Spin glass ordering of Zn0.75Co0.25Fe0.5Cr1.5O4 cubic spinel

The linear and nonlinear low field AC susceptibilities of Zn_0.75Co_0.25Fe_0.5Cr_1.5O₄ show peaks due to non-critical contributions, which mask the peak due to spin glass ordering. They extend into the region of temperatures in which Mössbauer spectra do not show any magnetic component. When a DC field of 200 Oe suppresses the non-critical contributions, peak due to spin glass ordering is clearly visible. The spin glass ordering is thus shown to be a thermodynamic transition. The critical exponent is found to fall within the range found using other spin glasses. Mössbauer spectra in zero fields provide T_SG, which agrees with the peak temperature of AC susceptibilities in the absence of non-critical contributions. 〈S_Z〉 determined using Mössbauer spectra does not show any anomaly. In the presence of a field of 5 T, the spectra show SG ordering at 4.2 K, which converts into ferrimagnetic ordering at higher temperatures.     

Spin-glass-like phase behaviour in CeNi2−xCuxSn2

We report the results of our investigation in CeNi_2−xCu_xSn₂ (x=0, 0.4, 1.0, 1.6 and 2.0), a new pseudoternary series with CaBe₂Ge₂-type tetragonal structure. Substitution of Cu for Ni leads to a linear increase in the constants a, c and the unit cell volume v. As probed by the low temperature dependence of ac susceptibility χ_ac(T), the T_f temperature, which corresponds to the freezing temperature of the spin-glass clusters, is annihilated above 2.0 K significantly for the samples with x≥1.6. This observation proves conclusively that the Ni-rich samples in the series CeNi_2−xCu_xSn₂ have the advantage of forming the spin-glass-like state.     

Magnetic properties of ZnFe2O4 nanoparticles produced by a low-temperature solid-state reaction method

ZnFe₂O₄ nanoparticles with average grain size ranging from 40 to 60 nm behaving superparamagnetic at room temperature have been produced using a low-temperature solid-state reaction (LTSSR) method without ball-milling process. Abnormal magnetic properties such as S-shape hysteresis loops and non-zero magnetic moments were observed. ZnFe₂O₄ nanoparticles were also synthesized using a NaOH coprecipitation method and a PVA sol-gel method to study the relationship between the preparation processes and the magnetic properties. Spin-glass behavior was observed in the low temperature solid-state reaction produced Zn ferrite in the zero-field cooled (ZFC) measurement. Our work proves that the various preparation methods will to some extent determine the properties of magnetic nanoparticles.     

Magnetic-field-induced transition from metastable spin glass to possible antiferromagnetic-ferromagnetic phase separation in Cd0.5Cu0.5Cr2O4

Using ac susceptibility, dc magnetization and heat-capacity measurements, we have investigated the magnetic properties of Cd_0.5Cu_0.5Cr₂O₄. Cd_0.5Cu_0.5Cr₂O₄ has an extraordinary magnetic phase including a metastable spin-glass (SG) phase at zero field, a possible phase separation scenario of AFM/FM above ∼0.5 T field, and at intermediate fields, an apparent pseudo reentrant spin-glass (RSG) plateau is observed. These phenomena are closely correlated with the pinning effect of the Cu²⁺ sublattice on the frustrated lattice.     

The role of iron in the formation of the magnetic structure and related properties of La0.8Sr0.2Co1−xFexO3 (x=0.15, 0.2, 0.3)

La_0.8Sr_0.2Co_1−xFe_xO₃ (x=0.15, 0.2, 0.3) samples were studied by means of AC magnetic susceptibility, magnetization, magnetoresistance and ⁵⁷Fe Mössbauer spectrometry. Iron was found to take on a high spin 3d^5−α electronic state in each of the samples, where α refers to a partly delocalized 3d electron. The compounds were found to exhibit a spin-cluster glass transition with a common transition temperature of ∼53 K. The spin-cluster glass transition is visualized in the ⁵⁷Fe Mössbauer spectra as the slowing down of magnetic relaxation below ∼70 K, thereby showing that iron takes part in the formation of the glassy magnetic phase. The paramagnetic-like phase found at higher temperatures is identified below T_c≈195 K as being composed of weakly interacting, magnetically ordered nanosized clusters of magnetic ions in part with a magnetic moment oriented opposite to the net magnetic moment of the cluster. For each of the samples a considerable low-temperature negative magnetoresistance was found, whose magnitude in the studied range decreases with increasing iron concentration. The observed results obtained on the present compounds are qualitatively explained assuming that the absolute strengths of magnetic exchange interactions are subject to the relation ∣J_Co–Co∣<∣J_Fe–Co∣<∣J_Fe–Fe∣.     

