57Fe Mössbauer study of Li x Fe1-y Co y PO4 (y = 0, 0.1, 0.2) as cathode material for Li-ion batteries

Lithium iron phosphates LiFe_1-y Co _y PO₄ (y = 0, 0.1, 0.2) exposed to a charging process were studied by ⁵⁷Fe Mössbauer spectroscopy taking into account XRD and SEM data. Hyperfine parameters of the spectra were determined above and below the magnetic ordering temperature for all the samples. It was shown that the presence of Co impurity atoms in lithium phosphates gives no effect on the hyperfine interaction of ⁵⁷Fe²⁺ cations. However, Co atoms in the nearest cation environment of Fe atoms lead to a significant change of the hyperfine interactions of ⁵⁷Fe³⁺ cations. The Co impurity atoms distribution over the positions of the iron atoms in the structure is found not to be statistical,but correlated.     

Hyperfine interactions in Sc<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript>x</Subscript>Fe<Subscript>2</Subscript> cubic Laves alloys

Effects of hybridization of 3d bands of iron with 3d bands of scandium and 4d bands of yttrium in Sc_1?xY_xFe₂ cubic Laves alloys (0≤_x≤1) are studied by the nuclear magnetic resonance method. The concentration dependences of the lattice parameters a, saturation magnetization σ, and hyperfine fields at the ⁵⁷Fe, ⁴⁵Sc, and ⁸⁹Y nuclei—as well as the ²⁷Al impurity nuclei, whose atoms substitute iron atoms in the lattices of these alloys—are measured. The “local” and “induced” contributions to hyperfine fields at the ⁵⁷Fe nuclei are separated and the magnetic moments at iron atoms are estimated. It is found that the hybridization effect leads to the formation of magnetic moments at Sc and Y atoms (whose direction is opposite to the direction of the magnetic moment at iron atoms) and is responsible for the ferrimagnetic structure in Sc_1?xY_xFe₂ alloys.     

Mößbauereffekt anFe 57 nach Neutroneneinfang in Fe56

Mößbauer effect measurements with the 14.4 keV gamma rays of Fe⁵⁷ following thermal neutron capture in Fe⁵⁶ are reported. During the transition from the capture level at 7.6 MeV to the first excited state at 14.4 keV recoil energies up to 549 eV are imparted to the Fe⁵⁷ nuclei. Thus the Mößbauer gamma rays are emitted by nuclei displaced from their normal lattice positions. The measurements have been performed in order to get informations about the final position of the recoiled nuclei in metallic iron and in ordered Fe-Al alloys. Mößbauer spectra of recoil atoms in metallic iron did not show any significant deviation from the spectra of atoms on normal lattice positions. In ordered FeAl alloys of CsCl structure changes in the isomer shift due to recoil effects have been found. In a Fe₃Al alloy of DO₃ type order additional changes in the internal magnetic field have been observed. All results are discussed in terms of possible final positions for the primary recoiled iron atoms in the lattice.     

Co-silicide layers studied by Mössbauer spectroscopy and Rutherford backscattering spectroscopy

Co-silicides were prepared with several techniques, such as annealing of evaporated Co-layers on a Si-substrate (silicide surface layers) and annealing of Co-implanted Si (buried silicide layers). By adding some⁵⁷Co to the stable⁵⁹Co, the formation of the various Co-silicides could clearly be followed as a function of annealing temperature by means of Mössbauer spectroscopy. In the case of surface silicide layers, Co₂Si, CoSi and CoSi₂ were formed subsequently. In the case of buried layers however, CoSi₂ was the only crystalline phase that could be observed. In both cases, the CoSi₂ spectra showed an anomalous side resonance. Moreover, it was found that when⁵⁷Fe was implanted (instead of⁵⁷Co), a drastic increase in the intensity of this side resonance could be detected by CEMS.     

Magnetic interaction in Tm3Fe5O12 studied by means of169Tm and57Fe Mössbauer spectroscopy

The temperature dependence of the hyperfine parameters of thulium iron garnet (Tm₃Fe₅O₁₂) powder was studied from 90 to 550 K using¹⁶⁹Tm and⁵⁷Fe Mössbauer spectroscopy (MB). The spectra were analyzed by least mean square fits to the transmission function. The temperature dependence of the magnetic fields of the thulium nuclei is well described by the mean field model. The coupling constants between the magnetic lattice occupied by the thulium atoms and the magnetic lattices occupied by the iron atoms were derived.     

