Superparamagnetic behavior of La0.67Sr0.33MnO3 nanoparticles prepared via sol-gel method

Magnetic nanoparticles of La_0.67Sr_0.33MnO₃ (LSMO) manganite were prepared by sol-gel method. Phase formation and crystal structure of the synthesized powder were examined by the X-ray diffraction (XRD) using the Rietveld analysis. The mean particle size was determined by the transmission electron microscopy (TEM). Infrared transmission spectroscopy revealed that stretching and bending modes are influenced by calcinations temperature. The temperature dependence of the ac magnetic susceptibility was measured at different frequencies and ac magnetic fields in the selected ranges of 40-1000 Hz and 80-800 A/m, respectively. The temperature dependence of ac susceptibility shows a characteristic maxima corresponding to the blocking temperature near room temperature. The frequency dependence of the blocking temperature is well described by the Vogel-Fulcher law. By fitting the experimental data with this law, the relaxation time τ₀=1.7×10⁻¹² s, characteristic temperature T₀=262±3 K, anisotropy energy E_a/k=684±15 K and effective magnetic anisotropy constant k_eff=2.25×10⁴ erg/cm³ have been obtained. dc Magnetization measurement versus magnetic field shows that some of LSMO nanoparticles are blocked at 293 K. The role of magnetic interparticle interactions on the magnetic behavior is also investigated.     

Magnetism in Zn1−xMnxO crystal prepared by hydrothermal method

Crystal Zn_1−xMn_xO magnetic semiconductors have been obtained by using a hydrothermal method for the first time at temperature of 703 K with substituent fraction ranging from x=0 to 0.04. X-ray diffraction and optical absorption measurements provide evidence for the locating at Zn site of Mn ion in ZnO crystals. The non-monotonic variation of band gap indicates the short-ranged interactions of sp-d electrons. However, no evidence of ferromagnetism is found in these systems down to T=2 K. The magnetization is found to be contributed from both free spins and spins associated with antiferromagnetic clusters. The antiferromagnetism is confirmed by fitting a Curie-Weiss function.     

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.     

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.     

Reentrant spin glass behaviour in Nd0.84K0.12MnO3

Polycrystalline Nd_0.84K_0.12MnO₃ was prepared in single phase form with Pbnm space group. The magnetic properties are studied from magnetization, linear and non-linear susceptibility, and thermoremanent magnetization measurements. The sample exhibits paramagnetic to ferromagnetic transition followed by low temperature spin glass like transition. From frequency variation of ac susceptibility measurements, the spin glass transition temperature is found to be 97.6±0.1 K with critical exponents zυ=1.13±0.06. The critical exponent γ corresponding to spin glass transition has been determined from the third harmonic susceptibility analysis and it is found to be 3.09±0.05. The effective number of spins blocked under frustration and their correlation length are determined from the analysis of thermoremanent magnetization.     

Electron hopping mechanism in hematite (α-Fe2O3)

The frequency dependence of the real (?′) and imaginary (?″) parts of the dielectric constant of polycrystalline hematite (α-Fe₂O₃) has been investigated in the frequency range 0-100 kHz and the temperature range 190-350 K, in order to reveal experimentally the electron hopping mechanism that takes place during the Morin transition of spin-flip process. The dielectric behaviour is described well by the Debye-type relaxation (α-dispersion) in the temperature regions T<233 K and T>338 K. In the intermediate temperature range 233 K<T<338 K a charge carrier mechanism takes place (electron jump from the O²⁻ ion into one of the magnetic ions Fe³⁺) which gives rise to the low frequency conductivity and to the Ω-dispersion. The temperature dependence of relaxation time (τ) in the −ln τ vs 10³/T plot shows two linear regions. In the first, T<238 K, τ increases with increasing T implying a negative activation energy −0.01 eV, and in the second region T>318 K τ decreases as the temperature increases implying a positive activation energy 0.12 eV. The total reorganization energy (0.12-0.01) 0.11 eV is in agreement with the adiabatic activation energy 0.11 eV given by an ab initio model in the literature. The temperature dependence of the phase shift in the frequencies 1, 5, 10 kHz applied shows clearly an average Morin temperature T_Mo=284±1 K that is higher than the value of 263 K corresponding to a single crystal due to the size and shape of material grains.     

