<Superscript>119</Superscript>Sn Mössbauer studies on ferromagnetic and photocatalytic Sn–TiO<Subscript>2</Subscript> nanocrystals

Diluted Sn doped TiO₂ nanocrystals (Sn/Ti ratio: x ≤ 1.37 %) were synthesized by a simple hydrothermal method using pure reagents without any surfactant and dispersant material. The XRD of these samples showed an anatase phase, anatase and rutile mixed phases, and a rutile phase of TiO₂ and SnO₂ with the increase of Sn dopant concentrations. ¹¹⁹Sn Mössbauer spectra gave the broad peaks, which were decomposed into doublets and sextets because almost all these samples showed magnetic hysteresis even at room temperature. The titanium oxides doped with x ≤ 0.12 % showed the relatively large magnetic hysteresis and high photocatalytic activity. Mössbauer spectra of samples doped with x > 0.3 % were analyzed by one doublet and two sextets although the samples showed weak ferromagnetism. Three kinds of Sn species may be distinguished as Sn ⁴⁺ substituted TiO₂ and two different magnetic arrangements of Sn doped TiO₂: one with more oxygen defects and other at the interface of TiO₂ and precipitated SnO₂ containing Ti atoms. The correlation between various amounts of Sn sites and photocatalytic activity and/ or magnetic property was discussed.     

Mössbauer investigations of the CaMn<Subscript>7</Subscript>O<Subscript>12</Subscript> double manganite with the nuclei of <Superscript>57</Superscript>Fe probe atoms

The CaMn₇O₁₂ double perovskite-like manganite is studied using Mössbauer spectroscopy with ⁵⁷Fe impurity atoms. The hyperfine parameters of the Mössbauer spectra are found to reflect the specific local structure of this oxide. It is found that the phase transition at T ≈ 90 K is associated with the ordering of the magnetic moments of manganese cations in the octahedral sublattice. The structural phase transition R \(\overline 3 \) ? Im \(\overline 3 \) is shown to occur in the temperature interval from 380 to 450 K, where the rhombohedral (R \(\overline 3 \)) and cubic (Im \(\overline 3 \)) phases of the manganite coexist.     

Mössbauer effect study of Bi<Subscript>0.8</Subscript>La<Subscript>0.2</Subscript>FeO<Subscript>3</Subscript> multiferroic on <Superscript>57</Superscript>Fe nuclei

The parameters of hyperfine interactions in the Bi_0.8La_0.2FeO₃ multiferroic have been measured by Mössbauer spectroscopy in the temperature range of 87–850 K. It has been found that the spatial spin-modulated structure that exists in BiFeO3 is destroyed in the substitution of La for 0.2 mol % of Bi and the homogeneous antiferromagnetic structure appears. The temperatures of the magnetic (Néel temperature, T _N = 677 ± 3 K) and ferroelectric (Curie temperature, T _C = 773 ± 3 K) transitions and the Debye temperature (Θ = 431 ± 12) have been measured.     

<Superscript>57</Superscript>Fe emission Mössbauer spectroscopy following dilute implantation of <Superscript>57</Superscript>Mn into In <Subscript>2</Subscript>O<Subscript>3</Subscript>

Emission Mössbauer spectroscopy has been utilised to characterize dilute ⁵⁷Fe impurities in In ₂O₃ following implantation of ⁵⁷Mn (T _1/2 = 1.5 min.) at the ISOLDE facility at CERN. From stoichiometry considerations, one would expect Fe to adopt the valence state 3 + , substituting In ³⁺, however the spectra are dominated by spectral lines due to paramagnetic Fe²⁺. Using first principle calculations in the framework of density functional theory (DFT), the density of states of dilute Fe and the hyperfine parameters have been determined. The hybridization between the 3d-band of Fe and the 2p band of oxygen induces a spin-polarized hole on the O site close to the Fe site, which is found to be the cause of the Fe²⁺ state in In ₂O₃. Comparison of experimental data to calculated hyperfine parameters suggests that Fe predominantly enters the 8b site rather than the 24d site of the cation site in the Bixbyite structure of In ₂O₃. A gradual transition from an amorphous to a crystalline state is observed with increasing implantation/annealing temperature.     

