Field induced sign reversal of magnetocaloric effect in Gd2In

We report the magnetocaloric effect in the metamagnetic compound Gd₂In obtained from magnetization measurement. Gd₂In was previously reported to have two magnetic transitions: (i) a paramagnetic to ferromagnetic transition below 190 K and (ii) a ferromagnetic to an antiferromagnetic state below 105 K. The low temperature antiferromagnetic state is unstable under an applied magnetic field and undergoes metamagnetic transition to a ferromagnetic like state. We observe conventional positive magnetocaloric effect (the magnetic entropy change, ΔS_M<0) around 190 K at all applied fields. The magnetocaloric effect is found to be inverse (negative) at low fields around 105 K (ΔS_M>0), however it turns positive at higher fields (ΔS_M<0). The observed anomaly is found to be related to the field induced transition which drives the system from an antiferromagnetic to a ferromagnetic state.     

Understanding the magnetic ground state of rare-earth intermetallic compound Ce4Sb3: Magnetization and neutron diffraction studies

Magnetization and neutron diffraction studies have been performed on Ce₄Sb₃ compound (cubic Th₃P₄-type, space group I4¯3d, no. 220). Magnetization of Ce₄Sb₃ reveals a ferromagnetic transition at ∼5 K, the temperature below which the zero-field-cooled and field-cooled magnetization bifurcate in low applied fields. However, a saturation magnetization (M_S) value of only ∼0.93μ_B/Ce³⁺ is observed at 1.8 K, suggesting possible presence of crystal field effects and a paramagnetic/antiferromagnetic Ce³⁺ moment. Magnetocaloric effect in this compound has been computed using the magnetization vs. field data obtained in the vicinity of the magnetic transition, and a maximum magnetic entropy change, −ΔS_M, of ∼8.9 J/kg/K is obtained at 5 K for a field change of 5 T. Inverse magnetocaloric effect occurs at ∼2 K in 5 T indicating the presence of antiferromagnetic component. This has been further confirmed by the neutron diffraction study that evidences commensurate antiferromagnetic ordering at 2 K in zero magnetic field. A magnetic moment of ∼1.24μ_B/Ce³⁺ is obtained at 2 K and the magnetic moments are directed along Z-axis.     

Electrical and magnetic properties of TmCoIn5 and YbCoIn5 single crystals

Electrical and magnetic properties of TmCoIn₅ and YbCoIn₅ single crystals were investigated by means of electrical resistivity and magnetization measurements in the temperature range from 300 to 0.5 K under the magnetic field up to 5 T. TmCoIn₅ is an antiferromagnetic metal with a Néel temperature T_N=2.6 K. YbCoIn₅ shows non-magnetic behavior, reflecting of divalent Yb ion.     

Magnetic ordering in the frustrated system FeSc2S4

The sample of FeSc₂S₄ was prepared by solid reaction method. The crystallographic structure and the magnetic properties of the fabricated compound were investigated by X-ray, and superconducting quantum interference device (SQUID) magnetometer and Mössbauer spectroscopy. The polycrystalline FeSc₂S₄ confirmed the normal cubic spinel structure (space group Fd3m). The lattice constants a₀ and anion parameter u are 10.519 Å and 0.255, respectively. The Mössbauer spectroscopy has been studied for the FeSc₂S₄ at various temperatures, ranging from 4.2 K to room temperature. The spectra consist of two doublets at 4.2 K while a single line at room temperature. It is noticeable that the Mössbauer spectra of two doublet patterns with large electric quadrupole splitting (ΔE_Q) remain over the Néel temperature. Those are interpreted as a result of large electric quadrupole interaction compared to magnetic dipole interaction. The magnetic susceptibility measurements were performed with a SQUID magnetometer for temperatures 2<T<320 K, in external fields up to 5 kOe. Magnetic behavior shows antiferromagnetic behavior and the magnetic superexchange interactions between the Fe ions are weakly antiferromagnetic. The paramagnetic susceptibilities follow Curie–Weiss (CW) law with CW temperature Θ_CW=−100 K, and frustration parameter f=−Θ_CW/T_N is of the order of 1000. We conclude that two sublattices are coupled antiferromagnetically, leading to strong frustration effects.     

Spin glass like behavior in Cd0.42Mn0.58In2S4

The magnetic behavior of the diluted magnetic semiconductor Cd_0.42Mn_0.58In₂S₄ has been study by dc magnetization and ac susceptibility experiments. Zero field cooled and field cooled measurements reveal irreversibility below T_irr=2.60±0.15 K. Ac susceptibility data, performed as a function of the temperature and the frequency, confirm the spin-glass like behavior of the material with T_f=2.75±0.15 K. High temperature susceptibility data follow a typical Curie-Weiss law with θ=−74±1 K which suggests predominant antiferromagnetic interactions. The randomness of the magnetic ions, necessary to explain the magnetic behavior of the material, has been determined by X-ray powder diffraction experiments.     

