Preparation and investigation of magnetic properties of wüstite nanoparticles

In this work wüstite nanoparticles have been prepared via high-energy ball milling, using high-purity hematite (Fe₂O₃) and iron (Fe) powders as the starting materials. In order to get a single-phase wüstite different mole ratios of (Fe/Fe₂O₃) were milled, using a planetary mill. X-ray diffraction studies of the as-milled powders show that a single-phase wüstite was formed for a mole ratio of 0.6. Lattice parameter of the wüstite was obtained from XRD data, by which a value of 0.072 was obtained for x in Fe_1−xO. A mean crystallite size of 13±1 nm was calculated for the single-phase wüstite, using Scherrer's formula. The morphology of the powders was also checked by TEM. Variations of pressure and temperature in the vial were recorded with respect to the milling time, using a GTM unit. Hysteresis loops of the as-milled powders at 5 K and room temperature have been obtained by SQUID and by VSM systems, respectively. The loops show non-zero coercivity, in contrast to the bulk wüstite. The observed magnetizations can be explained by a model based on the spinel-type defect clusters in non-stoichiometry wüstite.     

High pressure Mössbauer spectroscopy using a diamond anvil cell

Recent applications of high pressure Mössbauer spectroscopy using a diamond anvil cell are presented. High pressure Mössbauer studies of two perovskite-related iron oxides SrFeO_2.97 and CaFeO₃, magnetite Fe₃O₄, and wüstite Fe_1– O have been carried out at 300 K at pressures of up to 74 GPa. A preliminary result by the resonant forward scattering of synchrotron radiation for high pressure Mössbauer spectroscopy using a diamond anvil cell is also presented.     

Mixed hyperfine interactions in Fe-Mg-O: magnetic behaviour

The complex Mössbauer spectra exhibited by Fe_xO (x0.91) and (Fe_1–y Mg _y )_xO (y=0.15–0.85) powder samples at liquid helium temperature have been analysed by a Hamiltonian treatment to allow for the significant electric field gradients present at the Fe²⁺ defect sites. The magnetic behaviour of the defect clusters are considered in terms of antiferromagnetic couplings, consistent with the spin glass-like behaviour reported recently for magnesiowüstite.     

Fluorination of perovskite-related phases of composition La1−xSrxFe1−yCoyO3−δ

We report here on the fluorination of the perovskite-related phases La_1−xSr_xFe_1−yCo_yO_3−δ. The introduction of fluorine in place of oxygen is achieved through a low-temperature (400 °C) reaction with poly(vinylidene fluoride). X-ray powder diffraction data show that in all cases the fluorination leads to an expansion in the unit cell, which is consistent with partial replacement of oxygen by fluorine and consequent reduction in the oxidation state of iron and/or cobalt. This reduction in oxidation state is confirmed by X-ray absorption- and Mössbauer-spectroscopy. The Mössbauer spectra show complex magnetically split hyperfine patterns for the fluorinated samples, reflecting the interactions between Fe³⁺ ions, which are not possible in oxides containing Fe⁴⁺.     

Magnetoresistance in point contacts of the Heusler alloy Co2Cr0.6Fe0.4Al

Following a recent report predicting half-metallicity of Co₂Cr_0.6Fe_0.4Al, we have examined point contacts of this material. Large magnetoresistances (up to 80%) have been observed at room temperature in small fields (10 mT). Magnetostriction in these fields is negligible. A spin polarisation of 81% is inferred. Mössbauer spectra show that 90% of the iron is ordered. The magnetisation of the alloy is 3.65μ_B per formula unit, and its Curie temperature is 665 K.     

Mössbauer spectroscopy as a probe of magnetic states in La0.5Ca0.5FeO3−δ perovskite

Charge disproportionation in La_0.5Ca_0.5FeO_3−δ perovskite has been detected by zero-field Mössbauer spectra from 20 K to room temperature. On the basis of the parameters of center shifts and hyperfine fields, Mössbauer spectra identified that the iron ionic states are Fe³⁺ and Fe⁵⁺ below 150 K, Fe³⁺, Fe⁴⁺ and Fe⁵⁺ in the intermediate temperature region, as well as Fe³⁺ and Fe⁴⁺ above 220 K. At low temperatures, the system exhibits a cluster-glass-like state resulting from competition between antiferromagnetic interaction of Fe³⁺–Fe³⁺ and ferromagnetic interaction of Fe³⁺–Fe⁵⁺.     