Mössbauer studies of57Fe atoms isolated in CH4 and CO2 matrices

The Mössbauer absorption spectra of matrix isolated⁵⁷Fe atoms have been measured in the inert matrices CH₄ and CO₂ with matrix temperatures between ～3.3 and ～46 K. The isomer shift of the observed resonances is (?0.79±0.02) mm/s and (?0.76±0.05) mm/s with respect to iron metal at 300 K for⁵⁷Fe in CH₄ and for CO₂ respectively. This is within the experimental errors the same isomer shift as that of rare-gas matrix isolated⁵⁷Fe atoms. All spectra show quadrupole doublets due to the noncubic point symmetry of the lattice site occupied by the⁵⁷Fe atoms. The effective Debye temperatures as obtained from the temperature dependence of the resonance absorption areas are (46±4) K for the CH₄ matrix and (121±6) K for the CO₂ matrix annealed at ～20 K.     

57Fe Mössbauer study of Eu1−x Sr x FeO3−y

The samples of Eu_1–x Sr _x FeO_3–y (x=0.0–1.0) were prepared by the solid state reaction method. Their X-ray diffraction patterns and⁵⁷Fe Mössbauer spectra at room temperature were measured. It is found that Sr ions incorporate in the lattice of EuFeO₃, the change of crystal structure is related to the dopant.⁵⁷Fe Mössbauer spectra consist of one magnetic, one doublet and one single paramagnetic components. The Fe ions in the cubic phase are in intermediate valence state between Fe(III) and Fe(IV) and may participate in electron hopping.     

Mössbauer effect studies of Tb<Subscript>0.27</Subscript>Dy<Subscript>0.73</Subscript>(Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)2 intermetallics at 295 K

The synthesis of materials and the studies of crystal structure and ⁵⁷Fe Mössbauer effect were performed for Tb_0.27Dy_0.73(Fe_1?x Co _x )₂ intermetallics. Terfenol-D (Tb_0.27Dy_0.73Fe₂) is the starting compound of this Fe/Co-substituted series. X-ray measurements showed evidence of a pure cubic Laves phase C15, MgCu₂-type, and unit cell parameters were determined across the series. A Co substitution introduced local area, at sub-nanoscale, with random Fe/Co neighbourhoods of the ⁵⁷Fe atoms.Mössbauer effect spectra for the Tb_0.27Dy_0.73(Fe_1?x Co _x )₂ series at room temperature are composed of a number of locally originated subspectra due to the random distribution of Fe and Co atoms in the transition metal sublattice, and due to [1 1 1] an easy axis of magnetization. Isomer shift, magnetic hyperfine field and quadrupole interaction parameter were obtained from the spectra, both for the local area and for the bulk sample.As a result of Fe/Co substitution, a Slater-Pauling-type curve for the average magnetic hyperfine field vs. Co content was observed. It was found that the magnetic hyperfine fields corresponding to the local area also create a dependence of the Slater-Pauling-type vs. Co contribution in the Fe/Co neighbourhoods.     

57Fe Mössbauer study of SrFeO3 under ultra-high pressure

⁵⁷Fe Mössbauer absorption spectra under ultra-high pressure up to 53 GPa have been measured using a diamond anvil cell for SrFeO_2.97 which is one of the typical Fe⁴⁺ oxides having a cubic perovskite structure. External high pressure up to 53 GPa makes no indication of structural transformation and does not show any change in valence state of iron, however the Néel temperature of 131 K at 0 GP increases to 300 K and the⁵⁷Fe magnetic hyperfine field decreases from 32.9 T at 0 GPa and 6.5 K to 23.3 T at 53 GPa and 300 K.     

57Fe and57Co Mössbauer studies of highT c Y-Ba-Cu oxides

The⁵⁷Co emission Mössbauer spectra from YBa₂Cu₃O_6.92 (1-2-307) and YBa₂Cu₃O_6.00 (1-2-306) have been measured and compared with the⁵⁷Fe absorption spectra from YBa₂Cu_2.95Fe_0.05O_7?δ in order to clarify decisively the site assignments for the⁵⁷Fe quadrupole-split doublets in these compounds. Mössbauer spectra obtained from both specimens consist of four components whose hyperfine interaction parameters well agree with each other. It is shown that the Co and Fe atoms mainly substitute at Cu1 chain sites in 1-2-307, but in 1-2-306 the Co atoms occupy randomly the Cu2 plane sites and indicate magnetically-split sextet which converts to a paramagnetic doublet of S-state Fe³⁺ in 1-2-307 by a post-annealing in O₂ gas.     

Mössbauer and vibrational DOS studies of diluted magnetic tin oxides and nano iron oxides

The magnetic properties and Mössbauer results for SnO₂ doped with ⁵⁷Fe are reviewed, and the values of isomer shift and quadrupole splitting are compared with the results obtained by ab initio calculations. It is concluded that the exchange interactions between oxygen defects and magnetic atoms are responsible for long range magnetic interactions of dilute Fe ions dispersed in SnO₂. Fe atom precipitated clusters may be formed in highly Fe doped SnO₂ samples by annealing at relatively high temperatures for several hours. The reduction of the particle size to nano-scale dimensions induces magnetization, which can be associated with oxygen defects. We have measured the nuclear inelastic scattering (NIS) spectra of Fe oxides, and ⁵⁷Fe and (Co or Mn) doped SnO₂ synthesized mainly by sol–gel methods and we have derived the vibration density of states (VDOS). The local phonons are sensitive to the presence of precipitated clusters.     