Mössbauer study of SnO<Subscript>2</Subscript> powders doped with dilute <Superscript>57</Superscript>Fe prepared by a sol-gel method

SnO₂ powders, doped with various ⁵⁷Fe contents were prepared by a sol-gel method, and annealed finally at 500 °C and 650 °C. These samples were characterized by Mössbauer spectroscopy, vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), and X-ray diffraction (XRD) to investigate the relationship of magnetic properties, grain sizes, annealing temperatures and Mössbauer parameters. The particle sizes of SnO₂ powders reduced to less than 100 nm with the increase of Fe contents up to 5%. Rutile SnO₂ was the only phase obtained for all samples. Room temperature Mössbauer spectra suggest the presence of two different paramagnetic iron sites for all samples and one magnetically relaxed species for those samples with the lowest iron concentrations. The magnetization increased with the Fe content, but was reduced for the samples annealed at 650 °C perhaps due to a segregation of α-Fe₂O₃ doped with tin.     

<Superscript>151</Superscript>Eu Mössbauer study of multiferroic Eu<Subscript>0.75</Subscript>Y<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

We are herewith reporting the ¹⁵¹Eu Mössbauer spectra collected on a polycrystalline powder sample of Eu_0.75Y_0.25MnO₃ from 15 K to room temperature. All the spectra consist of a single line, whose shape and related sample thickness are dependent on the temperature T. The thermal trend of the mean square displacement of Eu ion, obtained from the spectra analysis, clearly reveals a large low-temperature anharmonicity and in concomitance with the onset of the magnetic ordering consists in a linear strong decrease interrupted by two narrow wells at 29.5 K and 40 K. This behavior is interpreted in connection with the transfer of spectral weight from the 120 cm^-1 optical phonon to the electromagnonic modes. The T-trend of the central shift shows that Eu³⁺ electronic ground state in the magnetically ordered phase differs from the one in the paramagnetic state. Finally, the temperature dependence of the hyperfine field under T _N gives a contribution to interpret some controversial features regarding the phase-diagram.     

<Superscript>57</Superscript>Fe Mössbauer study of the chainpur meteorite

The Chainpur meteorite is one of 23 ordinary chondrites classified as LL3-type (low-Fe & low-metal). It was observed as a shower of stones falling on May 9, 1907 in Uttar Pradesh, India. We report here the characterization of the Fe-bearing phases in this chondrite using ⁵⁷Fe Mössbauer spectroscopy carried out at 298 K, 120 K, 50 K and 13 K. The paramagnetic doublets of olivine and pyroxene dominate the room temperature spectrum, accounting for around 70 % of the spectral area. Moreover, a doublet present with a spectral area of 5 % and assigned to a superparamagnetic Fe ³⁺ phase is a consequence of terrestrial weathering. On the basis of the measured ⁵⁷Fe electric quadrupole splitting of the olivine component at room temperature we estimate the mean Fe:Mg ratio in this meteoritic olivine to be around 35:65 % although there is clearly a wide range of composition. The effects of magnetic ordering of the major components olivine and pyroxene are observed at 13 K.     

121Sb Mössbauer spectroscopy of Mn1+x Sb

¹²¹Sb Mössbauer spectra for ferromagnets, Mn_1+x Sb (0.00≤x≤0.22) in ε phase were measured at 77 K. The large unique hyperfine magnetic field (H _hf=361 kOc) atx=0 tends to decrease and to have a wide distribution with increase ofx. The decreasing ratio of the mean value ofH _hf for the nonstoichiometric samples is in accordance with that of their magnetizationM _S(x), i.c., the relation \(\overline {H_{hf} } (x)/H_{hf} (0) = M_S (x)/M_S (0)\) holds in this system.     

