Effect of Cr and Ni substitution on the hyperfine parameters of Fe-B based metallic glasses

Some features of the variation of isomer shift, quadrupole splitting and magnetic hyperfine field distribution in Fe_85?xCr_xB₁₅ (x=5–30), Fe_85?yCr₁₅B_y (y=10–20) and Fe_85?xNi_xB₁₅ (x=5–30) metallic glasses are reported. Changes in the isomer shift and quadrupole splitting for the Cr_x and B_y series are linked with a precursor stage for the onset of ferromagnetism.     

Non affinity of Fe2+ for B sites in iron thiochromites and compared band structures of oxides and sulfides spinels

Departure from stoichiometry in vapor grown FeCr₂S₄ was studied using Mössbauer spectroscopy. The paramagnetic Mössbauer spectra give evidence of two singlets and two doublets which correspond respectively to A site Fe²⁺ ? Fe³⁺, Fe^II in T_d symmetry and in symmetry lower than T_d. The following ionic distribution has been deduced:

$\text{(Fe}{}^{\mathrm{2+}}{}_{\mathrm{1?y}}\text{Fe}{}^{\mathrm{3+}}{}_{\mathrm{y}}\text{)|Cr}{}^{\mathrm{3+}}{}_{\mathrm{2?x}}\text{□}{}_{\mathrm{x}}\text{|S}{}_{\mathrm{4?z}}\text{□}{}_{\mathrm{z}}$

Compounds in the system Fe_1+xCr_2?xS₄ have been studied for 0 ? x ? 0.1. The spectra are solved assuming Fe^II in A site with T_d symmetry, A site Fe^II with lower symmetry and B site Fe³⁺. No Fe²⁺ appears in B site. These features are discussed in terms of schematic band structures implying single electron narrow bands. The non-affinity of Fe²⁺ for B sites of iron thiochromites is discussed in relation with B site Cr²⁺ level.     

Magneto-volume effect in invar-type amorphous Fe—B alloys

Amorphous Fe_100-xB_x(11.5 ≦ x ≦ 22) alloys having the invar characteristics were prepared by a single roller quenching method to investigate the magneto-volume effect. Forced volume magnetostriction, ?ω/?H, increased remarkably with decreasing boron content and the maximum value obtained was about 90 × 10^?10 Oe^?1 at 11.5 at.% boron. The estimated value of the pressure dependence of the Curie temperature, ?T_c/?P, was considerably large, being comparable to those of crystalline FeNi invar alloys. The ?T_c/?P curve plotted as a function of T_c approximately fitted Wohlfarth's expression.     

Improving magnetocaloric properties of Fe68–xCrxTb5B23Nb4 (x = 0, 2, 4, 6 and 8) metallic glasses having high glass-forming ability with tunable Curie temperature

Abstract

The impacts of adding Cr on the Curie temperature (T_C), glass-forming ability (GFA), and magnetocaloric effect were studied in Fe_68?xCr_xTb₅B₂₃Nb₄ (x = 0, 2, 4, 6 and 8) metallic glasses prepared by suction casting. GFA depends on Cr content in the composition. For Fe_68?xCr_xTb₅B₂₃Nb₄ bulk metallic glasses (BMGs), with critical diameters up to ~3 mm can be produced by suction casting and maximum value of GFA was found for x = 6. By exchanging Cr with Fe partially, T_C could effectively be adjusted in a quite broad temperature interval from 487 K for x = 0 to 267 K for x = 8, whereas maximum magnetic entropy change decreased from 1.16 to 0.53 Jkg^?1 K^?1 and refrigeration capacity (RC) changed from 116 to 45.05 J/kg under a low field change of 2 T. Though T_C is shifted to room temperature, maximum magnetic entropy change and RC decreased almost half of the base alloy. To enhance these properties (Fe_0.62Cr_0.06Tb_0.05B_0.23Nb_0.04)_100?yCu_y (y = 0.75, 1), metallic glasses are prepared. By the help of small addition of Cu, magnetocaloric properties can be effectively increased without changing the T_C. These findings show that the successful synthesis of the Fe-based Fe₆₂Cr₆Tb₅B₂₃Nb₄ and (Fe_0.62Cr_0.06Tb_0.05B_0.23Nb_0.04)_100?yCu_y (y = 0.75, 1) BMGs near room temperature, could be considered as promising candidates as magnetic refrigerant materials.     