Dependence of Néel temperature on the particle size of MnFe2O4

Mn-ferrite nanoparticles having diameter in the range 17-45 nm were synthesized by modified co-precipitation method using metal nitrate solutions. Different concentrations of NaOH were found to affect the growth of particle size. Néel temperature (T_N) was found to increase with increasing particle size. The obtained Néel temperature was higher than that of the bulk. The shift in the Néel temperature is described by the finite size-scaling theory [T_N(d)−T_N(bulk)]/T_N(bulk)=(d/d₀)^−1/v, where d is particle size, v=0.6±0.1 and d₀=1.7±0.1 nm.     

Fabrication, magnetism and high frequency application of exchange-coupled Fe65Co35±2-SiO1.7±0.2 granular films

A series of (Fe₆₅Co_35±2)_x-(SiO_1.7±0.2)_1−x nano-granular films with various metal volume fractions (x) were fabricated by rf sputtering. In a wide range, excellent soft magnetic properties have been achieved. In the x range from 0.7 to 0.48, the films exhibit small coercivity H_c not exceeding 4 Oe and high electrical resistivity ρ up to 1.15 × 10⁴ μΩ cm. And a minimum H_c value of 1.65 Oe was obtained for the sample of x = 0.57 with ρ = 2.86 × 10³ μΩ cm. At a frequency lower than 2.0 GHz, the real part μ′ of complex permeability of this sample is more than 170 and the FMR frequency is as high as 2.6 GHz, implying a high cut-off frequency for high frequency applications. With decreasing Fe₆₅Co_35±2 volume fraction, the resistivity of films increases remarkably and the grain size decreases obviously. At the same time, the coercivity H_c decreases with grain size decreasing, which is consistent with the conclusion resulted from random anisotropy model quoted by Herzer. Study on Henkel plots shows that intergranular ferromagnetic exchange coupling exists among grains and is important for realizing soft magnetic properties.     

Evidence of glassy ferromagnetic phase and kinetic arrest of electronic phase in Sm0.35Pr0.15Sr0.5MnO3 manganites

The effect of doping of rare earth Pr³⁺ ion as a replacement of Sm³⁺ in Sm_0.5Sr_0.5MnO₃ is investigated. Temperature dependent dc and ac magnetic susceptibility, resistivity, magnetoresistance measurements on chemically synthesized (Sm_0.5−xPr_x)Sr_0.5MnO₃ show various unusual features with doping level x=0.15. The frequency independent ferromagnetic to paramagnetic transition at higher temperature (∼191 K) followed by a frequency dependent reentrant magnetic transition at lower temperature (∼31 K) has been observed. The nature of this frequency dependent reentrant magnetic transition is described by a critical slowing down model of spin glasses. From non-linear ac susceptibility measurements it has been confirmed that the finite size ferromagnetic clusters are formed as a consequence of intrinsic phase separation, and undergo spin glass-like freezing below a certain temperature. There is an unusual observation of a 2nd harmonic peak in the non-linear ac susceptibility around this reentrant magnetic transition at low temperature (∼31 K). Arrott plots at 10 and 30 K confirm the existence of glassy ferromagnetism below this low temperature reentrant transition. Electronic- and magneto-transport measurements show a strong magnetic field—temperature history dependence and strong irreversibility with respect to the sweeping of magnetic field. These results are attributed to the effect of phase separation and kinetic arrest of the electronic phase in this phase separated manganite at low temperatures.     

Very high field magnetization and AC susceptibility of native horse spleen ferritin

The magnetization of native horse spleen ferritin protein is measured in pulsed magnetic fields to 55 T at T=1.52 K. The magnetization rises smoothly with negative curvature due to uncompensated Fe³⁺ spins and with a large high field slope due to the underlying antiferromagnetic ferritin core. Even at highest fields the magnetic moment is only ∼4% of the saturation moment of the full complement of Fe³⁺ in the ferritin molecule. The AC magnetic susceptibility, χ_AC(T,f), responding to the uncompensated spins, reaches a maximum near the superparamagnetic blocking temperature with the temperature of the maximum, T_M, varying with excitation frequency, T_M⁻¹ α log f for 10?f?10⁴ Hz.     

Suppression of low-temperature magnetic states in Mn3O4 nanoparticles

We have investigated the low-temperature magnetic properties of Mn₃O₄ nanoparticles using thermodynamic and magnetic measurements. While bulk Mn₃O₄ exhibits three magnetic transitions close to 42, 40 and 34 K, the two lower temperature transitions appear to be absent above 15 K in Mn₃O₄ nanoparticles. The magnetization and spin entropy associated with the ferrimagnetic transition at 42 K is smaller in the Mn₃O₄ nanoparticles than bulk Mn₃O₄, which is consistent with roughly 30-50% of the spins not contributing to the magnetic order. We tentatively attribute this suppression of the lower temperature transitions to a combination of finite size effects and effects arising from amorphous surface spins on the nanoparticles.     