Mössbauer spectroscopy of <Superscript>57</Superscript>Fe in <Emphasis Type="Italic">α</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> following implantation of <Superscript>57</Superscript>Mn<Superscript>*</Superscript>

Two Fe/MCM-41 systems, one of them sylilated, were obtained to be used as catalysts in Fischer–Tropsch reaction. They have more than 90% of the iron species located inside the support channels, leading to a narrow crystal size distribution accessible to reactive gases. The samples were characterized by X-ray diffraction, atomic absorption spectroscopy, N₂ adsorption, Mössbauer spectroscopy and Fourier transformer infrared spectroscopy. Mössbauer spectroscopy allowed us to demonstrate that the catalytic active species were the same in both catalysts. The only difference between them was the surface hydrophobicity, which decreases the “water gas shift reaction” in the sylilated catalyst. Besides, this solid is more active for hydrocarbon production, with a lower methane yield.     

Electrochemical properties of Ti-Ni-Sn materials predicted by <Superscript>119</Superscript>Sn Mössbauer spectroscopy

The electrochemical activity of TiNiSn, TiNi ₂Sn and Ti ₆Sn ₅ compounds considered as negative electrode materials for Li-ion batteries has been predicted from the isomer shift- Hume-Rothery electronic density correlation diagram. The ternary compounds were obtained from solid-state reactions and Ti ₆Sn ₅ by ball milling. The ¹¹⁹Sn Mössbauer parameters were experimentally determined and used to evaluate the Hume-Rothery electronic density [e _av]. The values of [e _av] are in the region of Li-rich Li-Sn alloys for Ti ₆Sn ₅ and outside this region for the ternary compounds, suggesting that the former compound is electrochemically active but not the two latter ones. Electrochemical tests were performed for these different materials confirming this prediction. The close values of [e _av] for Ti ₆Sn ₅ and Li-rich Li-Sn alloys indicate that the observed good capacity retention could be related to small changes in the global structures during cycling.     

Mössbauer studies of the spectra of <Superscript>57</Superscript>Fe nuclei in Late Cenozoic endogenous formations of the Eastern Caucasus

Three types of manifestations of Late Cenozoic endogenous activity (pyroclastic, hydrothermal explosive, and volcanogenic sedimentary formations) have been found over the last decade in different geostructural zones of the Terek–Caspian foretrough and the Alpine fold–thrust structure in the Eastern Caucasus. The results from Mössbauer studies show that these formations contain fractions of iron and its compounds with complex crystal structures in which ⁵⁷Fe atoms occupy nonequivalent positions in the lattice with respect to their magnetic and electric fields, exist in different physicochemical states, and occur in various phases of the endogenous process products.     

Mössbauer study of 1% <Superscript>57</Superscript>Fe doped ferromagnetic insulator La<Subscript>0.825</Subscript>Ca<Subscript>0.175</Subscript>MnO<Subscript>3</Subscript>

We have employed magnetization measurements, M?ssbauer and ESR spectroscopic techniques, in order to study the ferromagnetic insulating (FMI) compound La_1-xCa_xMnO₃ (x=0.175) doped with 1% ⁵⁷Fe. We have used two samples; one prepared in air which has cation vacancies and a second in inert atmosphere, which is stoichiometric. An abrupt change of the experimental results is obtained, by all techniques, in the ferromagnetic insulating regime, in the temperature region of T_O/O//≈60 K, where an orbital rearrangement is suggested to occur. An analysis of these findings points to an orbital rearrangement transformation. Ferromagnetic resonance reveals considerable differences between stoichiometric and cation deficient samples, indicating anisotropy of the exchange interactions in the former sample with significant temperature dependence, most pronounced in the vicinity of T_O/O//     

Single-crystalline M-type Sr Hexaferrites studied by <Superscript>57</Superscript>Fe Mössbauer spectroscopy