Investigations of crystal and magnetic properties of Dy-Fe intermetallic compounds

The crystal and magnetic properties of Dy₂Fe₁₇, Dy₆Fe₂₃, DyFe₃ and DyFe₂ intermetallic compounds are investigated with X-ray, magnetometric, ⁵⁷Fe and ¹⁶¹Dy Mössbauer effect methods. The X-ray analysis shows that investigated compounds are single phases with Th₂Ni₁₇, Th₆Mn₂₃, PuNi₃ and NgCu₂ type crystal structures, respectively. The magnetometric measurements prove their ferrimagnetic behaviour, localization of Fe magnetic moments and long range Fe-Fe exchange magnetic interactions. The crystal field effects induce magnetic anisotropy which results in local magnetic symmetry or iron atoms lower than the crystal one. This is observed by the Mössbauer effect method. The values of ¹⁶¹Dy hyperfine magnetic fields measured for investigated compounds exceed that found in metallic dysprosium due to polarization of conduction electrons by 3d-electrons of iron atoms. The weighted average value of ⁵⁷Fe hyperfine magnetic field decreases with the increase of Dy content in the compounds.     

Mössbauer study of cobalt and iron in the cyanobacterium (blue green alga)

Mössbauer emission and absorption studies have been performed on cobalt and iron in the cyanobacterium (blue-green alga). The Mössbauer spectrum of the cyanobacterium cultivated with⁵⁷Co is decomposed into two doublets. The parameters of the major doublet are in good agreement with those of cyanocobalamin (vitamin B₁₂) labeled with⁵⁷Co. The other minor doublet has parameters close to those of Fe(II) coordinated with six nitrogen atoms. These suggest that cobalt is used for the biosynthesis of vitamin B₁₂ or its analogs in the cyanobacterium. The spectra of the cyanobacterium grown with⁵⁷Fe show that iron is in the high-spin trivalent state and possibly in the form of ferritin, iron storage protein.     

Vibrations and chemical states of iron ions in soda‐lime glasses determined by element‐specific X‐ray analyses

We systematically study medium‐range structures including more than three neighboring atoms around iron ions (Fe²⁺ and Fe³⁺) in soda‐lime glass samples with low iron oxide concentrations (M_Fe2O3) and a wide number ratio of Fe²⁺ to all iron ions (Fe²⁺/Σ_nFe). The precise medium‐range structures around iron ions in glass have not yet been revealed because of a lack of the appropriate measurement methods. To avoid this problem, we used element‐specific nuclear resonant inelastic scattering (NRIS) with synchrotron X‐rays to observe the vibrations of iron ions (⁵⁷Fe). The vibrations are related to medium‐range structures with more than three neighboring atoms and to the potential asymmetry and the coordination environment, around iron ions. The NRIS method has high sensitivity and can measure over a wide concentration range. Linear combination fitting of the X‐ray absorption fine structure spectra, which measures only the first neighbors but is a faster than using the NRIS method, was also used additionally. A systematically produced set of glasses with 0.015–5 wt% M_Fe2O3 and 0–0.85 Fe²⁺/Σ_nFe was measured with these methods. It was found that the soda‐lime glass possessed two different medium‐range structures with different iron ion valences (~2+ or ~3+), which were determined by the Fe²⁺/Σ_nFe, and that these structures were generated during production of the glass. Moreover, these medium‐range structures were the same from 0.015 to 5 wt% M_Fe2O3.     

The charge states of iron in insulators implanted with57Co and57Fe

Single crystals of α-Al₂O₃ and LiNbO₃ were implanted with⁵⁷Co (dose: up to 2×10¹⁵ atoms/cm²) and with⁵⁷Fe (dose: 2×10¹⁵ atoms/cm²) ions. The Mössbauer spectra revealed the disordered atomic environment. Fe²⁺ and Fe³⁺ charge states were observed. The spectra were compared to the spectra of crystals doped with⁵⁷Co. It was remarkable that in the doped α-Al₂O₃ Fe³⁺ states with slow spin-spin relaxation have appeared. The CEMS study of the samples implanted with⁵⁷Fe resulted in Fe²⁺ ionic states indicating that a fraction of Co atoms can also be in Co²⁺ state.     