Temperature-dependent Fe Mössbauer spectroscopy and local structure of the mullite-type Bi2(FexGa1−x)4O9 (0.1≤x≤1) solid solution

The Bi₂(Fe_xGa_1−x)₄O₉ oxide solid solution possessing a mullite-type structure has been investigated by ⁵⁷Fe Mössbauer spectroscopy in dependence of composition (0.1≤x≤1) and temperature (293≤T/K≤1073). The spectra have been fitted with two doublets for tetrahedrally and octahedrally coordinated high-spin Fe³⁺ ions, respectively. The experimental areas of the subspectra were used to determine the distribution of iron on the two inequivalent structural sites. The fraction of iron cations occupying the octahedral site is found to increase with decreasing Fe content and the cation distribution is almost independent of temperature. The unusual temperature dependence of the quadrupolar splitting, QS, observed for the octahedral site with dQS/dT>0 is discussed in connexion with structural data for Bi₂Fe₄O₉. The temperature dependence of Mössbauer isomer shifts and signal intensities is examined in the context of local vibrational properties of iron on the two inequivalent sites of the mullite-type lattice structure.     

Structure and superconductivity in FexCu1−xBa2YCu2O7+y superconductors synthesized by high pressure

Comprehensive studies of X-ray diffraction, oxygen content, superconductivity and Mössbauer effect have been made on Fe_xCu_1−xBa₂YCu₂O_7+y superconductors (0.00≤x≤0.70) synthesized by ambient (AM) and high pressure (HP). Results indicate that all the HP-samples have tetragonal structure, smaller lattice parameter c and unit-cell volume than the AM-samples. The studies of oxygen content, and Mössbauer spectroscopy indicate that the HP-samples have higher oxygen content, carrier concentration and average valence of Fe than the AM-samples. Moreover, for the HP-samples more Fe atoms located in CuO_x chains have fivefold-oxygen coordination. These are important reasons for the enhancement of T_c in the HP-samples.     

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.     

Critical behaviour and magnetic properties of A-B spinel ZnxCu1−xFe2O4

Polycrystalline Zn_0.6Cu_0.4Fe₂O₄ ferrites have been prepared using a solid-state reaction technique. Their structural and magnetic properties have been studied, using X-ray diffraction and Mössbauer and magnetic measurements. These results have been compared to a more general theoretical study, on Zn_xCu_1−xFe₂O₄, based on mean field theory and high-temperature series expansions (HTSE), and extrapolated with the Padé approximant method. The nearest neighbour super-exchange interactions for the intra-site and the inter-site of Zn_xCu_1−xFe₂O₄ spinel ferrites, in the range 0≤x≤1, have been computed using the probability approach, based on Mössbauer data. The Curie temperature T_C is calculated as a function of Zn concentration. The theoretical results obtained are in good agreement with the experimental results obtained by magnetic measurements.     

Surface investigation of excimer laser irradiated phosphatized steel plates

Steel plates (St 14-05) of 1.5 mm thickness and coated with 1.5 m of ironzinc-phosphatehydrate (ASTM 29-1429) were irradiated with an XeCl-excimer laser (Siemens XP 2020) at energy densities of 20–80 mJ/mm² and with 2–32 pulses per spot. Depth-sensitive Mössbauer spectroscopy was carried out by means of conversion electron (CEMS) and conversion X-ray (CXMS) Mössbauer spectroscopy in order to determine the phases produced by the excimer laser treatment. Although the phosphate layer is mainly ablated during the laser treatment, there is a significant formation of Fe₂P. The phosphorous phase and the wüstite, with changing stoichiometries, were found in the very surface (CEMS). In deeper layers and in correlation with the energy density and the number of pulses, austenite was found in surprisingly high amounts (CEMS and CXMS). The austenite was found to be nitrogen austenite. The high Fe-N austenite content as well as the presence of some ferromagnetic Fe-N phase (-Fe_2+xN) must be ascribed to an unexpectedly high nitriding effect during the laser treatment.     

Relationship between structural and magnetic properties in (Ti,Fe)O2 powders obtained by mechanical milling

Fe-doped TiO₂ samples with different Fe content were prepared by mechanical alloying starting from TiO₂ rutile and FeO. The samples were structurally and magnetically characterized by XRD, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), AC-susceptibility and magnetization measurements. XAS results showed that Fe ions were incorporated into the rutile phase with oxygen coordination that was lower than that expected in this phase. The oxygen coordination number decreased with the increase of Fe²⁺ ions such as it was previously found in the milled samples of TiO₂ doped with hematite. The RT Mössbauer spectra were reproduced using two paramagnetic interactions, one corresponding to Fe²⁺ (δ∼0.87 mm/s) and the other to Fe³⁺ (δ∼0.31 mm/s). Magnetometry measurements showed the presence of paramagnetic and ferromagnetic-like interactions at room temperature. Although saturation and coercivity of the ferromagnetic phase increased with iron, the effective magnetic moment per iron atom decreased, probably due to the precipitation of Fe rich antiferromagnetic structures.     