Magnetic properties of the intermetallic compound Ce5Ge4

Magnetic and magnetocaloric properties of the compound Ce₅Ge₄ have been studied. This compound has orthorhombic Sm₅Ge₄-type structure (space group Pnma, no. 62) and orders ferromagnetically at ~12 K (T_C). The paramagnetic Curie temperature is ~−20 K suggesting the presence of competing ferromagnetic and antiferromagnetic interactions in this compound. The magnetization does not seem to saturate even in fields of 90 kOe at 3 K consistent with the presence of competing interactions. Saturation magnetization value (extrapolated to 1/H→0) of only 0.8μ_B/Ce³⁺ is obtained compared to the free ion value of 2.14μ_B/Ce³⁺. This moment reduction in the ordered state of Ce₅Ge₄ could be due to partial antiferromagnetic/paramagnetic ordering of the Ce moments and may also be due to crystalline electric field effects. Magnetic entropy change near T_C, calculated from the magnetization vs. field data, is found to be moderate with a maximum value of ~9 J/kg/K at ~11 K for a field change of 90 kOe.     

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.     

Some aspects of antiferromagnetic ordering in LiMnP0.85V0.15O4: Neutron diffraction and DC-magnetization studies

V-substituted LiMnPO₄ has been synthesized by the solid state reaction route. Combined Rietveld refinement of neutron and X-ray data revealed that all vanadium ions are located in the same positions as the phosphorus ions. The magnetic structure of LiMnP_0.85V_0.15O₄ was found to be the same as that described for undoped antiferromagnetic LiMnPO₄ (T_N=34.5 K). DC-magnetization measurements were carried out to study the peculiarities of magnetic ordering in LiMnP_0.85V_0.15O₄. An irreversible behavior of DC magnetization was found at magnetic fields less than ∼2 kOe. It was demonstrated that an increase in the magnitude of the applied field leads to a reduction of the discrepancy between zero-field-cooled and field-cooled processes. These effects were explained by the movement of domain walls and by transition of the system to a monodomain state. The anomaly in the magnetization vs field dependence attributed presumably to the spin-flop transition was observed at ∼40 kOe. The existence of magnetic inhomogeneity in the paramagnetic phase of LiMnP_0.85V_0.15O₄ was proved by the analysis of the χ?T product. It was concluded that the observed changes in χ?T are indicative of a competition between ferromagnetic and antiferromagnetic correlations at temperatures slightly exceeding T_N.     

Al-doping effect on the structural and physical properties of delafossite-type oxide CuCrO2

The structure, Raman spectroscopy, magnetization, and dielectric properties of delafossite-type oxide CuCr_1−xAl_xO₂ have been characterized. It was found that Al substitution generates an anisotropic effect on the structure, besides magnetic dilution. The temperature dependence of all samples exhibits paramagnetic behavior at high temperature. Above x=0.2 the ferromagnetic transition at 120 K disappears. It is argued that Al substitution destabilizes the antiferromagnetic order of Cr³⁺ ions and modulates the spin configuration, leading to a weak ferromagnetism. The coupling between the magnetic order and ferroelectric order is also characterized.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (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 (T_C) 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 (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Magnetic,electrical transport and electron spin resonance studies of Fe-doped manganite LaMn0.7Fe0.3O3+δ

We have investigated the magnetic, electrical transport and electron spin resonance (ESR) properties of polycrystalline Fe-doped manganite LaMn_0.7Fe_0.3O_3+δ prepared by sol–gel method. A typical cluster-glass feature is presented by DC magnetization and AC susceptibility measurements and a sharp but shallow memory effect was observed. Symmetrical Lorentzian lines of the Mn/Fe spectra were detected above 120 K, where the sample is a paramagnetic (PM) insulator. When the temperature decreases from 120 K, magnetic clusters contributed from ferromagnetic (FM) interaction between Mn³⁺ and Mn³⁺/Fe³⁺ ions develop and coexist with PM phase. At lower temperature, these FM clusters compete with antiferromagnetic (AFM) ones between Fe³⁺ ions, which are associated with a distinct field-cooled (FC) effect in characteristic of cluster-glass state.     

Spectroscopic analysis and magnetic susceptibility of CuO-TeO2-V2O5 glasses

This article reports on the structure of the glassy system xCuO-65TeO₂-(35−x)V₂O₅, 5≤x≤10 mol% which was studied using infrared (IR) and Raman spectroscopy methods as well as magnetic susceptibility measurements. IR and Raman spectroscopy analysis reveals the presence of four main absorption bands attributed to [TeO₃], [TeO₄], [VO₄], and [VO₅] structure units. It suggests that Cu²⁺ ions occupy the available open spaces of the Te-O network without straining the bonds too much. Increasing the concentration of Cu²⁺ ions beyond 5 mol% results in the modification of the glass by straining and locally distorting the surrounding of the Te-O network. The magnetic susceptibility of these materials was investigated in the temperature range of 5-200 K revealing the paramagnetic behavior described by the Curie-Weiss law and indicating the presence of weak antiferromagnetic exchange interactions between Cu ions. The magnetic entropy change of the glasses was determined based on the temperature and magnetic field dependence of magnetization.     