Atomic and magnetic structures of Fe<Subscript>70</Subscript>Al<Subscript>5</Subscript>B<Subscript>25</Subscript> amorphous alloys

The short-range order around boron, aluminum, and iron atoms in Fe₇₅B₂₅ and Fe₇₀Al₅B₂₅ amorphous alloys has been studied by ¹¹B and ²⁷Al nuclear magnetic resonance at 4.2 K and ⁵⁷Fe Mössbauer spectroscopy at 87 and 295 K. The average magnetic moment of iron atoms μ(Fe) in these alloys has been measured by a vibrating sample magnetometer. It has been revealed that the substitution of aluminum atoms for iron atoms does not disturb μ(Fe) in the Fe₇₀Al₅B₂₅ alloy, gives rise to an additional contribution to the ¹¹B NMR spectrum in the low-frequency range, and shifts maxima of the distribution of hyperfine fields at the ⁵⁷Fe nuclei. In the Fe₇₀Al₅B₂₅ amorphous alloy, the aluminum atoms substitute for iron atoms in the nearest coordination shells of boron and iron atoms. This alloy consists of nanoclusters in which boron and iron atoms have a short-range order of the tetragonal Fe₃B phase type.     

Spin-transition in nearly cubic site in [FeII(L)3][PF6]2

The spin-transition (¹A₁?⁵T₂) behaviour of a new mononuclear iron(II) compound [Fe^II(L)₃][PF₆]₂[L = 2-[3-(2′-pyridyl)pyrazole-1-ylmethyl]pyridine] has been investigated by ⁵⁷Fe Mössbauer spectroscopy. Analysis of the Mössbauer spectra revealed low value of the quadrupole splitting of the high-spin state which reflects iron(II) to be in nearly cubic lattice site. Mössbauer spectra under light show the light-induced excited spin state trapping effect and the observed quadrupole splitting of the metastable high-spin state is found little sensitive to the high-spin fraction value. DFT calculations are in progress to document the almost cubic nature of the ligand-field acting on the iron atom.     

A Mössbauer study of Bi2Sr2Ca n-1 (Cu,Fe) n O y (n=1,2,3) oxide superconductors

Mossbauer spectra of⁵⁷Fe have been measured for Bi₂Sr₂Ca_n-1(Cu, Fe)_nO_y (n=1,2,3) oxide superconductors. Each spectrum was decomposed to a single set or two sets of double peaks. The assignment of these peaks to the specific sites for the iron atoms are discussed. The 4 fold planar sites of Cu₂O plane are preferentially substituted by Fe atoms.     

Mössbauer emission study of57Co: YBa2Cu3O7−y HTSC

Mössbauer emission spectroscopy is performed on⁵⁷Co:YBa₂Cu₃O_7–y oxides in a temperature range from 300 K to 77 K. The spectra show, at least two different location for the⁵⁷Co(⁵⁷Fe) impurities. The isomer shift and quadrupole splitting values of the⁵⁷Fe daughter are coincident with those observed in⁵⁷Fe absorption experiments. From the analysis of theIS andQS values as well as from the relative location of Fe impurity levels in the HTSC matrix it is argued that:a) Co impurities enters into the lattice mainly in the Cu1 sites, but some of them have a higher coordination number.b) The daughter⁵⁷Fe exists as localized Fe⁴⁺ state.c) The parent⁵⁷Co enter as a localized Co³⁺ state. These conclusions appear consistent with the observed increase ofN(0) on doping with Fe or Co ions and with the existence of localized magnetic moments as determined from paramagnetic susceptibility measurements.     

A Mössbauer study of iron and iron–cobalt nanotubes in polymer ion-track membranes

Iron and iron–cobalt nanostructures that were synthesized in polymer ion-track membranes have been studied via Mössbauer spectroscopy combined with raster electron microscopy, energy-dispersion analysis, and X-ray diffraction data. The obtained nanostructures are single-phase bcc Fe_1–xCo_x nanotubes with a high degree of polycrystallinity, whose length is 12 μm; their diameter is 110 ± 3 nm and the wall thickness is 21 ± 2 nm. Fe²⁺ and Fe³⁺ cations were detected in the nanotubes, which belong to iron salts that were used and formed in the electrochemical deposition. The Fe nanotubes exhibit eventual magnetic moment direction distributions of Fe atoms, whereas Fe/Co nanotubes have a partial magnetic structure along the nanotube axis with a mean value of the angle between the magnetic moment and nanotube axis of 34° ± 2°. Substituting the Fe atom with Co in the nearest environment of the Fe atom within the Fe/Co structure of nanotubes leads to a noticeable increase in the hyperfine magnetic field at the ⁵⁷Fe nuclei (by 8.7 ± 0.4 kOe) and to a slight decrease in the shift of the Mössbauer line (by 0.005 ± 0.004 mm/s).