The magnetic structure of the compound Ho5Sb3

We have investigated the magnetic behavior of Ho₅Sb₃ compound (Mn₅Si₃-type, hexagonal; a=0.8865(1) nm, c=0.6232(1) nm, as derived from X-ray Guinier powder pattern) by using the techniques of magnetization, electrical resistivity, heat capacity and neutron diffraction. We find that Ho₅Sb₃ exhibits a ferrimagnetic type (Ferrimagnet I) ordering below 60 K with propagation vectors K₀=[0, 0, 1] and K₁=[±K_x, 0, 0]. Below 40 K, the thermal variation of magnetic reflections and the appearance of an additional magnetic component with propagation vector K₂=[0, 1/2, 0] show the onset of an antiferromagnetic type of ordering in the magnetic structure; which evolves into yet another ferrimagnetic structure (Ferrimagnet II) as the temperature is lowered down to 2 K. The magnetic moments of the Ho atoms at the (4d) and (6g) sites with magnitudes of nearly 7.4 and 6.3 μ_B at 2 K, respectively, are inclined approximately at 70° to the c-axis.     

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.     

Critical behavior and magnetic entropy change in the La0.6Sr0.4Mn0.8Fe0.1Cr0.1O3 perovskite

Critical behavior in the La_0.6Sr_0.4Mn_0.8Fe_0.1Cr_0.1O₃ ceramics was studied using magnetization methods. Results show that the paramagnetic–ferromagnetic transition is of second order. Based on the critical behavior analysis using the Banerjee criterion and the Kouvel–Fisher method, we find the critical exponents: β=0.395±0.010, γ=1.402±0.010, and δ=5.208±0.007, for which the magnetic interaction is satisfied within the three-dimensional Heisenberg model. Results indicate the presence of short-range interactions. The magnetic entropy change (−ΔS_M) reached maximum values of 1.75, 1.45, 1.15, 0.8 and 0.43 J Kg⁻¹ K⁻¹ under a magnetic field variation of 5, 4, 3, 2 and 1 T, respectively. Nevertheless, these (−ΔS_M) values are much low for any potential application at this moment. The nature of this phenomenon is discussed in relation to the characteristics of the magnetic phase transition and critical exponents.     

Exchange bias effect in multiferroic Eu0.75Y0.25MnO3

The exchange bias phenomenon has been investigated in multiferroic Eu_0.75Y_0.25MnO₃. The material shows a weak ferromagnetism with cone spin configuration induced by external magnetic field below 30 K. Consequently, the electric polarization coming from the cycloid spin order below 30 K can be suppressed by external magnetic fields. The magnetic hysteresis loops after cooling in a magnetic field exhibit characteristics of exchange bias below the spin glassy freezing temperature (T_g)∼16 K. The exchange bias field, coercivity field, and remanent magnetization increase with increasing cooling magnetic field. The exchange bias effect is ascribed to the frozen uncompensated spins at the antiferromagnetism/weak ferromagnetism interfaces in the spin-glass like phase.     

Probing the magnetic state by linear and non-linear ac magnetic susceptibility measurements in under-doped manganite Nd0.8Sr0.2MnO3

We have thoroughly investigated the entire magnetic states of under-doped ferromagnetic-insulating manganite Nd_0.8Sr_0.2MnO₃ through temperature-dependent linear and non-linear complex ac magnetic susceptibility measurements. This ferromagnetic-insulating manganite is found to have frequency-independent ferromagnetic to paramagnetic transition temperature at around 140 K. At around 90 K (≈T_?) the sample shows a second frequency-dependent re-entrant magnetic transition as explored through complex ac susceptibility measurements. Non-linear ac susceptibility measurements (higher harmonics of ac susceptibility) have also been performed (with and without the superposition of a dc magnetic field) to further investigate the origin of this frequency dependence (dynamic behavior at this re-entrant magnetic transition). Divergence of 3rd harmonic of ac susceptibility in the limit of zero exciting field indicates a spin-glass-like freezing phenomena. However, large value of spin-relaxation time (τ₀=10⁻⁸ s) and small value of coercivity (∼22 Oe) obtained at low temperature (below T_?) from critical slowing down model and dc magnetic measurements, respectively, are in contrast with what generally observed in a canonical spin glass (τ₀=10⁻¹²-10⁻¹⁴ s and very large value of coercivity below freezing temperature). We have attributed our observation to the formation of finite size ferromagnetic clusters which are formed as consequence of intrinsic phase separation and undergo cluster glass-like freezing below certain temperature in this under-doped manganite. The results are supported by the electronic- and magneto-transport data.     

