Pressure-induced magnetization in FeO: evidence from elasticity and Mössbauer spectroscopy

The complete elastic tensor of Fe0.94O (wüstite) has been determined to 10 GPa using acoustic interferometry at GHz frequencies inside a diamond-anvil cell. The soft mode (C44) elastic constant of FeO is reduced by 20% over the experimental pressure range. An unusual discontinuity in the pressure derivatives of C11 and C12 at 4.7+/-0.2 GPa corresponds to the pressure at which the onset of a magnetic ordering transition is observed by high-pressure M?ssbauer spectroscopy and neutron powder diffraction. Our new results combined with literature structural high P-T data suggest that there is a magnetic, although still cubic, phase of FeO between approximately 5 and approximately 17 GPa.     

High temperature Mössbauer spectroscopy of titanomagnetite and maghemite in basalts

Mössbauer spectroscopy of basalt lava samples, exhibiting reversible thermal magnetization (J _s -T) curves with Curie temperatures of about 840 K, has revealed considerable amounts of maghemite (-Fe₂O₃) in many samples. In view of the expected instability of maghemite at temperatures above 620 K, this reversibility came as a surprise. For further studies of the magnetization-temperature relationship of these minerals, we have constructed an elliptical radiation-heated furnace in which Mössbauer spectra can be acquired at temperatures between 300 and 900 K. Measurements at different temperatures have been obtained for two types of basalts, one in which the magnetic minerals are nearly pure magnetite and the other where the room temperature spectrum indicates a mixture of maghemite and magnetite. The two series show different features of the collapse of the internal magnetic hyperfine field, and the composition of minerals in the samples changes during the treatment, showing maghemite.     

Mössbauer and magnetization studies of iron oxide nanocrystals

Monodisperse iron oxide nanocrystals have been produced following non-hydrolytic, thermal decomposition routes. Spherically shaped particles with diameter of 4 and 12 nm and cubic shaped particles with an edge length of 9 nm have been studied. The particles have been shown to consist of mainly maghemite. A reduction of the saturation magnetic hyperfine field is observed for the 4 nm particles as compared to the corresponding bulk value. The anisotropy energy determined from the temperature variation of the magnetic hyperfine field was strongly enhanced for the 4 nm particles.     

Biodegradation of magnetic nanoparticles evaluated from Mössbauer and magnetization measurements

In order to extract a quantitative information about characteristics of the magnetic nanoparticles injected into a living organism it is necessary to define a model of the magnetic dynamics for fitting self-consistently the whole set of the experimental data, specifically, the evolution of Mössbauer spectral shape with temperature and external magnetic field as well as the magnetization curves. We have developed such a model and performed such an analysis of the temperature- and magnetic field-dependent spectra and magnetization curves of nanoparticles injected into mice. This allowed us to reliably evaluate changes in the characteristics of the residual particles and their chemical transformation to paramagnetic ferritin-like forms in different mouse organs as a function of time. Actually, the approach makes it possible to quantitatively characterize biodegradation and biotransformation of magnetic nanoparticles delivered in a body.     

Hyperfine interactions in icosahedral quasicrystals: a Mössbauer study

Icosahedral Al₆₅Cu₂₀Fe₁₅ and Al₄₀Cu_9.9Ge₂₅Mn₂₅ ⁵⁷Fe_0.1 quasicrystals are studied using⁵⁷Fe transmission Mössbauer experiments. The spectra are analyzed by distributions of electric-quadrupole interaction accounting for line asymmetries. Temperature dependences of the hyperfine parameters derived comprising average values ofP() distributions, corresponding standard deviations and center shifts are presented in a whole range from 8 to 300 K.     

