L'etude cristallographique et par effet mössbauer des solutions solides V2O5Fe2O3

Using the Mössbauer effect, we analyse the behaviour of (V₂O₅)_1?x(Fe₂O₃)_x solid solutions with the starting composition x = 1?15 mol.% Fe₂O₃. The number of iron ions dissolved in V₂O₅ lattice depends on the initial composition x of Fe₂O₃ and tends to a maximum value corresponding to 4 mol.% Fe₂O₃. The composition dependence of the quadrupole splitting and isomer shifts is presented.     

The coordination of Co2+ions in Co substituted magnetites,Fe3−xCoxO4, with x⩽0.04

⁵⁷Fe Mössbauer spectra at room temperature, both with and without external magnetic field, indicate that Co²⁺ ions in Co_xFe_3?xO₄spinels (x?0.04) are situated on the octahedral B sites. The Mössbauer parameters are listed and the existence of unpaired Fe³⁺ ions is evidenced.     

Investigations of crystal and magnetic properties of the Mn5−xFexGe3 intermetallic compounds

The Mn_5?xFe_xGe₃ intermetallic compounds are investigated with X-ray, neutron diffraction, magnetometric and Mössbauer effect methods. It is found that crystal structure of x = 1 compound is of D8₈ type while the structure of x = 3, 4 and 5 compounds is of B8₂ type. All are ferromagnets with collinearly ordered atomic spins. The lattice constants are derived from X-ray diffraction patterns, while magnetometric measurements yield the Curie temperatures and Weiss constants as well as the values of magnetic moments per molecule in ferromagnetic and paramagnetics states. The distributions of Fe and Mn atoms among two non-equivalent crystal sites are determined with the neutron diffraction method and are confirmed by the Mössbauer effect measurements. The parameters of hyperfine interactions are derived from Mössbauer absorption spectra and are attributed to iron atoms in two non-equivalent crystal sites.     

Spin rotations in HoxEr1−xFe2 cubic laves compounds

The temperature dependence of the elastic moduli and the Mössbauer effect in Ho_x,Er_1?x, Fe₂ cubic Laves compounds (x, between 0.3 and 0.9) has been investigated in the temperature region where spin rotation occurs. The composition-dependence minima in the elastic moduli, and the Mössbauer effect measurements, were used to determine the boundaries between the various directions of easy magnetization in these compounds. The experimental spin orientation diagram was found to deviate from the predictions of a one-ion model based on the rare-earth ions alone. From the Mössbauer effect measurement it was deduced that in compounds for which a spin reorientation was observed, the spin rotates continuously with temperature between the major axes of the cubic symmetry. This was attributed to the contribution of higher-order magnetocrystalline anisotropy constants. The ΔE effect, measured in external magnetic fields up to 25 kOe, was found to be constant, and relatively small, in the holmium composition range of x = 0.45–1.00 in the Ho_xEr_1?xFe₂; compounds.     

Observation by mössbauer spectroscopy of electron hoppings in the spinel series Zn1-xGexFe2O4

The Mössbauer spectra of the spinel series Zn_1-xGe_xFe₂O₄ with x = 0.25, 0.5 and 0.75 are observed between 77 and 623 K. In the detection limit of the Mössbauer spectrometry, the ferrous and ferric ions are all found on the B sites and the broadening of the spectra between the Curie point and 623 K is correlated with an electron hopping process via a conduction band. This process favors a “double exchange” which can explain the magnetic order in the compounds with x = 0.25 and x = 0.5 below 200 and 250 K.     

Synthesis and laser patterning of Bi-doped Y3Fe5O12 crystals in germanosilicate glasses

New germanosilicate glasses giving the crystallization of yttrium iron garnet Y₃Fe₅O₁₂ (YIG) and Bi-doped YIG, 23Na₂O-xBi₂O₃-(12−x)Y₂O₃-25Fe₂O₃-20SiO₂-20GeO₂ (mol%), are developed, and the laser-induced crystallization technique is applied to the glasses to pattern YIG and Bi-doped YIG crystals on the glass surface. It is clarified from the Mössbauer effect measurements that iron ions in the glasses are present mainly as Fe³⁺. It is suggested from the X-ray diffraction analyses and magnetization measurements that Si⁴⁺ ions are incorporated into YIG crystals formed in the crystallization of glasses. The irradiations (laser power: 32-60 mW and laser scanning speed: 7 μm/s) of continuous wave Yb:YVO₄ fiber laser (wavelength: 1080 nm) are found to induce YIG and Bi-doped YIG crystals, indicating that Fe³⁺ ions in the glasses act as suitable transition metal ions for the laser-induced crystallization. It is suggested that YIG and Bi-doped YIG crystals in the laser irradiated part might orient. The present study will be a first step for the patterning of magnetic crystals containing iron ions in glasses.     

Cation distribution in the spinels CoxFe3−xO4

Mössbauer spectra of four spinels having the general formulae Co_xFe_3?xO₄ and x ~ 1.0, 1.5, 2.0 and 2.5 have been obtained at liquid helium temperature and in a large transverse magnetic field. Intensity data have been used to determine the distribution of iron ions between octahedral and tetrahedral sites. The results are examined on the basis of two models. For one there is a competition between the Fe³⁺ ions and the cobalt ions for the two sites; while for the other there is a competition between Fe³⁺ ions and Co²⁺ ions for the two sites. The relative merits of these two extreme models are discussed.     