Effect of oxygen vacancy and dopant concentration on the magnetic properties of high spin Co doped TiO2 nanoparticles

Co doped TiO₂ nanoparticles have been synthesized by a simple sol-gel route taking 7.5, 9.5 and 10.5 mol% of cobalt concentration. Formation of nanoparticles is confirmed by XRD and TEM. Increase in d-spacing occurs for (0 0 4) and (2 0 0) peak with increase in impurity content. Valence states of Co and its presence in the doped material is confirmed by XPS and EDX. The entire vacuum annealed samples show weak ferromagnetism. Increased magnetization is found for 9.5 mol% but this value again decreases for 10.5 mol% due to antiferromagnetic interactions. A blocking temperature of 37.9 K is obtained, which shows shifting to high temperature as the dopant concentration is increased. The air annealed sample shows only paramagnetic behavior. Temperature dependent magnetic measurements for the air annealed sample shows antiferromagnetic behavior with a Curie-Weiss temperature of −16 K. Here we report that oxygen vacancy and cobalt aggregates are a key factor for inducing ferromagnetism-superparamagnetism in the vacuum annealed sample. Appearance of negative Curie-Weiss temperature reveals the presence of antiferromagnetic Co₃O₄, which is the oxidation result of metallic Co or cobalt clusters present on the host TiO₂.     

Large vertical loop shifts in mechanically synthesized (Mn,Fe)2O3−t nanograins

Magnetic properties of zero field cooled (ZFC) and field cooled (FC) sample of (Mn,Fe)₂O_3−t nanograins have been investigated by magnetometry (up to 70 kOe) and Mössbauer spectroscopy (up to 60 kOe) in the temperature interval 4.2–300 K. Large horizontal (up to 0.8 kOe) and vertical (up to 80%) shifts of the magnetization hysteresis loops are observed in the FC regime. The obtained results are discussed in terms of exchange interaction between an antiferromagnetic core and a spin-glass-like state of the nanograins boundaries. It is shown that hysteresis loop shifts (horizontal and vertical) depend on the field cooling magnitude, an effect that can be understood by the change of the boundary magnetic structure induced by the external magnetic field. The vertical magnetization shift is described by a phenomenological model, which takes into account the magnetic interaction between the spin-glass like boundary spins and the applied field.     

Thermal and magnetic properties of DyB62 at low temperatures

Temperature dependences of heat capacity C_P(T) and magnetization M(T) of an icosahedral dysprosium boride (DyB₆₂) single crystal have been experimentally investigated in the temperature range of 2-300 K. The magnetic susceptibility χ(T) of DyB₆₂ follows Curie-Weiss law with a paramagnetic Curie temperature of −3.7 K, which implies that the antiferromagnetic interactions are dominant in this material and suggests the possibility of magnetic ordering at low temperatures. This conjecture is supported by the temperature dependence of heat capacity C_P(T), which decreases upon heating from 2 to 7 K. The heat capacity of DyB₆₂ at 2 K is analyzed as a sum of magnetic, Debye, two-level system and soft atomic potential components.     

Magnetic properties and charge ordering in Pr0.75Na0.25MnO3 manganite

The structural and magnetic properties of Pr_0.75Na_0.25MnO₃ have been investigated experimentally. At room temperature, the compound shows paramagnetic characteristic. Along with decreasing temperature, a peak appears in the magnetization versus temperature curve around 220 K. To clarify whether this peak is associated with the ordering arrangement of Mn³⁺ and Mn⁴⁺ ions, electron diffraction experiments were carried out below and above 220 K respectively. Only basic Brag diffraction spots can be observed at high temperatures, however, superlattice diffraction appears below 220 K. This provides direct evidence for the existence of charge ordering in Pr_0.75Na_0.25MnO₃. We find the Mn³⁺ and Mn⁴⁺ cations form zigzag chains in a-c plane by analyzing the diffraction patterns. Combining with the magnetization measurements and the results of electron spin resonance, we confirm the antiferromagnetic phase and ferromagnetic component coexist in Pr_0.75Na_0.25MnO₃ below 120 K.     