Concerning the cation distribution in MnFe2O4 synthesized through the thermal decomposition of oxalates

A single phase manganese ferrite powder have been synthesized through the thermal decomposition reaction of MnC₂O₄·2H₂O-FeC₂O₄·2H₂O (1:2 mole ratio) mixture in air. DTA-TG, XRD, Mössbauer spectroscopy, FT-IR and SEM techniques were used to investigate the effect of calcination temperature on the mixture. Firing of the mixture in the range 300-500 °C produce ultra-fine particles of α-Fe₂O₃ having paramagnetic properties. XRD, Mössbauer spectroscopy as well as SEM experiments showed the progressive increase in the particle size of α-Fe₂O₃ up to 500 °C. DTA study reveals an exothermic phase transition at 550 °C attributed to the formation of a Fe₂O₃-Mn₂O₃ solid solution which persists to appear up to 1000 °C. At 1100 °C, the single phase MnFe₂O₄ with a cubic structure predominated. The Mössbauer effect spectrum of the produced ferrite exhibits normal Zeeman split sextets due to Fe³⁺ions at tetrahedral (A) and octahedral (B) sites. The obtained cation distribution from Mössbauer spectroscopy is (Fe_0.92Mn_0.08)[Fe_1.08Mn_0.92]O₄.     

57Fe Mössbauer spectroscopy on disordered crystalline media with Ca-gallogermanate type structure. I. In the paramagnetic range

Polycrystalline strontium iron germanates of the type Sr_3–y Ln _y Fe_2+y Ge_4–y O₁₄(Ln=La, Nd;y=0, 1) were investigated by⁵⁷Fe Mössbauer spectroscopy in the temperature range 4.2–300 K. The crystal chemistry and the distribution of Fe³⁺ ions in the structure, as well as the crystallographic inequivalence of the oxygen polyhedra occupied by iron, were studied over the whole paramagnetic temperature region. A correlation of the experimental data with a local environment computation is given.     

Magnetic properties of nanocrystalline Ni0.7Mn0.3Gd0.1Fe1.9O4 ferrite at low temperatures

Mössbauer spectra and magnetic measurement of Ni_0.7Mn_0.3Gd_0.1Fe_1.9O₄ ferrite were investigated by Oxford MS-500 Mössbauer spectrometer and superconducting quantum interference device (SQUID) magnetometer with a field 5 T. Ni_0.7Mn_0.3Gd_0.1Fe_1.9O₄ nanoparticles have a considerable coercivity of 1040 Oe when the test temperature is reduced to 2 K. Mössbauer spectra show that Ni_0.7Mn_0.3Gd_0.1Fe_1.9O₄ nanoparticles exhibit superparamagnetism at room temperature and ferrimagnetism at 77 K.     

Effects of annealing temperature on structure and magnetic properties of CoAl0.2Fe1.8O4/SiO2 nanocomposites

CoAl_0.2Fe_1.8O₄/SiO₂ nanocomposites were prepared by sol–gel method. The effects of annealing temperature on the structure and magnetic properties of the samples were studied by X-ray diffraction, transmission electron microscopy, vibrating sample magnetometer and Mössbauer spectroscopy. The results show that the CoAl_0.2Fe_1.8O₄ in the samples exhibits a spinel structure after being annealed. As annealing temperature increases from 800 to 1200 °C, the average grain size of CoAl_0.2Fe_1.8O₄ in the nanocomposites increases from 5 to 41 nm while the lattice constant decreases from 0.8397 to 0.8391 nm, the saturation magnetization increases from 21.96 to 41.53 emu/g. Coercivity reaches a maximum of 1082 Oe for the sample annealed at 1100 °C, and thereafter decreases with further increasing annealing temperature. Mössbauer spectra show that the isomer shift decreases, hyperfine field increases and the samples transfer from mixed state of superparamagnetic and magnetic order to the completely magnetic order with annealing temperature increasing from 800 to 1200 °C.     

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 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.     

A Mössbauer study of octahedral site symmetries in systems Co x Mn3−x−y Fe y O4 and Ni x Mn3−x−y Fe y O4

A Mössbauer study of cation distribution in systems Co _x Mn_3?x?y Fe _y O₄ and Ni _x Mn_3?x?y Fe _y O₄ has been made. It has been found that in both systems all specimens withy<0.6 value exhibit quadrupole doublets corresponding to site symmetries Fe³⁺(I) and Fe³⁺(II) of octahedral site. As more and more cobalt or nickel is introduced into the matrix the intensity of the inner quadrupole doublet increases while on introducing iron that of the outer quadrupole doublet increases. After a certain concentration of iron the inner doublet starts becoming more intense. It is suggested that this arises possibly from the substitution of cations in the second co-ordination sphere of Fe³⁺(I) and Fe³⁺(II) sites. Fory>0.6 the Mössbauer spectra show relaxation effects.