Site occupancy and magnetic study of Al and Cr co-substituted Y3Fe5O12

Single-phased polycrystalline Y₃Fe_5−2xAl_xCr_xO₁₂ garnet samples (x=0, 0.2, 0.4 and 0.6) have been prepared by the conventional ceramic technique. Rietveld refinement of X-ray diffraction patterns of the samples shows them to crystallize in the Ia3d space group and the corresponding lattice constant to decrease with increasing Al³⁺ and Cr³⁺ contents (x). Mössbauer results indicate that Cr³⁺ substitutes for Fe³⁺ at the octahedral sites whilst Al³⁺ essentially replaces Fe³⁺ at the tetrahedral sites. This result indicates that co-doping of Y₃Fe₅O₁₂ does not affect the preferential site occupancy for separate individual substitution of either Cr³⁺ or Al³⁺. The magnetization measurements reveal that the Curie temperature (T_c) monotonically decreases with increasing x while the magnetic moment per unit formula decreases up to x=0.4 and then slightly increases for x=0.6. This reflects a progressive weakening of the ferrimagnetic exchange interaction between the Fe³⁺ ions at octahedral and tetrahedral sites due to co-substitution. The magnetic moment was calculated using the cations distribution inferred from the Mössbauer data and the collinear ferrimagnetic model, and was found to agree reasonably with the experimentally measured value. The phenomenological amplitude crossover, characterized by the temperature T*, has also been observed in the doped YIG and briefly discussed.     

Mössbauer investigation of Mn2Sb doped with Fe and Cr

The alloy systems Mn_2?xFe_xSb and Mn_1.98?xCr_xFe_0.02Sb have been investigated by Mössbauer spectroscopy of ⁵⁷Fe in the region x? 0.2.In Mn_2?xFe_xSb the spinflop transition known to exist in pure Mn₂Sb at T_t = 240 K is observed. At T_t the magnetic hyperfine field H changes from -50 to -80 kOe and the electric quadrupole interaction QS from positive to negative with increasing T. The value of ΔH at T_t can be understood in terms of dipolar contributions to H. Fe is deduced to occupy the Mn_I sites in the lattice.In Mn_1.98?xCr_xFe_0.02Sb the transition from the ferrimagnetic to the antiferromagnetic state is observed. In the antiferromagneti c state we find | H| ≈ 15 kOe.     

57Fe Mössbauer spectroscopy studies of Sr2Fe1−x Cr x Mo1−x W x O6 double perovskite compounds

Polycrystalline double perovskites Sr₂Fe_1?x Cr _x Mo_1?x W _x O₆ with x = 0, 0.05, 0.10, 0.15, 0.20, and 0.30 have been prepared by sold state reactions. A continuous decrease of the tetragonal unit cell parameters α and c with increasing x values is observed. The highest Curie temperature T _C = 426 K is recorded for the x = 0.10 compound. ⁵⁷Fe Mössbauer spectroscopy measurements indicate a non-integral electronic configuration of ～3d^5.3 for the Fe ions at the ordered double perovskite structure for x ≤ 0.20, which reaches ～3d^5.4 for x = 0.30. Fe–Mo/W anti-site and anti-phase boundary defects are observed in all samples in equal concentrations of around 3% of the total number of Fe ions in their structure.     

The proximity effect in an Fe-Cr-V-Cr-Fe system

The proximity effect was studied in a thin-film Fe-Cr-V-Cr-Fe layered system. As the chromium layer thickness (d_Cr) increases at a fixed thickness of iron layers (d_Fe), the dependence of the superconducting transition temperature (T_c) on d_Cr exhibits a maximum at d_Cr ? 40 Å followed by a sharp decrease. Investigation of the dependence of T_c on d_Fe at a fixed d_Cr showed that the depth of penetration of the Cooper pairs into a chromium layer does not exceed 40 Å. Analysis of the results obtained suggests that, at d_Cr ? 40 Å, chromium layers exhibit the transition from a nonmagnetic state to an incommensurate spin density wave state.     

Resistivity variation near the critical temperature in some Ni-Fe base amorphous alloys

Accurate measurements of the electrical resistivity of three Ni_80?xFe_xP₁₄B₆ alloys (with x=10, 20 and 30) were performed in the temperature interval 1.5–500 K. Resistivity (ρ) and dρ/dT behaviours near T_c for the alloys with different x values are mutually very different. In particular $\text{dρ}\text{dT}$ variation near T_c for the alloys with x=10 and 20 is Ornstein-Zernicke like while for the alloy with x=30 is of more usual energy like type. A tentative explanation of this behaviour in terms of the influence of the percolation limit on the nature of the magnetic transition is offered.     