Mössbauer study of tektites

Room temperature ⁵⁷Fe Mössbauer spectroscopy has been used to investigate the structural and oxidation state of Fe in tektites from different strewn fields. Spectra have been analyzed in terms of two quadrupole splitting distributions corresponding to Fe^3?+? and Fe^2?+?. All tektites show similar distribution of quadrupole splitting. Each distribution has one peak. The Fe^2?+? sites show a narrow region of Mössbauer line shift (δ) and quadrupole splitting (ε), δ?= 1.02–1.10 mm/s and ε?= 0.85–1.00 mm/s relative to α-Fe. These values have been assigned to intermediate coordination between tetrahedral and octahedral. The Fe^3?+? sites show wider regions of hyperfine parameters: δ?= 0.25–0.45 mm/s and ε?= 0.65–0.90 mm/s. The Fe^3?+?/Fe^2?+? ratio was found to be 0.05–0.15.     

Mössbauer and EPR study of nitrosyl hemoglobin

Nitrosyl hemoglobin was prepared by bubbling fresh⁵⁷Fe-enriched rat hemoglobin with NO. S- and X-band EPR spectra at 77 K are typical for anS=1/2 system with an anisotropicg-tensor and exhibit hyperfine interactions of¹⁴N with the electronic spin. Mössbauer spectra at 4.2 and 100 K consist of a superposition of spectra from high- and low-spin Fe(III), deoxygenated hemoglobin and a component corresponding toS=1/2,g=2, hyperfine constantsA _xx /g _{n n} =A _yy /g _{n n} =–19.6 T,A _zz /g _{n n} =6.8 T, quadrupole splitting E _Q=1.5 mm s^–1, isomer shiftI _s=0.42 mm s^–1 and linewidth 0.4 mm s^–1. The spin-lattice relaxation rate at 100 K is <2×10⁶ s^–1.     

A Mössbauer and X-ray diffraction study of nonstoichiometry in magnetite

The paper deals with the applicability of Mössbauer spectroscopy and X-ray diffraction methods for the determination of the deviation of magnetite from stoichiometry. The results show that among the data obtainable by both methods, the ratio of intensities of two partial spectra composing the Mössbauer spectrum of magnetite enables to evaluate the deviation of magnetite from stoichiometry quantitatively.The authors express their gratitude to Prof. Dr. Ing. J.Cirák who enabled them to perform all measurements of Mössbauer spectra at the Department of Nuclear Physics and Technics, Slovak Technical University, Bratislava. The authors are also indebted to Ing. P.Holba (Institute of Solid State Physics, Czechoslovak Academy of Sciences) and to Ing. Z.Drbálek (Research Institute of Sound and Picture) for the preparation of magnetite samples, and to Mr. P.Chaloupek (Faculty of Mathematics and Physics, Charles University, Praha) for computer calculation of lattice constants. The aid provided by members of the G. V. Akimov State Research Institute for the Protection of Materials, Dipl. Chem. K.Jendelová who carried out chemical analysis of the samples and Ing. K.Turecká who took part in X-ray diffraction measurements, is gratefully acknowledged.     

A mössbauer spectroscopy study of superparamagnetic amorphous alloy particles in a ferrofluid

A ferrofluid prepared by thermal decomposition of Fe(CO)₅ has been studied by use of Mössbauer spectroscopy. From the magnetic field dependence of the spectra obtained above the superparamagnetic blocking temperature, we estimate a particle size of about 4.2 nm. At low temperatures the magnetic properties of the sample seem to be influenced by magnetic coupling among the particles. An upper limit for the magnetic anisotropy energy constant of about 0.6x10⁵ J m^-3 is estimated. This is considerably smaller than that of crystalline α-iron particles prepared on a support.     

Defect-fluorite oxides: Ln (Eu and Gd) Mössbauer study coupled with new defect-crystal-chemistry model

A recently proposed lattice-parameter (a ₀(ss)) model for parent fluorite-type MO₂-LnO_1.5 solid solutions (M^4?+? ?=? Ce and Th; Ln^3?+? ?=? lanthanide) has been extended to more complex LnO_1.5-stabilized zirconia (hafnia) (M^4?+? ?=? Zr(Hf)) with pyrochlore-type ordering and its-associated broad a ₀(ss) hump, using key Ln (Eu and Gd)-Mössbauer and related local-structure data.     

