Co measuring thermal diffusivity, specific heat and thermal conductivity, at low temperature. There are two phase transitions, both of which present singularities in the three variables. The antiferromagnetic to paramagnetic phase transition at 42 K complies with the short range, isotropic universality class, 3D-Heisenberg (alfaexp = -0.133 for specific heat, bexp = -0.145 for thermal diffusivity, alfatheor = btheor = -0.13). In the case of the lower transition where there is a rearrangement of the antiferromagnetic spin ordering at 32 K the critical behavior shows a deviation from isotropy. These results are linked to magnetic measurements already found in literature.This work has been supported by Universidad del País Vasco/Euskal Herriko Unibertsitatea (UPV/EHU-GIU16/93) and also partially supported by FASO of Russia (themes No 01201463328 and 01201463334)
Peculiar magnetocaloric properties and critical behavior in antiferromagnetic Tb3Ni with complex magnetic structure
A study on the magnetocaloric properties of a Tb3Ni single crystal (which crystallizes in the orthorhombic Pnma space group) has been undertaken and combined with the study of the character and critical behavior of its magnetic transitions. It presents two important magnetocaloric effects in the temperature range 3–90 K due to the richness and variety of its temperature and magnetic field induced phase transitions. There is a conventional (direct) magnetocaloric effect with a maximum at 65 K and very competitive properties: = 16.6 J/kgK, RCFWHM = 432 J/kg, with a 50 K span, for μ0ΔH = 5 T, which is due to the transition from a magnetically ordered state to the paramagnetic (PM) state with a combined antiferromagnetic to ferromagnetic (AFM-FM) metamagnetic transition. Besides, it also presents an inverse magnetocaloric effect at very low temperature for which the presence of metamagnetic transitions between AFM and FM states is responsible (=19.9 J/kgK, RCFWHM = 245 J/kg, with a 15 K span, for μ0ΔH = 5 T). At low field (<2 T), the character of the AFM-PM transition which takes place at ≈ 61 K has been well established to be second order and governed by short range order interactions, as the critical parameters α, A+/A- obtained from the specific heat at μ0H = 0 T point to the 3D-Heisenberg universality class. Conversely, the metamagnetic transitions between AFM and FM states, which appear for magnetic fields higher than 2 T, have a first order character, as proved by the magnetization behavior as a function of field and temperature. These properties make this material extremely interesting for magnetic refrigeration applications in the gas liquefaction range 4–77 K.This work has been supported by Universidad del País Vasco UPV/EHU (GIU16/93). A. Herrero thanks the Department of Education of the Basque Government as grantee of the programme “Programa Predoctoral de Formación de Personal Investigador No Doctor”. The authors thank for technical and human support provided by SGIker of UPV/EHU. This work was also supported by Russian Science Foundation (project No. 18-72-10022)
Effect of Nd doping on the crystallographic, magnetic and magnetocaloric properties of NdxGd3-xCoNi
The crystal structure, magnetic and magnetocaloric properties, and the critical behavior of representative compounds in the pseudo-ternary NdxGd3-xCoNi series have been investigated (x = 0.15, 0.5, 1.0, 1.5). All these phases are isotypic with the parent compound Gd3CoNi, crystallizing with the monoclinic Dy3Ni2-type (mS20, C2/m, No. 12). All samples present a paramagnetic to ferromagnetic (PM-FM) second order phase transition with decreasing Curie temperature as the Nd concentration is increased (TC = 171 K, 150 K, 120 K and 96 K, respectively) and, at lower temperatures, there is a spin reorientation which leads to a complex magnetic ground state. The critical exponents (beta, gamma, delta) have been retrieved for the PM-FM transitions. On the one hand, in x = 0.15, 0.5, 1.5 the value of γ ≈ 1 indicates that the magnetic interactions are long-range order while the values of β point to a certain deviation from the 3D-Heisenberg universality class; on the other hand, NdGd2CoNi has a particular critical behaviour, as β is close to the Mean Field model while γ is close to the uniaxial 3D-Ising one. Concerning the magnetocaloric properties, the magnetic entropy change and refrigerant capacity present competitive values, interesting for cryogenic applications. Finally, the thermal diffusivity values of these compounds are extremely good for practical magnetocaloric refrigeration systems, as they are in the range 1.5-3 mm2/s.This work has been supported by Departamento de Educación del Gobierno Vasco (Project No. IT1430-22)