Mossbauer study of the Cu-Cd ferrite system

The magnetic properties of the Cd_xCu_1?xFe₂O₄ ferrite system (x = 0 to 1) have been investigated by means of Mossbauer Spectroscopy. Mossbauer Spectra for x = 0.0 to 0.6 suggest the existence of two hyperfine fields, one due to the Fe³⁺ tetrahedral ions (A-sites) and the other due to Fe³⁺ octahedral ions (B-sites), while for x = 0.7 it shows relaxation behaviour and for x ? 0.8 it exhibits a paramagnetic quadrupole doublet. The systematic dependence of the isomer shift, quadrupole interactions and nuclear fields of ⁵⁷Fe³⁺ ions in both A- and B-sites has been determined as a function of cadmium content. The variation of nuclear magnetic fields at the A- and B-sites are explained on the basis of A-B and B-B supertransferred hyperfine interactions. Analysis of the relaxation spectrum observed at x = 0.7 (300 K) suggests that the relaxation mechanism is due to domain wall oscillations. It has been found here that the QS increases from CuFe₂O₄ as the cadmium concentration is increased.     

Mössbauer study of Fe57 and Co57 in Co1 + xV2−xO4

Mössbauer sources and absorbers, prepared by doping Fe⁵⁷ and radioactive Co⁵⁷ into samples of Co_1?xV_2?xO₄ (0 ? x ? 1), were studied in the temperature range of 80–500 K. The source and absorber spectra are very similar. The absence of any Fe²⁺ at the A site can be understood by partial covalent bond formation with an anion. However, the predominance of Fe³⁺ at the B site (with some Fe²⁺ for x = 1) cannot be explained by simple crystal-field or molecular-orbital theories. The x dependence of the isomer shift and of the Fe³⁺B-site quadrupole interaction can be related to changes in the lattice constant and the oxygen parameter. The temperature dependence of the Fe²⁺B-site quadrupole interaction can be fitted in the motional-averaging model. In the range of 0 ? x ? 0.5 the temperature dependence of the isomer shift shows effects of chemical bonding beyond the second-order Doppler shift.     

Nuclear spin relaxation in itinerant electron antiferromagnetic Cr1−xVx system

Nuclear spin relaxation rate T^?1₁ for ⁵¹V in an incommensurate antiferromagnetic Cr_1?xV_x system has been measured in a temperature range between 1.3 and 4.2 K and in a range of magnetic field from 0 to 13.3 kOe by using a field-cycling nuclear magnetic resonance technique. In the (T₁T)^?1 vs x curve a pronounced maximum was observed near the critical concentration (x_c～0.040). Furthermore for alloys with x = 0.038 and 0.040 a deviation from the Korringa relation, T₁T = constant, was observed. The experimental results of (T₁T)^?1 are interpreted in terms of the spin-fluctuation and d-orbital contributions.     

EPR study of the symmetry breaking effect in ferroelectric cesium dihydrogen phosphate doped with Cr5+ ions

The (PO₄)^3? units in a CsH₂PO₄ (CDP) crystal were replaced in a small fraction of sites by (CrO₄)^3? groups and the EPR of the Cr⁵⁺ center was investigated. Splitting of the EPR line appears at T¹_c=245 K, 91 K higher that the ferroelectric transition temperature T_c=154 K. The electronic wave function of Cr⁵⁺ (3d¹) is identified as d_x2_?y2. The d_x2_?y2 function couples with the near protons and the reorientation of this unit in the two possible configurations occurs in the paraelectric phase and breaks the symmetry far above T_c. The observed correlation time 10^?9 sec and associated activation energy ΔU=0.215 eV are discussed.     

Magnetotransport and magnetic properties of sulfospinels Zn x Fe1−x Cr2S4

Cr-based chalcogenide spinels, which do not have heterovalency and distortion-induced ions such as manganese oxides with perovskite structure, have demonstrated the existence of colossal magnetoresistance. In order to investigate the magnetotransport phenomena and magnetic properties of sulfospinels Zn _x Fe_1?x Cr₂S₄, polycrystalline Zn _x Fe_1?x Cr₂S₄ samples were synthesized in the 0?≤?x?≤?0.2 range by a solid reaction method. The crystal structure for x?=?0.05, 0.1, and 0.2 turned out to be cubic at room temperature by X-ray diffraction measurement. In magnetoresistance measurement, Zn _x Fe_1?x Cr₂S₄ samples indicate that this system is semiconducting below about 150 K. The temperature of maximum magnetoresistance is almost consistent with Curie temperature. The isomer shift and the electric quadrupole shift of Zn _x Fe_1?x Cr₂S₄ samples by Mössbauer experiment show that Fe²⁺ ions occupy the tetrahedral site in the spinel structure. As the Zn ions are substituted for Fe ions, the Jahn–Teller relaxation slows down and the electric quadrupole shift increases. The magnetotransport phenomena of Zn _x Fe_1?x Cr₂S₄ is related to Jahn–Teller effect and half-metallic electronic structure, which are different from the double exchange interactions of the manganite La–Ca–Mn–O system or the triple exchange interactions of sulfospinel Cu _x Fe_1?x Cr₂S₄.     