Mössbauer and magnetization studies of the U1−xNpxO2 fluorites

²³⁷Np Mössbauer effect and magnetic susceptibility measurements of the U_1?Np_xO₂ fluorite solid solution have been performed in the composition range 0.15 ? x ? 0.75. For x = 0.15 and 0.25, the Np ions order magnetically at a lower temperature T₀ than the bulk material (T_N) (T₀ ～ 19 K, T_N ～ 27 K for x = 0.15). For x = 0.50, T₀ ～ 10 K (T_N ～ 12 K from recent neutron diffraction measurements). For x = 0.75, T₀ ～ T_N ～ 9 K. The Np (induced) ordered moment is ～ 0.5 μ_B. The ²³⁷Np Mössbauer isomer shift shows that the Np ions are in a IV charge state.     

Magnetic properties and spin order of Sr7Fe10O22

The magnetic properties of Sr₇Fe₁₀O₂₂ have been investigated by means of magnetic susceptibility and Mössbauer absorption measurements. This compound proved to be antiferromagnetic with a Néel temperature T_N = 425 K; the magnetic susceptibility is constant from the lowest measuring temperature (78 K) up to T_N.The Mössbauer measurements and the analogies with “brownmillerite” type compounds indicate that iron ions occupy one octahedral and two tetrahedral different sites. An antiferromagnetic spin configuration with moments lying in the ab plane appears to be consistent with the experimental results. A small spontaneous magnetic moment was observed at room temperature with features resembling those of strontium hexaferrite; a weak ferromagnetic behavior can not however be excluded taking into account the aforementioned susceptibility behaviour.     

Mössbauer, X-ray, electrical and magnetic properties of lithium borosilicate glasses containing iron and manganese Part I. Mössbauer measurements

The effect of the replacement of MnO₂ by Fe₂O₃ on the oxidation states of iron in some lithium borosilicate glasses were studied using Mössbauer spectroscopy. DTA and infrared measurements showed the presence of two glassy phases, one of them containing iron and the other manganese. The Mössbauer spectra were measured at room temperature for all the glass samples. The spectra revealed the presence of Fe ions only in ferric state in both tetrahedral and octahedral coordination. Also, it was observed that the ratio between the number of iron ions in both coordination states has not changed with the increase of MnO₂ content.     

Magnetic interactions between Fe(III) ions in the solid solutions CuM1 − xFexS2 (M = Al,Ga, In) and AgM1 − xFexO2 (M = Al,Ga).

Magnetic properties of CuM_{1 ? x}Fe_xS₂ (M = Al, Ga, In) and β-AgM_{1 ? x}, Fe_xO₂ (M = Al, Ga) solid solutions have been studied by Mössbauer spectroscopy (only on CuGa _{1 ? x}Fe_xS₂), magnetization measurements and EPR spectroscopy.In the structures studied all ions have tetrahedral co-ordination.The magnetic interactions between Fe(III) ions are shown to be very strong for nn sites ($\text{J}\text{k}$～100 K). More distant exchange interactions are found to fall off rather slowly as the distance between Fe(III) ions increases and are suggested to depend essentially on the number of bonds traversed.     

Mössbauer spectroscopy on57Fe in highT c superconductor Bi2Sr2Ca1Cu2O y

Mössbauer measurements were performed on polycrystalline⁵⁷Fe: Bi₂Sr₂Ca₁Cu₂O _y , super-conductor in the temperature range of 77–296 K. The samples were obtained in a solid phase synthesis using 0.01, 0.03, 0.1 and 0.5 mol fractions of α-Fe₂O₃ (96% enriched in⁵⁷Fe). A prevailing quadrupole doublet practically independent of temperature and iron concentration characterizes the obtained Mössbauer spectra. The corresponding hyperfine parameters suggest the presence of high spin Fe¹¹¹ ions in a strongly distorted octahedral symmetry which indicates a probable copper substitution by iron in the system.     

Mössbauer and magnetic study of Mn2+- and Cr3+-substituted spinel magnesioferrites of the composition Mg1−xMnxFe2−2xCr2xO4

Chromium and manganese co-substituted spinel magnesioferrites of the composition Mg_1?x Mn _x Fe_2?2x Cr_2x O₄ (x?=?0.0, 0.1, 0.2, 0.3, and 0.5) were investigated with X-ray diffraction (XRD), Mössbauer spectroscopy and magnetic measurements. The cation distribution inferred suggests that Mn²⁺ and Cr³⁺ ions dominantly occupy the A- and B-sites respectively. The gradual decrease of the hyperfine fields and Curie temperatures with increasing x reflects a gradual weakening in the AB exchange interaction. Mössbauer data of the sample with x = 0.5 is suggestive of cation clustering and/or superparamagnetism. The magnetization data is suggestive of Yafet-Kittel-type canted magnetism.     