The ⁵⁷Fe Mössbauer spectra of the single crystalline and the finely ground Sr_1?x La _x Fe_12?y Co _y O₁₉ (x = 0 : y = 0, x = 0.192 : y = 0.152 and x = 0.456 : y = 0.225) samples have been measured to investigate the La-Co substitution effects. All observed spectra at 150 K were well fitted using the five subspectra which correspond to the five crystallographical nonequivalent Fe sites in the M-type hexaferrite, indicating that the valence changes to Fe²⁺ ions in the Fe³⁺ ions were not observed in our Sr_1?x La _x Fe_12?y Co _y O₁₉ samples. In SrFe₁₂O₁₉, the relative absorption intensities in the five subspectra show the large anisotropies in the recoilless fractions at the five Fe sites whereas these anisotropies were not observed in Sr_0.544La_0.456Fe_11.775Co_0.225O₁₉. These results indicate the chemical compositional dependence on the anisotropies of the recoilless fractions at the five Fe sites. The substitution of a Co²⁺ ion for the Fe³⁺ ion changes the center shifts of the Fe³⁺ ions near the Co²⁺ ion by the perturbation of the Fe-O-Co hybridizations. Therefore, the Co²⁺ ions occupy the 4f ₁ and the 4f ₂ sites due to the chemical compositional dependences of the refined magnetic hyperfine field and center shifts of the Fe³⁺ ions.     

Mössbauer study of the modulated magnetic structure of FeVO<Subscript>4</Subscript>

Mössbauer spectroscopy is used to study the FeVO₄ multiferroic, which undergoes two magnetic phase transitions at T _N1 ≈ 22 K and T _N2 ≈ 15 K. The first transition (T _N1) is related to transformation from a paramagnetic state into a magnetically ordered state of a spin density wave, and the second transition (T _N2) is associated with a change in the type of the spatial magnetic structure of the vanadate. The electric field gradient tensor at ⁵⁷Fe nuclei is calculated to perform a crystal-chemical identification of the partial Mössbauer spectra corresponding to various crystallographic positions of Fe³⁺ cations. The spectra measured in the range T _N2 < T < T _N1 are analyzed on the assumption about amplitude modulation of the magnetic moments of iron atoms μ_Fe. The results of model intersection of the spectra recorded at T < T _N2 point to a high degree of anharmonicity of the helicoidal magnetic structure of the vanadate and to elliptic polarization of μ_Fe. These features are characteristic of type-II multiferroics. The temperature dependences of the hyperfine interaction parameters of ⁵⁷Fe nuclei that were obtained in this work are analyzed in terms of the Weiss molecular field model on the assumption of orbital contribution to the magnetic moments of iron cations.     

A study of thermodynamic properties of dilute Fe-Ru alloys by <Superscript>57</Superscript>Fe Mössbauer spectroscopy

The room temperature Mössbauer spectra of ⁵⁷Fe were measured for Fe_1?x Ru _x solid solutions with x in the range 0.01 ≤ x ≤ 0.08. The obtained data were analysed in terms of short-range order parameter (SRO) and the binding energy E _b between two ruthenium atoms in the studied materials using the extended Hrynkiewicz-Królas idea. The extrapolated value of E _b for x = 0 was used to compute the enthalpy of solution H _FeRu of Ru in Fe matrix. The result was compared with corresponding values given in the literature which were derived from experimental calorimetric data as well as with the value resulting from the cellular atomic model of alloys by Miedema. It was found that all the H _FeRu values are negative or Ru atoms interact repulsively. At the same time, the Mössbauer data were used to determine values of the short-range order parameter α ₁. For the as-obtained samples in which atoms are frozen-in high temperature state, close to the melting point, the negative α ₁ values were found. The findings indicates ordering tendencies in such specimens. On the other hand, in the case of the annealed samples where the observed distributions of atoms should be frozen-in state corresponding to the temperature 700 K, the Fe_1?x Ru _x alloys with x ≥ 0.05 exhibit clustering tendencies (a predominance of Fe-Fe and Ru-Ru bonds), which manifest themselves by positive values of the calculated SRO parameter. The clustering process leads to a local increase in ruthenium concentration and nucleation of a new ruthenium-rich phase with the hcp structure.     

