Anti-Invar properties and magnetic order in fcc Fe-Ni-C alloy

Anti-Invar effect was revealed in the fcc Fe-25.3%Ni-0.73%C (wt%) alloy, which demonstrates high values of thermal expansion coefficient (TEC) (15-21)×10⁻⁶ K⁻¹ accompanied by almost temperature-insensitive behavior in temperature range of 122-525 K. Alloying with carbon considerably expanded the low temperature range of anti-Invar behavior in fcc Fe-Ni-based alloy. The Curie temperature of the alloy T_C=195 K was determined on measurements of temperature dependences of magnetic susceptibility and saturation magnetization. The Mössbauer and small-angle neutron scattering (SANS) experiments on the fcc Fe-25.3%Ni-(0.73-0.78)%C alloys with the varying temperatures below and above the Curie point and in external magnetic field of 1.5-5 T were conducted. Low value of the Debye temperature Θ_D=180 K was estimated using the temperature dependence of the integral intensity of Mössbauer spectra for specified temperature range. The inequality B_eff=(0.7-0.9)B_ext was obtained in external field Mössbauer measurement that points to antiferromagnetically coupled Fe atoms, which have a tendency to align their spins perpendicular to B_ext. Nano length scale magnetic inhomogeneities nearby and far above T_C were revealed, which assumed that it is caused by mixed antiferromagnetically and ferromagnetically coupled Fe atom spins. The anti-Invar behavior of Fe-Ni-C alloy is explained in terms of evolution of magnetic order with changing temperature resulting from thermally varied interspin interaction and decreasing stiffness of interatomic bond.     

Mössbauer study of CoFeRhO4

CoFeRhO₄ has been studied by Mössbauer spectroscopy and X-ray diffraction. The crystal is found to have a cubic spinel structure with the lattice constant a₀=8.451±0.005 Å. The iron ions are in ferric states. The temperature dependence of the magnetic hyperfine field is analyzed by the Néel theory of ferrimagnetism. The intersublattice superexchange interaction is antiferromagnetic and strong with a strength of J_AB=−12.39k_B while the intrasublattice superexchange interactions are weak with strengths of J_AA=−4.96k_B and J_BB=6.20k_B. As the temperature increases toward the Néel temperature T_N, a systematic line broadening effect in the Mössbauer spectrum is observed and interpreted to originate from different temperature dependences of the magnetic hyperfine fields at various iron sites.     

Medium range ordering and some magnetic properties of amorphous Fe90Zr7B3 alloy

High-resolution electron microscopy (HREM) reveals in the as-quenched Fe₉₀Zr₇B₃ alloy the existence of medium range ordered (MRO) regions 1-2 nm in size. Transmission Mössbauer spectroscopy confirms that these regions are α-Fe MRO ones. Above the Curie point of the amorphous phase (T_C=(257±2)K) they behave like non-interacting superparamagnetic particles with the magnetization decreasing linearly with the temperature. For these particles the average magnetic moment of 390μ_B and the average size of 1.7 nm, in excellent agreement with HREM observations, were estimated. The maximum of the isothermal magnetic entropy change at the maximum magnetizing field induction of 2 T occurs at the Curie temperature of the amorphous phase and equals to 1.05 Jkg⁻¹ K⁻¹. The magnetic entropy changes exhibit the linear dependence on the maximum magnetizing field induction in the range 0.5-2 T below, near and above T_C. Such correlations are attributed to superparamagnetic behavior of α-Fe MRO regions.     