Mössbauer study of Fe0.92−xCoxP0.08 nanowire arrays

Arrays of Fe_0.92−xCo_xP_0.08 (0.22≤x≤0.78) ternary alloy nanowires were fabricated in anodic aluminium oxide templates by electrochemical deposition. The broadened peaks in transmission Mössbauer spectra and the halo in selected area electron diffraction patterns indicate that the structure of Fe_0.92−xCo_xP_0.08 nanowires is amorphous. However, the short-range order of Fe_0.92−xCo_xP_0.08 nanowires has a bcc structure with a [110]-preferred orientation that is parallel to the nanowires. The magnetic texture results in the magnetic moment direction of the Fe atoms being along the nanowires. The short-range order around the Fe atoms reaches a minimum at x=0.45. With increasing Co content, the average hyperfine field decreases, while the isomer shift and quadrupole splitting remain almost constant, which result from the variation of 3d and 4s electron volume density at the Fe sites.     

Synthesis and magnetic properties of CoFe2O4 ferrite nanoparticles

CoFe₂O₄ ferrite nanoparticles were prepared by a modified chemical coprecipitation route. Structural and magnetic properties were systematically investigated. X-ray diffraction results showed that the sample was in single phase with the space group . The results of field-emission scanning electronic microscopy showed that the grains appeared spherical with diameters ranging from 20 to 30 nm. The composition determined by energy-dispersive spectroscopy was stoichiometry of CoFe₂O₄. The Curie temperature in the process of increasing temperature was slightly higher than that in the process of decreasing temperature. This can be understood by the fact that heating changed Co²⁺ ion redistribution in tetrahedral and in octahedral sites. The coercivity of the synthesized CoFe₂O₄ samples was lower than the theoretical values, which could be explained by the mono-domain structure and a transformation from ferrimagnetic to superparamagnetic state.     

Mössbauer studies on the superparamagnetic behavior of CoFe2O4 with a few nanometers

CoFe₂O₄ nanoparticles with a cubic spinel structure are prepared by a high-temperature thermal decomposition method. The average particle sizes are 4.6  and 5.7 nm for CoFe₂O₄ made with two kinds of solvents by TEM. Mössbauer spectra of 4.6 nm particles displayed a superparamagnetic behavior as demonstrated by a single line with zero hyperfine fields, but that of 5.7 nm particles did not at room temperature. It is considered that anisotropy energy was still more superior to thermal energy because of particle size of 5.7 nm CoFe₂O₄. Furthermore, Mössbauer spectra exhibited the typical spectrum shapes of the CoFe₂O₄ at 4.2 K. The spectrum at 4.2 K was fitted using two magnetic components of hyperfine fields _Hhf=540.4,512.6$H_{\mathrm{hf}}=540.4,512.6$ kOe and isomer shifts δ=0.40,0.30$\delta =0.40,0.30$ mm/s for 4.6 nm and _Hhf=542.7,512.8$H_{\mathrm{hf}}=542.7,512.8$ kOe and δ=0.41,0.29$\delta =0.41,0.29$ mm/s for 5.7 nm corresponding to Fe³⁺ ions at site A and site B, respectively.     

