Effect of Co or Mn addition on the soft magnetic properties of amorphous Fe89−xZr11Bx (x=5, 10) alloy ribbons

The temperature and field dependent magnetic properties of melt-spun amorphous Fe_89−x−yZr₁₁B_x(Co,Mn)_y (x=5, 10 and 0≤y≤10) alloys in the temperature range 5-1200 K are reported. The Curie temperature and saturation magnetization at room temperature increase (decrease) almost linearly with Co (Mn) addition. With increasing Co concentration, the room temperature coercivity increases at the rate of 2.26 (0.28) A/m per at% for the x=5 (10) samples. The high-field magnetic susceptibility and local magnetic anisotropy decrease (increases) rapidly with increasing Co (Mn) concentration. The thermomagnetic curves show a marked increase in magnetization above 850 K corresponding to the crystallization of α-FeCo (α-Fe) phase in samples containing Co (Mn). The Curie temperature of the crystalline phase increases (remains same) with increasing Co (Mn) concentration with the formation of α-FeCo (α-Fe). Addition of Co up to 10 at% in Fe-Zr-B improves the room temperature saturation magnetization from 0.56 to 1.2 T, and Curie temperature from 315 to 476 K. Also, the coercivity increases with Co addition from 1.27 to 23.88 A/m for x=5 and from 7.64 to 10.35 A/m for x=10 alloy. The non-collinear spin structures that characterize Fe rich Fe-Zr-B amorphous alloys have been used to describe the observed results.     

Mössbauer spectroscopy studies of spin reorientations in amorphous and crystalline (Co0.2Fe0.8)72.5Si12.5B15 glass coated micro-wires

Thermo-gravimetric, differential scanning calorimetry and comprehensive ⁵⁷Fe Mössbauer spectroscopy studies of amorphous and crystalline ferromagnetic glass coated (Co_0.2Fe_0.8)_72.5Si_12.5B₁₅ micro-wires have been recorded. The Curie temperature of the amorphous phase is T_C(amorp) ∼730 K. The analysis of the Mössbauer spectra reveals that below 623 K the easy axis of the magnetization is axial-along the wires, and that a tangential or/and radial orientation occurs at higher temperatures. At 770 K, in the first 4 hours the Mössbauer spectrum exhibits a pure paramagnetic doublet. Crystallization and decomposition to predominantly α-Fe(Si) and Fe₂B occurs either by raising the temperature above 835 K or isothermally in time at lower temperatures. Annealing for a day at 770 K, leads to crystallization. In the crystalline material the magnetic moments have a complete random orientation. After cooling back to ambient temperature, both α-Fe(Si) and Fe₂B in the glass coated wire show pure axial magnetic orientation like in the original amorphous state. The observed spin reorientations are associated with changes in the stress induced by the glass coating.     

Hydrothermal synthesis and Magnetocaloric effect of La0.5Ca0.3Sr0.2MnO3

The hydrothermal synthesis and magnetic entropy change for the perovskite manganite La_0.5Ca_0.3Sr_0.2MnO₃ have been studied. The La_0.5Ca_0.3Sr_0.2MnO₃ can be produced as phase-pure, crystalline powders in one step from solutions of metal salts in aqueous potassium hydroxide solution at a temperature of 513 K in 72 h. Scanning electron microscopy shows that the materials are made up of cuboid-shaped particles in typical dimension of 4.0×2.5×1.6 μm. Heat treatment can improve the magnetocaloric effect for the hydrothermal sample. The maximum magnetic entropy change ΔS_M for the as-prepared sample is 0.88 J kg⁻¹ K⁻¹ at 315 K for a magnetic field change of 2.0 T. It increases to 1.52 J kg⁻¹ K⁻¹, near its Curie temperature (317 K) by annealing the sample at 1473 K for 6 h. The hydrothermal synthesis method is a feasible route to prepare high-quality perovskite material for magnetic refrigeration application.     

Influence of boron on the giant magnetocaloric effect of La(Fe0.9Si0.1)13

The influences of boron addition on the phase formation, Curie temperature and magnetic entropy change of the NaZn₁₃-type La(Fe_0.9Si_0.1)₁₃ compound have been investigated. Eight boron containing La(Fe_0.9Si_0.1)₁₃B_x samples were prepared with x=0, 0.03, 0.06, 0.1, 0.2, 0.3, 0.5 and 0.6, respectively. Experimental results show that a small amount of B addition in La(Fe_0.9Si_0.1)₁₃ forms the solid solution NaZn₁₃-type structure phase by substituting B for Si or doping B into interstitial position of the lattice, preserves its giant magnetocaloric effects due to their first-order structural/magnetic transition, as well as increase its Curie temperature T_c slightly. The maximum magnetic entropy changes in the magnetic field change of 0–1.6 T are around 20 J kg^–1 K^–1 for the samples with Boron addition less than 0.3, while improving the Curie temperatures by 2 K.     