Magnetic anomalies in single crystalline ErPd2Si2

Considering certain interesting features in the previously reported ¹⁶⁶Er Mössbauer effect, and neutron diffraction data on the polycrystalline form of ErPd₂Si₂ crystallizing in the ThCr₂Si₂-type tetragonal structure, we have carried out magnetic measurements (1.8–300 K) on the single crystalline form of this compound. We observe significant anisotropy in the absolute values of magnetization (indicating that the easy axis is c-axis) as well as in features due to magnetic ordering in the plot of magnetic susceptibility χ versus temperature T at low temperatures. The χ(T) data reveal that there is a pseudo-low-dimensional magnetic order setting in at 4.8 K, with a three-dimensional antiferromagnetic order setting in at a lower temperature (3.8 K). A new finding in the χ(T) data is that, for H∥〈1 1 0〉 but not for H∥〈0 0 1〉, there is a broad shoulder in the range 8–20 K, indicative of the existence of magnetic correlations above 5 K as well, which could be related to the previously reported slow-relaxation-dominated Mössbauer spectra. Interestingly, the temperature coefficient of electrical resistivity is found to be isotropic; no feature due to magnetic ordering could be detected in the electrical resistivity data at low temperatures, which is attributed to magnetic Brillioun-zone boundary gap effects. The results reveal the complex nature of magnetism of this compound.     

Magnetism of ferriprotoporphyrin IX monomers and dimers

The SQUID and the ⁵⁷Fe Mössbauer spectroscopy studies of the magnetic properties of monomeric and dimeric forms of iron porphyrin were performed between 2 and 305 K. The effective magnetic relaxation rate of the Fe atoms in iron porphyrin monomers exhibits complex temperature dependence, resulting from the competing spin-spin and spin-lattice relaxation processes. The dimerization of iron porphyrin dramatically speeds up the magnetic relaxation. The Fe-Fe antiferromagnetic exchange coupling constant in Fe-O-Fe dimer is J≈−110 cm⁻¹. The complementary application of SQUID and the Mössbauer spectroscopy is proposed as a new precise quantitative analytical methodology for monitoring of the aggregation process of iron porphyrin.     

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.     

Mössbauer spectroscopic study of the thermal spin crossover in [Fe(II)(isoxazole)6](ClO4)2

The ⁵⁷Fe Mössbauer spectroscopy of mononuclear [Fe(II)(isoxazole)₆](ClO₄)₂ has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S=0) and high-spin (S=2) states. Temperature-dependent spin transition curves have been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures between 84 and 270 K during a cooling and heating cycle. This compound exhibits an unusual temperature-dependent spin transition behaviour with T_C(↓)=223 and T_C(↑)=213 K occurring in the reverse order in comparison to those observed in SQUID observation and many other spin transition compounds. The compound has three high-spin Fe(II) sites at the highest temperature of study of which two undergo spin transitions. The compound seems to undergo a structural phase transition around the spin transition temperature, which plays a significant role in the spin crossover behaviour as well as the magnetic properties of the compound at temperatures below T_C. The present study reveals an increase in high-spin fraction upon heating in the temperature range below T_C, and an explanation is provided.     

Magnetic properties of CdSb doped with Ni

Magnetic properties of the group II–V semiconductor CdSb single crystals doped with Ni (2 at%) are investigated. Deviation of the zero-field-cooled susceptibility, χ_ZFC, from the field-cooled susceptibility is observed below 300 K, along with a broad maximum of χ_ZFC (T) at T_b in fields below the anisotropy field B_K∼4 kG. T_b(B) obeys the law [T_b(B)/T_b(0)]^1/2=1–B/B_K with T_b(0)∼100 K. The magnetization exhibits saturation above ∼20–30 kG, a weak temperature dependence and anisotropy of the saturation value M_s. The coercive field is much smaller then B_K and displays anisotropy inverted with respect to that of M_s. Such magnetic behavior is expected for spheroidal Ni-rich Ni_1−xSb_x nanoparticles with high aspect ratio, broad distribution of the sizes and with orientations of the major axis distributed around a preferred direction.     

Fabrication and magnetic properties of Fe3O4 nanowire arrays in different diameters

Fe₃O₄ nanowire arrays with different diameters of D=50, 100, 150 and 200 nm were prepared in anodic aluminum oxide (AAO) templates by an electrodeposition method followed by heat-treating processes. A vibrating sample magnetometer (VSM) and a Quantum Design SQUID MPMS magnetometer were used to investigate the magnetic properties. At room temperature the nanowire arrays change from superparamagnetism to ferromagnetism as the diameter increases from 50 to 200 nm. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization measurements show that the blocking temperature T_B increases with the diameter of nanowire. The ZFC curves of D=50 nm nanowire arrays under different applied fields (H) were measured and a power relationship between T_B and H were found. The temperature dependence of coercivity below T_B was also investigated. Mössbauer spectra and micromagnetic simulation were used to study the micro-magnetic structure of nanowire arrays and the static distribution of magnetic moments of D=200 nm nanowire arrays was investigated. The unique magnetic behaviors were interpreted by the competition of the demagnetization energy of quasi-one-dimensional nanostructures and the magnetocrystalline anisotropy energy of particles in nanowires.     