Preparation and characterizations of SiO2-coated nanoparticles of Mn0.4Zn0.6Fe2O4

Core/shell nanoparticles consisting of a magnetic core of zinc-substituted manganese ferrite (Mn_0.4Zn_0.6Fe₂O₄) and a shell of silica (SiO₂) are prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) as a precursor material for silica and salts of iron, manganese and zinc as the precursor of the ferrite. Three weight percentages of the shell materials of SiO₂ are used to prepare the coated nanoparticles. The X-ray diffractograms (XRD) of the coated and uncoated magnetic nanoparticles confirmed that the magnetic nanoparticles are in their mixed spinel phase in an amorphous matrix of silica. Particles sizes of the samples annealed at different temperatures are estimated from the width of the (3 1 1) line of the XRD pattern using the Debye-Sherrer equation. The information regarding the crystallographic structure together with the particles sizes extracted from the high-resolution transmission electron microscopy (HRTEM) of a few selected samples are in agreement with those obtained from the XRD. HRTEM observations revealed that particles are coated with silica. The calculated thickness is in agreement with that obtained from the HRTEM pictures. Hysteresis loops observed in the temperature range 300 down to 5 K and Mössbauer spectra at room temperature indicate superparamagnetic relaxation of the nanoparticles.     

Hyperfine interactions in some Aurivillius Bim+1Ti3Fem−3O3m+3 compounds

X-ray diffraction and Mössbauer spectroscopy were applied as complementary methods to investigate the structure and hyperfine interactions in the series of Bi_m+1Ti₃Fe_m−3O_3m+3 Aurivillius compounds with m=4, 6, 7 and 8. Samples were synthesized by the solid-state sintering method at various temperatures. As X-ray diffraction analysis proved, the compounds formed single phases at temperature above 993 K. Mössbauer studies have confirmed diffraction measurements. Compounds synthesized at 993 K contained residual hematite, however these sintered at elevated temperatures were single-phased materials. Room-temperature Mössbauer spectra of Bi_m+1Ti₃Fe_m−3O_3m+3 compounds revealed their paramagnetic properties, what is consistent with the literature data concerning the Néel temperature of these ceramics (T_N is smaller than room temperature). Detailed analysis of MS spectra allowed to state that iron ions may occupy both tetrahedral and octahedral sites in the crystallographic lattice of Aurivillius compounds.     

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.     

Morphology and magnetic properties of Co0.8Fe2.2O4 films prepared by the chemical solution deposition

Co_0.8Fe_2.2O₄ ferrite thin films have been prepared on Si(0 0 1) substrates by the chemical solution deposition. Structural characteristics indicate all films are single phase with spinel structure and the space group and the mean grain size increases from 8 to 30 nm with the increase of annealing temperature. The magnetic properties of Co_0.8Fe_2.2O₄ thin films are highly dependent on annealing temperature. The sample annealed at 800 °C possesses high saturation magnetization, moderate coercivity and squareness ratio, making it a promising application candidate in high-density record and magneto-optical materials.     

Bulk Sn1−xMnxO2 magnetic semiconductors without room-temperature ferromagnetism

Polycrystalline Sn_1−xMn_xO₂ (0≤x≤0.05) diluted magnetic semiconductors were prepared by solid-state reaction method and their structural and magnetic properties had been investigated systematically. The three Mn-doped samples (x=0.01, 0.03, 0.05) undergo paramagnetic to ferromagnetic phase transitions upon cooling, but their Curie temperatures are far lower than room temperature. The magnetization cannot be attributed to any identified impurity phase. It is also found that the magnetization increases with increasing Mn doping, while the ratio of the Mn ions contributing to ferromagnetic ordering to the total Mn ions decreases.     

Structure and magnetic properties of (Nd,Dy)16(Fe,Co)76−xTixB8 powders prepared by mechanical alloying

Nanocrystalline (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ magnets were prepared by mechanical alloying and respective heat treatment at 973–1073 K/30–60 min. An addition of 0.5 at % of Ti results in an increase of coercivity from 796 to 1115 kA m⁻¹. Partial substitution of Nd by Dy results in an additional increase of coercivity up to 1234 kA m⁻¹. Mössbauer investigations shows that for x?1 the (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ powders are single phase. For higher Ti contents (x>1) the mechanically alloyed powders heat treated at 973 K are no more single phase, and the coercivity decreases due to the presence of an amorphous phase. A heat treatment at a higher temperature (1073 K) for longer time (1 h) results in the full recrystallisation of powders. The mean hyperfine field of the Nd₂Fe₁₄B phase decreases for titanium contents of 0?x?1, and remains constant for x>1. This indicates that the Ti content in the Nd₂Fe₁₄B phase reaches its maximum value.     

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.     