Synthetic versiliaite and apuanite: investigation by <Superscript>57</Superscript>Fe Mössbauer spectroscopy

The minerals versiliaite and apuanite have been synthesised for the first time. The ⁵⁷Fe Mössbauer spectra recorded at 298 and 4 K are reported. The results are indicative of a formulation for versiliaite as \(\left (\text {Fe}_{4}^{2+}\text {Fe}_{4}^{3+}\right )^{\text {oct}}\left [\text {Fe}_{4}^{3+}\text {Sb}_{12}^{3+}\right ]^{\text {tet}}\textit {O}_{32}\textit {S}_{2}\) and of apuanite as \(\left (\text {Fe}_{4}^{2+}\text {Fe}_{8}^{3+}\right )^{\text {oct}}\left [\text {Fe}_{8}^{3+}\text {Sb}_{16}^{3+}\right ]^{\text {tet}}\textit {O}_{48}\textit {S}_{\mathrm {4.}}\) The spectra recorded at low temperature are indicative of complex magnetic interactions. The results indicate the potential for the synthesis of further new structurally-related materials with different compositions and new low dimensional physical properties.     

Temperature investigations of the spatial spin-modulated structure of multiferroic BiFeO<Subscript>3</Subscript> by means of Mössbauer spectroscopy

The results from ⁵⁷Fe Mössbauer spectroscopic studies of multiferroic BiFeO₃ in a range of tem-peratures including that of the magnetic phase transition are presented. The Mössbauer spectra are processed and analyzed by reconstructing the hyperfine magnetic field distributions and interpreting the spectra with a cycloid-type spatial spin-modulated structure model. The temperature dependences of the hyperfine spectrum parameters (the Mössbauer line shift, the quadrupole shift, and the isotropic and anisotropic contributions to the hyperfine magnetic field) are obtained, along with the anharmonicity parameter of an incommensurate spin wave.     

Electrical properties of polycrystalline TiO<Subscript>2·</Subscript> Thermoelectric power

The present work determined thermoelectric power for high-purity polycrystalline TiO₂ at elevated temperatures (1,123–1,323 K) and in the gas phase of controlled oxygen activity, . The slope of the thermoelectric power vs logp(O₂) is 1/10, instead of 1/6 expected by the theory and observed for TiO₂ single crystal. The discrepancy between the two is considered in terms of the effect of the local grain boundary structure on thermoelectric power. A comparison between the electrical conductivity and thermoelectric power data indicates that the oxygen activity values related to the n–p transition point determined by thermoelectric power are lower than those determined by electrical conductivity. This project was performed as part of UNSW R&D program on solar–hydrogen.     

Mössbauer studies of spatial spin-modulated structure and hyperfine interactions in multiferroic Bi<Superscript>57</Superscript>Fe<Subscript>0.10</Subscript>Fe<Subscript>0.85</Subscript>Cr<Subscript>0.05</Subscript>O<Subscript>3</Subscript>

Results of Mössbauer investigations on ⁵⁷Fe nuclei in multiferroic material Bi⁵⁷Fe_0.10Fe_0.85Cr_0.05O₃ in the temperature range from 5.2 to 300 K are presented. Bulk rhombohedral samples were obtained by solidstate synthesis at high pressure. Mössbauer spectra were analyzed using the model of spatial incommensurate spin-modulated structure of the cycloidal type. Information on the influence of substituting Cr cations for Fe cations on hyperfine spectral parameters was obtained: the shift and quadrupolar shift of a Mössbauer line, and isotropic and anisotropic contributions into the hyperfine magnetic field. The anharmonicity parameter m of the spatial spin-modulated structure increases almost 1.7 times at 5.2 K when BiFeO₃ is doped with chromium. The data on m were used for calculation of the uniaxial magnetic anisotropy constants and their temperature dependences for pure and chromium-doped BiFeO₃.