Structure and magnetic properties of magnetostrictive compounds Tb0.36Dy0.64(Fe0.85Co0.15)2−xBx (0⩽x⩽0.15)

Crystal structure and magnetic properties of magnetostrictive compounds Tb_0.36Dy_0.64(Fe_0.85Co_0.15)_2−xB_x (0?x?0.15) have been investigated at room temperature. The matrix of these compounds keeps a cubic MgCu₂-type structure. Lattice parameter a of the Laves phase decreases to reach a minimum at x=0.10, then increases with increasing boron content. Through analyzing the Mössbauer spectra, the easy magnetization direction (EMD) for all samples is confirmed to lie along 〈111〉 direction at room temperature, suggesting the presence of the giant magnetostriction. The mean hyperfine field H_hf and the deduced iron moment μ_Fe increase with increasing boron content, resulting in the enhancement of both Curie temperature T_C and spin reorientation temperature T_r. Although the addition of B enlarges the magnetocrystalline anisotropy constant K₁, the composition dependence of the ratio λ/K₁ for Tb_0.36Dy_0.64(Fe_0.85Co_0.15)_2−xB_x, however, reaches a maximum value at x=0. 05 under high magnetic fields.     

Magnetic ordering above room temperature in the sigma-phase of Fe66V34

Magnetic properties of four sigma-phase Fe_100−xV_x samples with 34.4?x?55.1 were investigated by Mössbauer spectroscopy and magnetic measurements in the temperature interval 4.2-300 K. Four magnetic quantities, viz. hyperfine field, Curie temperature, magnetic moment and susceptibility, were determined. The sample containing 34.4 at% V was revealed to exhibit the largest values found up to now for the sigma-phase for average hyperfine field, 〈B〉=12.1 T, average magnetic moment per Fe atom, 〈μ〉=0.89 μ_B, and Curie temperature, T_C=315.3 K. The quantities were shown to be strongly correlated with each other. In particular, T_C is linearly correlated with 〈μ〉 with a slope of 406.5 K/μ_B, as well as 〈B〉 is so correlated with 〈μ〉, yielding 14.3 T/μ_B for the hyperfine coupling constant.     

Ultrasmall iron oxide nanoparticles: Magnetic and NMR relaxometric properties

Ultrasmall iron oxide (USPIO) nanoparticles, with diameter mostly less than 3 nm dispersed in an organic carrier fluid were synthesized by polyol route. The evolution of ZFC-FC magnetization curves with temperature, as well as the shift of the ac susceptibility peaks upon changing the frequency, reveal that the nanoparticles in the fluid are non-interacting and superparamagnetic with the blocking temperature T_B ∼10 K. The Mössbauer spectra analysis proposed the core/shell structure of the nanoparticles consisting of stoichiometric γ-Fe₂O₃ core and non-stoichiometric shell. The nanoparticle surface layer has a great influence on their properties which is principally manifested in significant reduction of the magnetization and in a large increase in magnetic anisotropy. Magnetic moments do not saturate in fields up to 5 T, even at the lowest measured temperature, T = 5 K. The average magnetic particle diameter is changed from 1.3 to 1.8 nm with increasing magnetic field from 0 to 5 T which is noticeably smaller than the particle sizes measured by TEM. The estimated effective magnetic anisotropy constant value, K_eff = 2 × 10⁵ J/m³, is two orders of magnitude higher than in the bulk maghemite. Measurements of the longitudinal and transverse NMR relaxivity parameters on water diluted nanoparticle dispersions at 1.5 T gave the values r₁ = 0.028 mmol⁻¹ s⁻¹, r₂ = 0.050 mmol⁻¹ s⁻¹ and their ratio r₂/r₁ = 1.8. Continuous increase of the T₁-weighted MRI signal intensity with increasing Fe concentration in the nanoparticle dispersions was observed which makes this ferrofluid to behave as a positive T₁ contrast agent.     