Magnetic study of Mg0.95Mn0.05Fe2O4 ferrite nanoparticles

The magnetic properties of Mg_0.95Mn_0.05Fe₂O₄ ferrite samples with an average particle size of ∼6.0±0.6 nm have been studied using X-ray diffraction, Mössbauer spectroscopy, dc magnetization and frequency dependent real χ^′(T) and imaginary χ^″(T) parts of ac susceptibility measurements. A magnetic transition to an ordered state is observed at about 195 K from Mössbauer measurements. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization have been recorded at low field and show the typical behavior of a small particle system. The ZFC curve displays a broad maximum at , a temperature which depends upon the distribution of particle volumes in the sample. The FC curve was nearly flat below , as compared with monotonically increasing characteristics of non-interacting superparamagnetic systems indicating the existence of strong interactions among the nanoparticles. A frequency-dependent peak observed in χ^′(T) is well described by Vogel-Fulcher law, yielding a relaxation time and an interaction parameter . Such values show the strong interactions and rule out the possibility of spin-glass (SG) features among the nanoparticle system. On the other hand fitting with the Néel-Brown model and the power law yields an unphysical large value of τ₀ (∼6×10⁻⁶⁹ and 1.2×10⁻²² s respectively).     

Ferromagnetism and antiferromagnetism in Ni2+x+yMn1−xAl1−y alloys

The magnetic behavior of Ni_2+xMn_1−xAl alloys around the stoichiometric 2:1:1 composition was investigated with several experimental techniques. The results of low-temperature magnetization measurements indicate that a competition mechanism between ferromagnetism and antiferromagnetism is expected in off-stoichiometric alloys. Although the Curie temperature is strongly dependent on the composition, the saturation magnetization has an unsystematic variation for deviations from the stoichiometric Ni₂MnAl alloy. A reentrant-spin-glass behavior is observed below 50 K.     

Antiferromagnetic versus spin-glass like behavior in MnIn2S4

The low-temperature magnetic properties of MnIn₂S₄ have been studied using AC magnetic susceptibility and magnetization experiments. High-temperature susceptibility fits indicate the presence of antiferromagnetic interactions. Low-field magnetization data show a peak at 5.6±0.1 K, below which strong irreversibility is observed between zero-field-cooled (ZFC) and field-cooled (FC) cycles suggesting that the observed peak corresponds to a spin-glass-like transition instead of the antiferromagnetic one previously reported. Further evidence of this magnetic state comes from AC susceptibility data at different frequencies. The in-phase component χ′(T) exhibits the behavior expected of spin glasses, i.e. a shift of the cusp to higher temperatures for higher frequencies.     

Effect of atomic environment on the Fe hyperfine structure and the thermal stability of magnetic order in L10 ordered Fe-Pt alloys

The ⁵⁷Fe Mössbauer effect measurements were made for the L1₀ ordered Fe-Pt alloys with 39-62 at% Pt and the effect of local atomic environment on the hyperfine structure was investigated. Furthermore, the thermal stability of magnetic order was investigated for the alloys with high Pt concentration. From the analyses of the observed Mössbauer spectra, we found that dipole-field-like anisotropic transferred hyperfine fields are mainly responsible for the large difference in hyperfine field between Fe-site and Pt-site in the Fe-rich alloys. In the Pt-rich region far from stoichiometry, the existence of many Fe-sites occupied by excess Pt atoms causes a distribution of exchange fields. Therefore, the iron atoms in different local environments may have their several hyperfine fields with different temperature dependence. The anomalous temperature dependence of the averaged hyperfine field and line broadening observed for the 61, 62 at% Pt alloys can be understood from the co-existence of various sub-spectra with different temperature dependence. As a result, the thermal stability of magnetic order is largely reduced as the Pt concentration exceeds 60 at%.     

Synthesis and properties of Mn1−XFeXS single-crystals at room temperature

Results of the first synthesis of Mn_1−XFe_XS single-crystals and its structural, electrical and magnetic properties at room temperature are presented. The Mn²⁺→Fe²⁺ substitution in Mn_1−XFe_XS solid solutions is accompanied by a compression of the NaCl lattice and a small deformation of the octahedral environments, and the concentration transition from dielectric to semimetal. Single-line Mossbauer spectra indicate the paramagnetic state Mn_1−XFe_XS sulfides at room temperature.