Temperature dependence of the upper critical field as an indicator of boson effects in superconductivity in Nd2−x CexCuO4−y

The temperature dependence of the upper critical field B _c 2 was determined from the shift of the resistive transition ΔT(B) in nearly optimally doped Nd_2?x Ce_xCuO_4?y single crystals. Within the experimental accuracy, the weak-field data are described by the power function B _c 2∝(ΔT)^3/2. This result is compared with the data on heat capacity and analyzed in the context of possible manifestations of boson effects in superconductivity. The T dependence of B _c 2 persists down to the lowest temperatures, but the numerical values of B _c 2 below 1 K are different for different samples.     

Influence of annealing on magnetic properties of Co-based metallic glasses

The influence of low-temperature annealing on the magnetic hysteresis loop parameters of magnetostrictive Co-Si-B and nonmagnetostrictive Co-Fe-Si-B glasses was studied. The dependence of Curie temperature (T_C), crystallization temperature (T_x), full-stress-relaxation temperature, saturation magnetostriction constant, saturation magnetization and coercive field H_c on metalloids contents for as quenched Co_100-x(Si_0.5B_0.5)_x glasses was determined.It was found that annealing enhances remanence magnetization for all investigated Co-Si-B glasses. The coercive field of these glasses is influenced by annealing owing to: stress relaxation (resulting in an H_c decrease) and domain structure stabilization (resulting in an H_c increase). Significant H_c reduction for both magnetostrictive and non-magnetostrictive glasses was observed, after annealing above T_C. For glasses with T_C<>T_x, it was necessary to apply an external magnetic field in ord er to decrease H_c.It was found that non-magnetostrictive metallic glasses with low Curie temperatures (T_C ? 450 K) exhibit the most stable magnetic hysteresis loop parameters.     

Giant forced volume magnetostriction of Fe-rich iron-cobalt-zirconium amorphous alloys

The forced volume magnetostriction has been measured as a function of composition and temperature in amorphous (Fe_1?xCo_x)₉₀Zr₁₀ alloys. The maximum value of $\text{δω}\text{δH}$ (T = 0 K), equal to 285 × 10^-10 Oe^-1, has been observed for Fe₉₀Zr₁₀ alloys. The effect of pressure on the magnetization σ₀ at T = 0 K was calculated from $\text{δω}\text{δH}$ data. The pressure dependence of the Curie temperature T_c and σ₀ behaves in a similar way as those observed for crystalline NiPd and NiRh alloys.     

Magnetic moments and electronic structure of Co-base metallic glasses

Magnetization of Co_80-xT_xB₂₀ glasses (0 ≤ × ≤ 12 at%, T = Fe, Mn, Cr, V) has been measured from 4.2 K to approximately 700 K. The data are well described in terms of the virtual bound states introduced above the center of the d band of the matrix by the light T solutes. Details of the electronic structure, some aspects of which would not be revealed by photoemission, are thereby inferred.     

Magnetostriction of ferromagnetic metallic glasses

Linear saturation magnetostrictions (295 K) of Fe_80t-xCo_xB₂₀, 0?x?80, and Fe_80?xNi_xB₂₀, 0?x?60 (at. %) glasses are reported. The saturation magnetostrictions of the Fe-Ni-base glasses vary as the sqaure of their respective saturation magnetizations. The behavior in the Fe-Co-base glasses is strikingly different. The compositional trends suggest a difference in origin of magnetostrictions between Fe-Ni-base and Co-containing glasses. When magnetostrictions for these glasses are compared with those for Fe-Co and Fe-Ni polycrystalline alloys, the most significant discrepancies appear in the Fe-rich compositions. This is probably related to the difference in short range order between the crystalline and non-crystalline Fe-rich alloys: α-Fe is 8-fold coordinated whereas all of the metallic glasses studied show ～ 12-fold metal coordination.     

The hyperfine interaction of gadolinium and holmium in cubic Ho: (Gd,Ce)Fe2 compounds

The low-temperature hyperfine parameters of the ferrimagnetic C15 intermetallic system Ho_0.03Ce_xGd_0.97-xFe₂ have been measured at Gd using the 87 keV γ-ray of ¹⁵⁵Gd and at Ho using spin echo nmr of ¹⁶⁵Ho. A linear decrease of the hyperfine field B_t with increasing x is observed, the slope being almost the same for both nuclei. The observed slope (dB_t/dx ? -37T) is nearly three times greater than that found for ¹⁵⁵Gd in the analogous H₀:(Y, Gd)Fe₂ system; this is attributed to the influence of the increased conduction electron density when trivalent lanthanide ions are replaced by Ce⁴⁺.