Magnetocaloric properties, magnetic interactions and critical behavior in Ho6(Fe,Mn)Bi2 intermetallics
Four polycrystaline Fe2P-type Ho6(Fe,Mn)Bi2 intermetallic compounds (space group , No. 189, hP9) have been studied using magnetic techniques in order to explore their ability as magnetocaloric materials, and study the critical behavior of the paramagnetic (PM) to ferromagnetic (FM) transitions to obtain a deeper understanding of the range of the magnetic interactions. The obtained critical exponents β, γ and δ for the four compounds studied (Ho6MnBi2, Ho6FeBi2, Ho6(Mn0.5Fe0.5)Bi2, Ho6(Mn0.75Fe0.25)Bi2) point to long-range order interactions, as they are close to those of the Mean Field Universality class. All of the compounds show relevant magnetocaloric properties over a very broad temperature range, limited by the PM-FM transition and a spin-reorientation one, well separated in all cases. They present very high values of the refrigerant capacities (from 520 J/kg to 709 J/kg at 5 T), good magnetic entropy changes (from 3.4 to 5.7 J/(kgK) at 5 T), and a flat and wide temperature span for the working temperature range (nearly 200 K for Ho6MnBi2, 80 K for Ho6FeBi2 at 5T). The change in properties with composition proves that the magnetocaloric properties can be tuned in Fe2P-type compounds to accommodate different refrigeration applications. Finally, the magnetocaloric scaling laws have been successfully tested and universal curves for the magnetic entropy change have also been obtained in the PM-FM transition region.This work has been supported by Universidad del País Vasco UPV/EHU (GIU16/93)
Magnetocaloric properties and unconventional critical behavior in (Gd,Tb)6(Fe,Mn)Bi2 intermetallics
The magnetic and magnetocaloric properties of the intermetallic family (Gd,Tb)6(Fe,Mn)Bi2 have been studied from 2 K to temperatures above the respective Curie temperatures TC. The substitution of Gd by Tb (Gd6FeBi2, Gd3Tb3FeBi2, Tb6FeBi2) tunes TC in the range 350-250 K and favors the apparition of a metamagnetic transition at very low temperature (below 10 K) from a complex magnetic state to a ferromagnetic one, as well as a spin reorientation transition below Tm = 72 K. As a consequence, an important inverse magnetocaloric effect (IMCE) appears below 20 K and an interesting direct magnetocaloric effect (DMCE) appears over a wide temperature span between TC and Tm with maxima at those temperatures. The partial substitution of Fe by Mn in Tb6Fe0.5Mn0.5Bi2 shifts these effects upwards in temperature while expanding the region of the direct magnetocaloric effect between 70 and 400 K. The combination of adjoint IMCE and DMCE as well as the wide span of the latter shows that tuning this family allows to locate the magnetocaloric effect in different regions of interest. The critical behavior of the PM-FM transitions has been studied obtaining the critical exponents α, β, γ, δ and checking that the respective magnetocaloric effects also scale with the critical parameters n and δ. The transition in Gd6FeBi2 belongs to the Heisenberg universality class with deviations due to magnetocrystalline anisotropies; the critical exponents for Gd3Tb3FeBi2 (in agreement with the Mean Field model) suggest the presence of long range order magnetic interactions, while Tb6FeBi2 and Tb6Fe0.5Mn0.5Bi2 present an unconventional critical behavior aligned with long range order interactions.This work has been supported by Universidad del País Vasco UPV/EHU (project GIU19/305) and the Russian Fund for Basic Research (project N° 20-03-00209-a). A. Herrero thanks the Department of Education of the Basque Government as grantee of the programme “Programa Predoctoral de Formación de Personal Investigador No Doctor”. The authors thank for technical and human support provided by SGIker of UPV/EHU
Tailoring the magnetocaloric, magnetic and thermal properties of Dy6(Fe,Mn)X2 intermetallics (X==Sb, Te, Bi)