Thermomagnetic transitions and coercivity mechanism in bulk composite Nd60Fe30Al10 alloys

The thermomagnetic behaviour (within the temperature range 553-300 K) for the bulk composite Nd₆₀Fe₃₀Al₁₀ alloy is described in terms of a transition from paramagnetic to superferromagnetic state at T=553 K, followed by a ferromagnetic ordering for T<473 K. For the superferromagnetic regime, the alloy thermomagnetic response was associated to a homogeneous distribution of magnetic clusters with mean magnetic moment and size of 1072 μ_B and 2.5 nm, respectively. For T<473 K, a pinning model of domain walls described properly the alloy coercivity dependence with temperature, from which the domain wall width and the magnetic anisotropy constant were estimated as being of ≈8 nm and ≈10⁵ J/m³, typical values of hard magnetic phases. Results are supported by microstructural and magnetic domain observations.     

Temperature dependence of magnetic anisotropy in nanoparticles of CoxFe(3−x)O4

In this paper we present a study of the magnetic anisotropy constant of nanocrystalline magnetic particles of Co_xFe_(3−x)O₄, with x ranging from 0.05 to 1.6, synthesized by a combustion reaction. The magnetic anisotropy constants were obtained by fitting the high-field part of the major hysteresis loops with the law of approach equation down to temperatures of 4 K and up to fields of 60 kOe. The anisotropy constant depends strongly on both temperature and cobalt content x, exhibiting a nonmonotic dome-shaped dependence on x with a maximum at x=1.0. We found that fits at lower temperatures, i.e., 4 and 72 K, give values of K₁ that are approximately one order of magnitude higher than those at higher temperatures, i.e., 272 and 340 K. For example, K₁ for specimens with x=0.8 and 1.0 are 4.21×10⁷ and 4.22×10⁷ ergs/cm³ at 4 K, and 7.64×10⁶ and 7.51×10⁶ ergs/cm³ at 340 K, respectively. Thus, our determination of temperature-dependence of the anisotropy constant represents an improvement over existing works.     

Effect of Mn on the magnetic properties of Fe3B/Nd2Fe14B nanocomposites

The magnetic properties of Nd_4.5Fe_77−xMn_xB_18.5 (x=0, 1 and 2) nanocomposites prepared by the crystallization of amorphous precursors were investigated. Addition of Mn is found to decrease the crystallization temperature of the amorphous ribbons. The intrinsic coercivity _iH_c and maximum energy product (BH)_max increase from 2.6 kOe and 9.1 MGOe for x=0 to 3.1 kOe and 10.3 MGOe for x=1, respectively, and the remanence ratio M_r/M_s increases from 0.70 to 0.72. The effect of Mn on Curie temperature T_C and the thermal stability of M_r and _iH_c were also studied. ⁵⁷Fe Mössbauer spectra have been recorded for x=0, 1 and 2 ribbons at room temperature and site preference of the Mn atoms in Fe₃B and Nd₂Fe₁₄B phases is discussed using the Mössbauer spectroscopy.     

Temperature and composition dependence of magnetic properties of cobalt–chromium co-substituted magnesium ferrite nanomaterials

The temperature and composition dependence of magnetic properties of Co–Cr co-substituted magnesium ferrite, Mg_1−xCo_xCr_xFe_2−xO₄ (x=0.0–0.5), prepared by novel polyethylene glycol assisted microemulsion method, are studied. The synthesized materials are characterized by the Mössbauer spectrometer and standard magnetic measurements. Major hysteresis loops are measured up to the magnetic field of 50 kOe at 300, 200 and 100 K. The high field regimes of these loops are modeled using the Law of Approach to saturation to determine the first-order cubic anisotropy coefficient and saturation magnetization. Both the saturation magnetization and the anisotropy coefficient are observed to increase with the decrease in temperature for all Co–Cr co-substitution levels. Also, both the saturation magnetization and the anisotropy coefficient achieved maximum value at x=0.3 and x=0.2, respectively. Explanation of the observed behavior is proposed in terms of the site occupancy of the co-substituent, Co²⁺ and Cr³⁺ in the cubic spinel lattice.     