Fe65B22Nd9Mo4 bulk nanocomposite permanent magnets produced by crystallizing amorphous precursors

The Fe₆₅B₂₂Nd₉Mo₄ nanocomposite permanent magnets in the form of a rectangular cross sectioned rod have been prepared by annealing the amorphous precursors. The thermal behavior, structure and magnetic properties of the magnets have been investigated by differential scanning calorimetry, X-ray diffractometry, electron microscopy and magnetometry techniques. The as-cast Fe₆₅B₂₂Nd₉Mo₄ alloy showed soft magnetic properties, which changed into magnetically hard after annealing. Results provoke that the magnetic properties of the alloy are sensitive to thermal processing conditions. The optimum hard magnetic properties with a remanence (B_r) of 0.56 T, coercivity (_iH_c) of 920.7 kA/m and maximum energy product (BH)_max of 50.15 kJ/m³ were achieved after annealing the alloy at 983 K for 10 min. The good magnetic properties of Fe₆₅B₂₂Nd₉Mo₄ magnets are ascribed to the exchange coupling between the nano-scaled soft α-Fe, Fe₃B and hard Nd₂Fe₁₄B magnetic grains.     

Magnetization behavior and magnetocaloric effect in bulk amorphous Fe60Co5Zr8Mo5W2B20 alloy

Microstructure by X-ray diffraction and Mössbauer spectroscopy, and isothermal magnetic entropy changes in the bulk amorphous Fe₆₀Co₅Zr₈Mo₅W₂B₂₀ alloy in the as-quenched state and after annealing at 720 K for 15 min are studied. The as-cast and heat treated alloy is paramagnetic at room temperature. The quadrupole splitting distribution is unimodal after annealing indicating the more homogenous structure in comparison with that for the as-cast alloy. Curie temperature slightly increases after annealing from 265±2 K in the as-quenched state to 272±2 K and the alloy exhibits the second order magnetic phase transition. The maximum of isothermal magnetic entropy changes appears at the Curie points and is equal to 0.30 and 0.42 J/(kg·K) for the alloy in the as-quenched state and after annealing, respectively. In the paramagnetic region the material behaves as a Curie-Weiss paramagnet.     

Effect of Mn-site vacancies on the magnetic entropy change and the Curie temperature of La0.67Ca0.33Mn1−xO3 perovskite

Single-phase polycrystalline samples of La_0.67Ca_0.33Mn_1−xO₃ (x=0.00, 0.02, 0.04, 0.06) have been prepared using the sol-gel method. The structure, magnetocaloric properties and the Curie temperature of the samples with different Mn vacancy concentrations have been investigated. The experimental results show that vacancy doping at the Mn-sites has a significant influence on the magnetic properties of La_0.67Ca_0.33Mn_1−xO₃. The Curie temperature decreases monotonically with increasing the Mn-site vacancy concentration x. A remarkable enhancement of the magnetic entropy change has been obtained in the La_0.67Ca_0.33Mn_0.98O₃ sample. The entropy change reaches |ΔS_M|=3.10 J kg⁻¹ K⁻¹ at its Curie temperature (264 K) under an applied magnetic field H=10 kOe, which is almost the same value as that of pure Gd.     

Magnetic properties and domain structures of FeSiB thin films

Smooth Fe₇₈Si₁₀B₁₂ thin films were prepared by r.f. sputtering with the very slow deposition rate of 0.59 nm/min. The as-deposited films were not fully amorphous, instead α-Fe(Si) nanocrystallites were found to be embedded in the amorphous matrix. The saturation magnetostriction λ_s of the as-deposited film is about 6.5 × 10⁻⁶. After annealing at 540 °C for 1 h in an ultrahigh vacuum (4.5 × 10⁻⁵ Pa), the fraction of α-Fe(Si) crystalline phase largely increased, and correspondingly the λ_s decreased to 4.5 × 10⁻⁷. Ripple domain structures were observed in the as-deposited film, while dense stripe domains were observed in the annealed sample, characterized by a very narrow domain width of 80 nm. (1 1 0) texture and island-like configuration of α-Fe(Si) nanocrystallites formed by the annealing treatment are responsible for the perpendicular anisotropy. For the as-deposited film, the magnetization curves increased linearly with the increase of the magnetic field, and showed the very small hysteresis. On the other hand, the annealed sample clearly showed a very steep jump near the origin, which is due to the switch process of the dense stripe domain.     