[EN] The structural, magnetic, magnetocaloric (MCE) and thermal properties of seven Fe2P-type Dy6(Fe,Mn)X2 (X=Sb, Bi, Te) intermetallics (space group P 6 over line 2 m, N 189, hP9) have been experimentally studied. They present a paramagnetic to ferromagnetic transition (in the range 129-370 K), followed, as temperature decreases, by a spin-reorientation one (from 52 to 170 K) and a ground magnetic state at 2 K with anti-ferromagnetic components. This state turns into a ferromagnetic state when a magnetic field is applied. The critical exponents beta,gamma,delta related to the PM-FM transition point to long range order interactions but in most compounds their values severely deviate from the Mean Field class, presenting an unconventional critical behavior, probably due to magnetocrystalline anisotropies. This magnetic complexity has the consequence that in every intermetallic three MCE effects arise: Two direct magnetocaloric effects (DMCE) with a table-like effect in between (from 40 K to more than 400 K), with moderate values of the magnetic entropy maxima (up to 6.9 J/kgK for 140 Delta H = 5 T, with the tableau in-between being around 4 J/kgK, for Dy6FeSb2 and Dy6FeSbTe). The calculation of the Thermal Average Entropy Change allows to place the properties of two compounds (Dy6FeSb2 and Dy6FeSbTe) close to other rare earth based high entropy alloys described in literature. The seven compounds present a relevant third MCE, inverse, below 25 K, with a value as high as 17.8 J/kgK (140 Delta H = 5 T) for Dy6FeSbTe. The maximum of the magnetic entropy change at the Curie tem-perature has been shown to scale with the critical exponents found and universal curves have been built. Finally, the thermal diffusivities in the range of the DMCE have been measured, with the result that they present good values (between 1 and 3 mm2/s) to be used in real magnetocaloric refrigeration systems.This work has been supported by Universidad del Pais Vasco UPV/EHU (project GIU19/058) and the Russian Fund for Basic Research (project No 20-03-00209-a). A. Herrero thanks the Department of Education of the Basque Government as grantee of the programme "Programa Predoctoral de Formacion de Personal Investigador No Doctor". The authors thank for technical and human support provided by SGIker of UPV/EHU, specially the fruitful discussions with Dr. I. Orue
Selecting optimal R6TX2 intermetallics (R = Gd, Tb, Dy; T = Mn, Fe, Co, Ni; X = Sb, Te) for magnetic refrigeration
A complete experimental study of the physical properties playing a relevant role on magnetic refrigeration application (structural, magnetic, magnetocaloric and thermal) has been performed over nine selected Fe2P-type R6TX2 (R= Gd, Tb, Dy; T= Mn, Fe, Co, Ni; X=Sb, Te) intermetallic compounds, to work close to room temperature. Two magnetic phase transitions are present on these materials: a paramagnetic to ferromagnetic transition in the range 182-282 K and a spin reorientation transition in the range 26-76 K. As a consequence, two peaks related to a direct magnetocaloric effect (DMCE) appear in the magnetic entropy change, generating a wide table-like plateau region in between both peaks, which is required to improve the efficiency of refrigerators following an Ericsson cycle. The highest magnetic entropy peak value for μ0ΔH = 5 T is found for Tb2Dy4FeSb2, with 7.72 J/kg K around 182 K. For the same applied field the other compounds show moderate values around room temperature (2.88-4.53 J/Kg K). However, the superposition of the two peaks results in huge refrigerant capacity values, up to RCFWHM(5 T)=1103.04 J/kg in the case of Tb2Dy4FeSb2. The thermal diffusivity, effusivity conductivity and specific heat have been measured at room temperature, and the temperature dependence of the former has been obtained around the relevant magnetic phase transition region, with values in the range 1.3-2.3 mm2/s, which are good for magnetic refrigerators under high working frequencies. The study is completed with a rigorous critical behavior analisis of the second order PM-FM transition. The critical exponent γ points to long range order interactions, in general, while β values are in the range (0.59-0.90), indicating a deviation from theoretical models as a reflection of the magnetic complexity in these compounds. The critical exponents have been used to confirm the scaling relations of magnetocaloric properties, and the scaling of refrigerant capacity (RC) values in materials presenting two magnetic phase transitions is addressed, concluding that for a correct scaling of RC the magnetic entropy change peak must be considered symmetric. The role of each atom on the properties of the compounds is discussed.This work was supported by Departamento de Educación del Gobierno Vasco (project IT1430-22) and the Russian Fund for Basic Research through the project no. 20-03-00209-a, as well as by an ICDD (International Centre for Diffraction Data) (USA) grant n 05-07