Magnetic properties of the mixed spinel Mg1+xMnxFe2-2xO4

The structural and magnetic properties of the mixed spinel Mg_1+xMn_xFe_2-2xO₄ system for 0.1<= x <= 0.9 have been studied by means of X-ray diffraction, magnetization, a.c. susceptibility and Mössbauer spectroscopy measurements. X-ray intensity calculations indicate that Mn⁴⁺ ions occupy only octahedral (B) sites replacing Fe³⁺ ions and the added Mg²⁺ ions substitute for A-site Fe³⁺ ions. All samples are magnetic at 12 K displaying Mössbauer spectra that have magnetic sextets coexisting with a central doublet that increases in population with increasing Mn concentration, indicating the presence of short range ordering (clustering). The Mössbauer intensity data show that Mn possesses a preference for the B-site of the spinel over the whole range of concentration. As expected, the hyperfine field and Curie temperature determined from a.c.susceptibility data decrease with increasing Mn content. Magnetization results indicate that on increasing dilution x, the collinear ferrimagnetic phase breaks down at x = 0.3 before reaching the ferrimagnetic percolation limit (x=0.6), as a result of the presence of competing exchange interactions, which is well supported by Mössbauer results. From all the above results, it is proposed that with increasing Mn content from x=0.6 to 0.9, the frustration and disorder increase in the system suppressing the ferrimagnetic ordering, and the system approaches to a cluster spin glass type of ordering at x=0.8 as reflected in the a.c.susceptibility and Mössbauer spectrum.     

Mössbauer effect on YFe3 compound

The thermal variation of the Mössbauer parameters of the YFe₃ compound between 78 K and T_c is studied. The results agrees well with the magnetic measurements. For the iron site 18 (h) the presence of an anisotropic interaction splits the Mössbauer spectrum into two six-lines patterns with the intensities in 2:1 ratio but above 400 K the intensities of the Mössbauer spectra of the sublattices are in 1 : 2: 6 ratio in agreement with crystallographic data.     

Investigations of Dy(FexAl1−x)2 laves phases by x-ray,magnetometric and Mössbauer effect methods

The crystal and magnetic properties of the Dy(Fe_xAl_1-x)₂ (0≤x≤1.0) system are investigated with the X-ray, magnetometric and Mössbauer effect methods. The system constitutes two cubic C15 structure regions separated by hexagonal C14 structure region. The X-ray investigations indicate the structure disorder of the C15 type phases. All compounds of the investigated system are ferrimagnets. Some of them exhibit a pronounced magnetic anisotropy. Substitution of Al for Fe decreases the Curie temperature and the Fe hyperfine magnetic field. The distribution of hyperfine magnetic field at iron sites is correlated with their nearest neighbours configurations. The Mössbauer effect data indicate the existence of the appreciable amount of the covalent apart from the long-range metallic bond in the investigated phases.     

X-Ray Diffraction and Mössbauer Studies of the Structural Features of BiFe<Subscript>1 ‒ <Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> Multiferroics

The structure of ceramic BiFe_1?xZn_xO₃ multiferroic samples is investigated using the X-ray diffraction method and Mössbauer spectroscopy. X-ray diffraction analysis of the samples indicates the existence of the Bi₁₂(Bi_0.5Fe_0.5)O_19.5 impurity phase. High-temperature heating of the samples generates additional phases. The parameters of the Mössbauer spectra depend on the zinc concentration. In this case, for pure bismuth ferrite, the spectrum is a superposition between two Zeeman sextets and two paramagnetic doublets arising from two nonequivalent magnetic and electrical positions occupied by iron ions at the crystallattice sites of a sample. The replacement of iron ions with zinc ions substantially affects the spectrum parameters. This is probably related to changes in the spin-cycloid structure typical of multiferroics, the destruction of which stimulates the appearance of significant magnetoelectric interactions.     

57Fe and 151Eu Mössbauer studies of magnetoresistive Europium based cobalt perovskites

Eu_0.8Sr_0.2Fe _x Co_1?x O_3?z CMR perovskites with different iron concentrations (x?=?0, 0.025, 0.075, 0.15, 0.3) were investigated by X-ray diffraction, AC magnetic susceptibility, magnetotransport, as well as ⁵⁷Fe and ¹⁵¹Eu Mössbauer spectrometry. The valence state of europium ions was found to be trivalent, independently of the iron concentration. ⁵⁷Fe Mössbauer spectra and magnetic susceptibility of the investigated perovskites presented complementary results for the magnetic transitions.     

Mössbauer study of the spinel system GexCu1−xFe2O4

The magnetic properties of the spinel series Ge_xCu_1?xFe₂O₄ (X = 0 to 0.8) have been investigated by means of Mössbauer spectroscopy. Mössbauer 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 = 0.8 it shows the superposition of hyperfine field split spectra from A- and B-site ions and a broad central line spectrum. For 0.2 ? X ? 0.4, fast electron exchange among octahedral iron ions occurs as in Fe₃O₄. The variations of nuclear magnetic fields at the A- and B-sites are explained on the basis of AB and BB supertransferred hyperfine interactions.