Magnetic characterization of dual phase FeZrB soft magnetic alloy

The magnetic properties and the annealing process of Fe₇₈Zr₇B₁₅ amorphous ribbons are investigated by X-ray diffraction (XRD), differential scanning calorimetry, and vibrating sample magnetometer. The fully amorphous structure of the as-quenched ribbons is confirmed by the XRD pattern. The Curie temperature and the saturation magnetization M_s of the ribbons are 305 °C and 124.3 emu/g, respectively. Annealing at 550 °C can result in an increase in M_s with annealing time due to the increasing crystallized volume fraction of α-Fe phase. The optimized annealing process is established at 550 °C for 20-30 min with maximum M_s of 146.6 emu/g. The morphology of the ribbons annealed at 550 °C is observed by scanning electron microscopy, showing that nanocrystalline α-Fe grains are dispersed in an amorphous matrix.     

The effect of different temperature annealing on phase relation of LaFe11.5Si1.5 and the magnetocaloric effects of La0.8Ce0.2Fe11.5−xCoxSi1.5 alloys

The phase relation of LaFe_11.5Si_1.5 alloys annealed at different high-temperature from 1223 K (5 h) to 1673 K (0.5 h) has been studied. The powder X-ray diffraction (XRD) patterns show that large amount of 1:13 phase begins to form in the matrix alloy consisting of α-Fe and LaFeSi phases when the annealing temperature is 1423 K. In the temperature range from 1423  to 1523 K, α-Fe and LaFeSi phases rapidly decrease to form 1:13 phase, and LaFeSi phase is rarely observed in the XRD pattern of LaFe_11.5Si_1.5 alloy annealed at 1523 K. With annealing temperature increasing from 1573  to 1673 K, the LaFeSi phase is detected again in the LaFe_11.5Si_1.5 alloy, and there is La₅Si₃ phase when the annealing temperature reaches 1673 K. There almost is no change in the XRD patterns of LaFe_11.5Si_1.5 alloys annealed at 1523 K for 3-5 h. According to this result, the La_0.8Ce_0.2Fe_11.5−xCo_xSi_1.5 (0≤×≤0.7) alloys are annealed at 1523 K (3 h). The analysis of XRD patterns shows that La_0.8Ce_0.2Fe_11.5xCo_xSi_1.5 alloys consist of the NaZn₁₃-type main phase and α-Fe impurity phase. With the increase of Co content from x=0 to 0.7, the Curie temperature T_C increases from 180 to 266 K. Because the increase of Co content can weaken the itinerant electron metamagnetic transition, the order of the magnetic transition at T_C changes from first to second-order between x=0.3 and 0.5. Although the magnetic entropy change decreases from 34.9 to 6.8 J/kg K with increasing Co concentration at a low magnetic field of 0-2 T, the thermal and magnetic hysteresis loss reduces remarkably, which is very important for the magnetic refrigerant near room temperature.     

Synthesis, structural and magnetic properties of the nanocomposite Fe63B23Nd7Y3Nb3Cr1 magnets

The Fe₆₃B₂₃Nd₇Y₃Nb₃Cr₁ nanocomposite magnets in the form of sheets have been prepared by copper mold casting technique. The phase evolution, crystal structure, microstructural and magnetic properties have been investigated in the as-cast and annealed states. The as-cast sheets show magnetically soft behaviors which become magnetically hard by thermal annealing. The optimal annealed microstructure was composed of nanosize soft magnetic α-Fe (19-29 nm) and hard magnetic Nd₂Fe₁₄B (45-55 nm) grains. The best hard magnetic properties such as intrinsic coercivity, _jH_c of 1119 kA/m, remanence, B_r of 0.44 T, magnetic induction to saturation magnetization ratio, M_r/M_s=0.61 and maximum energy product, (BH)_max of 55 kJ/m³ was obtained after annealing at 680 °C for 15 min. The annealing treatment above 680 °C results in non-ideal phase grains growth, which degrade the magnetic properties.     

Magnetocaloric properties of (La0.67−xGdx)Sr0.33MnO3 polycrystalline nanoparticles

In this paper, magnetic property and magnetocaloric effect (MCE) in nanoparticles perovskite manganites of the type (La_0.67−xGd_x)Sr_0.33MnO₃ (x=0.10, 0.15, 0.20) synthesized by using an amorphous molecular alloy as precursor have been reported. From the magnetic measurements as function of temperature and magnetic applied field, we have discovered that the Curie temperature (T_C) of the prepared samples is found to be strongly dependent on Gd content. The Curie temperature of samples is 358.4, 343.2, and 285.9 K for x=0.1, 0.15, and 0.2, respectively. A large magnetocaloric effect close to T_C has been observed with a maximum of magnetoentropy change in all the samples, ∣ΔS_M∣_max of 1.96 and 4.90 J/kg K at 2 and 5 T, respectively, for a substitution rate of 0.15. In addition, the maximum magnetic entropy change observed for samples with different concentration of Gd, exhibits a linear dependence with the applied high magnetic field. These results suggest that (La_0.67−x Gd_x)Sr_0.33MnO₃ (x=0.10, 0.15, 0.20) compounds could be a suitable candidate as working substance in magnetic refrigeration near room temperature.     