Magnetic and structural features of amorphous FeMo-based alloys

NANOPERM-type FeMoCuB alloys are studied using magnetic and Mössbauer measurements in the as-prepared amorphous state. It is shown that the Fe₇₆Mo₈Cu₁B₁₅ (A) and Fe₇₄Mo₈Cu₁B₁₇ (B) alloys exhibit the magnetic dipole and electrical quadrupole interactions well detected in the room-temperature Mössbauer spectra. The thermomagnetic measurements above the room temperature indicate a vanishing of the magnetic interactions at approximately 310 K (A) and at 340 K (B), respectively. The low-temperature DC magnetic measurements show an anomaly around 200 K which is also a boundary at which zero-field Mössbauer measurements of both samples reflect the gradual “vanishing” of the electrical quadrupole interactions and appearance of another magnetically ordered component. The Mössbauer measurements in the field of 4 MA/m yield a survival of quadrupole and an enhancement of magnetic dipole interactions.     

Mössbauer study of Na0.82Co0.99Fe0.01O2

We studied by Mössbauer spectroscopy the Na_0.82CoO₂ compound using 1% ⁵⁷Fe as a local probe which substitutes for the Co ions. Mössbauer spectra at T=300 K revealed two sites which correspond to Fe³⁺ and Fe⁴⁺. The existence of two distinct values of the quadrupole splitting instead of a continuous distribution should be related with the charge ordering of Co⁺³, Co⁺⁴ ions and ion ordering of Na(1) and Na(2). Below T=10 K part of the spectrum area, corresponding to Fe⁴⁺ and all of Fe³⁺, displays broad magnetically split spectra arising either from short-range magnetic correlations or from slow electronic spin relaxation.     

Effect of Cu-Cr co-substitution on magnetic properties of nanocrystalline magnesium ferrite

This study deals with the temperature and composition dependence of magnetization and magnetic anisotropy of Cu²⁺-Cr³⁺ co-substituted magnesium ferrite, Mg_1−xCu_xCr_xFe_2−xO₄ (x=0.0-0.5). The synthesized materials are characterized using thermo gravimetric analysis, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray fluorescence, Mössbauer spectrometer, superconducting quantum interference device magnetometer and vibrating sample magnetometer. The M-H loops measured up to 50 kOe at 300, 200 and 100 K, revealed narrow hysteresis curves with a coercive field and saturation magnetization varying for different compositions. The high field regimes of these loops are modeled using the Law of Approach to saturation to extract anisotropy information and saturation magnetization. Both the saturation magnetization and the anisotropy constant are observed to increase with the decrease in temperature while decrease with the Cu-Cr co-substituents for all the samples. Explanation of the observed behavior is proposed in terms of the preference of the co-substituent ions of Cu²⁺ and Cr³⁺ and their predominant choice to substitute into the octahedral sites of the cubic spinel lattice.     

Hopping conductivity of Ni-doped p-CdSb in strong magnetic fields

Magnetoresistance (MR) of oriented single crystals of the anisotropic semiconductor p-CdSb doped with 2 at% of Ni is investigated between T=1.5 and 300 K in transversal pulsed magnetic fields up to B=30 T. In fields B∼4-15 T at T below 4.2 K, the resistivity obeys the law ln ρ∼η[B?(B)]^1/2 with ?(B)=a(0)/a(B), where a is the carrier localization radius and parameter η depends on a(0), on the acceptor concentration N_A and on the direction of the magnetic field with respect to the crystallographic axes, but does not depend on T. Such behavior gives evidence for MR realized by hopping charge transfer over the nearest-neighbor sites in strong magnetic field. The analysis of the experimental data yields the values of η, agreeing with calculated ones within an error of 10%, taking into account the effects of the anisotropy of the acceptor states and of the explicit dependence of a(B) due to the increase in the activation energy of shallow acceptors in magnetic field and the sensitivity of the metal-insulator transition to B.