Ferromagnetic resonance observation of a phase transition in magnetic field-aligned Fe2O3 nanoparticles

Fe₂O₃ hematite (alpha) nanoparticles suspended in the liquid phase of the liquid crystal 4,4-azoxyanlsole (PAA) are cooled below the freezing temperature (397 K) in a 4000 G dc magnetic field. The in field solidification locks the direction of maximum magnetization of the particles parallel to the direction of the applied dc magnetic field removing the effects of dynamical fluctuations of the nanoparticles on the magnetic properties allowing a study of the intrinsic magnetic properties of the nanoparticles as well as the anisotropic behavior of the ferromagnetic resonance (FMR) signal. Freezing in PAA allows temperature-dependent measurements to be made at much higher temperature than previous measurements. The field position, line width and intensity of the FMR signal as a function of temperature as well as the magnetization show anomalies in the vicinity of 200 K indicative of a magnetic transition, likely the previously observed Morin transition shifted to lower temperature due to the small particle size. Weak ferromagnetism is observed below T_c in contrast to the bulk material where it is antiferromagnetic below T_c. The Raman spectrum above and below 200 K shows no evidence of a change in lattice symmetry associated with the magnetic transition.     

Unusual magnetization suppression induced by higher magnetic field in (La0.83Bi0.17)0.67Ca0.33MnO3

Magnetization behavior of (La_0.83Bi_0.17)_0.67Ca_0.33MnO₃ has been investigated in the temperature range from 100 to 180 K. A metamagnetic transition was observed in the temperature region, where the magnetization was measured after a zero-field-cooling from room temperature to a selected temperature. Experimental results show that, after a higher magnetization route, the field-increasing branches of the magnetization curves shows an unusual training effect: below a magnetic field H₀, the applied magnetic field enhances the value of magnetization; however, above H₀ the magnetic field suppresses the value, and the behavior cannot be totally attributed to the enhancement effect of the applied magnetic field on ferromagnetic phase fraction. It is proposed that, in the two-phase coexistence region, the higher magnetic field promotes the phase separation and leads to both the fraction of ferromagnetic domain and the stabilization of antiferromagnetic domain increase.     

Spin-glass-like behavior in ZnxCryAlzSe4

The magnetic and electrical properties of the Al-doped polycrystalline spinels Zn_xCr_yAl_zSe₄ (0.13≤z≤0.55) with the antiferromagnetic (AFM) order and semiconducting behavior were investigated. A complex antiferromagnetic structure below a Néel temperature T_N≈23 K for the samples with z up to 0.4 contrasting with the strong ferromagnetic (FM) interactions evidenced by a large positive Curie-Weiss temperature θ_CW decreasing from 62.2 K for z=0.13 to 37.5 K for z=0.55 was observed. Detailed investigations revealed a divergence between the zero-field-cooling (ZFC) and field-cooling (FC) susceptibilities at temperature less than T_N suggesting bond frustration due to competing ferromagnetic and antiferromagnetic exchange interactions in the compositional range 0.13≤z≤0.4. Meanwhile, for z=0.55 a spin-glass-like behavior of cluster type with randomly oriented magnetic moments is observed as the ZFC-FC splitting goes up to the freezing temperature T_f=11.5 K and the critical fields connected both with a transformation of the antiferromagnetic spin spiral via conical magnetic structure into ferromagnetic phase disappear.     

Anisotropy and FOMP in Tb3 (Fe28−xCox) V1.0 (x=0, 3 and 6) compounds

In this work, the structural and magnetic properties of Tb₃ (Fe_28−xCo_x) V_1.0 (x=0, 3, 6) compounds have been investigated. The structural characterization of compounds by X-ray powder diffraction is an evidence for a monoclinic Nd₃(Fe, Ti)₂₉-type structure (A2/m space group). The refined lattice parameters a and b (but not c) and the unit cell volume V, obtained from the XRD data by the Rietveld method, are found to decrease with increasing Co concentration. The unit cell parameters behavior has been attributed to the smaller Co atoms and a preferential substitution of Fe by Co. The anisotropy field (H_a) as well as critical field (H_cr) was measured using the singular point detection (SPD) technique from 5 to 300 K in a pulsed magnetic field of up to 30 T. At T=5 K, a FOMP of type 2 was observed for all samples and persists at all temperatures up to 300 K. For sample x=0, H_cr=10.6 and 2.0 T at 5 and 300 K, respectively, is equal to that reported earlier. The occurrence of canting angles between the magnetic sublattices during the magnetization process instead of high-order anisotropy contributions (at room temperature are usually negligible) has been considered to explain the survival of the FOMP at room temperature. The anisotropy and critical fields behave differently for samples with x=0, 3 compared with x=6. The observed behavior has been related to the fact that the Co substitution for Fe takes place with a preferential entrance in the inequivalent crystallographic sites of the 3:29 structure. The contribution of the Tb-sublattice in the Tb₃(Fe, V)₂₉ compound with uniaxial anisotropy has been scaled from the anisotropy field measured on a Y₃(Fe, V)₂₉ single crystal with easy plane anisotropy.