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.     

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.     

The existence of giant magnetocaloric effect and laminar structure in Fe73.5−xCrxSi13.5B9Nb3Cu1

Amorphous soft magnetic ribbons Fe_73.5−xCr_xSi_13.5B₉Nb₃Cu₁ (x=1–5) have been fabricated by rapid quenching on a single copper wheel. The differential scanning calorimetry (DSC) patterns showed that the crystallization temperature of α-Fe(Si) phase is ranging from 542 to 569 °C, a little higher than that of pure Finemet (x=0). With the same annealing regime, the crystallization volume fraction as well as the particle size of α-Fe(Si) crystallites decreased with increasing Cr amount substituted for Fe in studied samples. Especially, the interesting fact is that the laminar structure of heat-treated ribbons on the surface contacted to copper wheel in the fabricating process has been firstly discovered and explained to be related to the existence of Cr in studied samples. The hysteresis loop measurement indicated that there is the pinning of displacement of domain walls. The giant magnetocaloric effect (GMCE) has been found in amorphous state of the samples. After annealing, the soft magnetic properties of investigated nanocomposite materials are desirably improved.     

Anisotropic and large low-field magnetic entropy change in a La4/3Sr5/3Mn2O7 single crystal

We have studied the magnetocaloric effect (MCE) in a bilayered La_4/3Sr_5/3Mn₂O₇ single crystal with applied field along both ab-plane and c-direction. Due to the quasi-two-dimensional structure, the crystal exhibits a strong anisotropy in the MCE. The difference of magnetic entropy change between two crystallographic directions depends on external magnetic fields and has a maximum of 2 J/kg K. A large low-field magnetic entropy change, reaching 3.2 J/kg K for a magnetic field change of 15 kOe, is observed when the applied field is along ab-plane. This large low-field magnetic entropy change is attributed to the rapid change of magnetization in response to external magnetic fields in the easy magnetizing plane.     

Curie temperatures and crystallization behavior of amorphous Fe81−xNixZr7B12 (x=10, 20, 30, 40, 50, 60) alloys

Curie temperature, crystal structure and crystallization behavior of amorphous alloys with the stoichiometry Fe_81−xNi_xZr₇B₁₂ (x=10–60) have been studied by X-ray diffractometry (XRD), differential scanning calorimetry (DSC) and AC-magnetization (TMAG) measurements as functions of temperature. The thermal stability of long-range magnetic order, T_C vs. Ni content in as-quenched amorphous alloys exhibits maximum at 352 °C for x=40. The primary crystallization has been detected during annealing at the first crystallization stage of all ribbons investigated.     

Preparation of nanocrystalline MnFe2O4 by doping with Ti ions using solid-state reaction route

Nanostructured manganese ferrites (MnFe₂O₄) with diameters in the range of 45–30 nm were synthesized by Ti⁴⁺ ion doping, using conventional solid-state reaction route. The substitution of Ti⁴⁺ ions created vacancies at Mn²⁺ sites and the coupling of ferrimagnetically active oxygen polyhedra was broken. This created nanoscale regions of ferrites. A reduction of magnetization for decreasing particle size was observed. Coercivity showed an increasing trend. This was explained as arising due to multidomain/monodomain magnetic behaviour of magnetic nanoparticles. DC resistivities of the doped specimens indicated the presence of an interfacial amorphous phase formed by the nanoparticles. Zero-field cooled and field-cooled curves from 30 nm sized particles showed a peak at T_B (∼125 K), typical of superparamagnetic blocking temperature.     

Room temperature magnetic entropy change and magnetoresistance in La0.70(Ca0.30−xSrx)MnO3:Ag 10% (x=0.0−0.10)

The magnetic and magnetocaloric properties of polycrystalline La_0.70(Ca_0.30−xSr_x)MnO₃:Ag 10% manganite have been investigated. All compositions are crystallized in single phase orthorhombic Pbnm space group. Both, the insulator–metal transition temperature (T^IM) and Curie temperature (T_c) are observed at 298 K for x=0.10 composition. Though both T^IM and T_c are nearly unchanged with Ag addition, the MR is increased. The MR at 300 K is found to be as large as 31% with magnetic field change of 1 T, whereas it reaches up to 49% at magnetic field of 3 T for the La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample. The maximum entropy change (ΔS_Mmax) at near its T_c (300.5 K) is 7.6 J kg⁻¹ K⁻¹ upon the magnetic field change of 5 T. The La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample having good MR (31%^1 T, 49%^3 T) and reasonable change in magnetic entropy (7.6 J kg⁻¹.K⁻¹, 5 T) at 300 K can be a potential magnetic refrigerant material at ambient temperatures.     

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.