Mössbauer characterization of tin dopant ions in the antiferromagnetic ilmenite MnTiO3

Mössbauer parameters of ¹¹⁹Sn diamagnetic dopant cations in an antiferromagnetic compound having the ilmenite structure are for the first time reported. The spectra reveal a well resolved hyperfine splitting pattern of combined magnetic and quadrupole interactions (at 5 K, δ=0.19 mm/s, H₁=52.5 kOe, eV_ZZQ_3/2=−0.80 mm/s, θ≈0°). This spectral component whose contribution (A₁=82%) represents more than four fifths of the total amount of the dopant (Sn/(Mn+Ti)=1/200) is assigned to Sn(IV) ions located in the bulk of MnTiO₃, on the Mn(II) site, and with a Mn(II) vacancy in their nearest surrounding. Two spectral components with minor contributions are also observed: one of them (H₂≈25 kOe, A₂=8%) can be assigned to Sn(IV) ions, in the MnTiO₃ lattice as well, on a site where they exhibit a weaker spin polarization (this site could be the Ti(IV) one) and the other (H₃=0 kOe, A₃=10%) to SnO₂ or/and Ti_1−xSn_xO₂ clusters. The Néel temperature of MnTiO₃ probed by the ¹¹⁹Sn dopant (T_N=69±2 K) agrees well with the values previously provided by ESR and antiferromagnetic resonance measurements. Variation of H₁ with temperature follows close the Brillouin function for S=5/2. No perturbation appears in the Mössbauer spectra around T=90 K where a broad peak, characteristic of 2D magnetic interactions, is observed on the static magnetic susceptibility curve.     

Production and corrosion resistance of NdFeBZr magnets with an improved response to thermal variations during sintering

This study describes an attempt to produce NdFeB magnets that are insensitive to the sintering temperature. It was found that addition of Zr to NdFeB magnets significantly augmented the thermal stability of this magnetic material during sintering at high temperature even at industrial scale. The best sintered magnets were produced by jet-milling the powder (to achieve an average 3.4 μm particle size), and then aligned, pressed and sintered under argon at 1100 °C for 3 h followed by appropriate heat treatment. The magnetic properties of the resulting magnets were: (BH)_m=403.8 kJ m⁻³ (±4.7 kJ m⁻³), B_r=1430 mT (±9 mT) and _iH_c=907 kA m⁻¹ (±12 kA m⁻¹). Large grain growth, in excess of 100 μm in the Zr-free magnets, was observed during sintering at 1100 °C. This did not occur in the presence of Zr. These observations imply that the sensitivity of this class of magnets to high sintering temperatures is greatly reduced by Zr addition. Corrosion resistance of NdFeB was therefore significantly improved by the addition of small amounts of Zr.     

Electrical and magnetic properties of ε-Fe3N nanoparticles synthesized by chemical vapor condensation process

ε-Fe₃N nanoparticles synthesized by chemical vapor condensation (CVC) are covered with shells of disordered Fe₃O₄ phase, as observed by a transmission electron microscopy. The zero-field cooling and field cooling temperature dependence of magnetization, ac susceptibility as a function of frequency, magnetic hysteresis loops, and the temperature dependence of resistivity of the ε-Fe₃N nanoparticles are systematically studied. The results indicate the existence of complex magnetic properties, such as superparamagnetic behavior, exchange bias, magnetic dipole interaction, and the possible coexistence of ferromagnetic and spin-glass-like states and/or disordered surface spins of the shells at low temperatures. The temperature dependence of resistivity ρ(T) for compacted ε-Fe₃N nanoparticles in a temperature range of 110 K< T< 300 K can be well described by the mechanism of fluctuation-induced tunneling conduction, while that below 110 K can be ascribed to conducting electrons scattered by localized magnetic moments and impurity as well as the influence of freezing of spin-glass-like moments and/or disordered surface spins of the shells.