Mössbauer study of spatial dispersion of magnetization at Fe/Cr superlattice interfaces

From an analysis of Mössbauer CEMS spectra, it was found experimentally that a magnetic anisotropy field has an angular spatial dispersion at Fe/Cr superlattice interfaces, due to the roughness and inhomogeneity of the interlayer boundary. The value of the magnetoresistive effect is determined by the spatial dispersion of both the interface and the Fe layer, for which the deviation angle of the magnetization vector depends on the substrate irregularity.     

Mössbauer study of Brazilian soapstone

Steatite mineral rocks, soapstone, have been studied by X-ray diffraction, optical microscopic analysis (modal analysis), electron probe micro analysis and Mössbauer spectroscopy for characterization, mineral percentages and chemical composition. Mössbauer spectra show both, magnetic interactions corresponding to magnetite and doublets corresponding to talc. chlorite, dolomite and tremolite. The temperature dependence of the quadrupole splitting in dolomite has been explained in terms of crystal field interaction.     

Mössbauer spectroscopy and magnetic studies of orientated textured Fe3O4 ferrofluid

Nano scale magnetite based ferrofluid is synthesized by chemical co pre cipitation technique and stabilized with oleic acid. Magnetization and viscosity measurements were used to optimize for texturing purpose. The freeze-textured ferrofluid in two configurations, namely, (1) field texture system (FTS) and (2) zero field texture system (ZTS) are investigated by magnetization measurements at 298 K and Mössbauer spectroscopy measurements at 77 and 298 K. These results are analysed on the basis of the contributions from collective superparamagnetic reversal and the strength of the inter particle interactions.     

Fe57 Mössbauer study in cobalt substituted magnetite

The Mössbauer effect has been studied in the mixed ferrites Co _x Fe_3–x O₄ (forx=0.8, 0.9 and 1) with the spinel structure in the temperature range between 78 and 380 K. The composition withx=1, showed an expected Zeeman spectrum with two overlapping magnetic hyperfine patterns related to the Fe³⁺ ions in tetrahedral and octahedral sites. While for samples withx=0.8 and 0.9 the Mössbauer spectrum for each compound was successfully analysed into three different patterns corresponding to the ferric ions placed at the tetrahedral and octahedral sites and ferrous ions at the octahedral sites, indicating no electron transfer between Fe³⁺ and Fe²⁺, where the quantity of cobalt is sufficiently large to be located at the six nearest neighbours to ferrous ions. The Mössbauer effect parameters were calculated for these observed sites and their variation with temperature reported. The reduced hyperfine magnetic fields of the Fe³⁺ (B) ions were found to follow the Brillouin curve forS=5/2 and one third power law. The magnetic ordering temperature was determined to be 815 K and the possible magnetic interactions were discussed.     

Mössbauer study of iron removal in a montmorillonite

⁵⁷Fe Mössbauer spectroscopy in conjunction with atomic absorption spectrometry and X-ray powder differaction analyses have been used to study the iron present in a montmorillonite prior to and after different successive stages of two deferration processes. Fe³⁺ ions occupy mainly octahedrical M(2) sites in the mineral structure; no impurities of iron oxides were detected. The quite efficient deferration by HCl refluxing produced a substantial alteration of lamellar structure of montmorillonite, whilst dithionite/citrate treatment did not induce severe structural changes but had low iron removal efficiency.     

Mössbauer study of natural wolframites

Natural Wolframite, (Fe _x Mn_1?x )WO₄ withx=0.95 to 0.41, obtained from seven different sites of two quartz-wolframites deposits of Degana and Sirohi in Rajasthan. India, have been studied by Mössbauer spectroscopy down to 20 K. X-ray diffraction studies with a monochromatic Cu radiation (λK_a-1.5405 Å), were carried out to determine the value ofx. The Mössbauer spectra of all seven samples were recored at 300, 200, 100, 50, 40, 30 and 20 K, and were least square fitted for different sites. The Mössbauer parameters are attributed to a high spin ferrous ion in a quite distorted octahedral symmetry, and only one sextet has been resolved below transition temperature.     

Mössbauer study of197Au in Zn and Cd single crystals

The 77.3 keV Mössbauer transition of¹⁹⁷Au was used to study the hyperfine interactions and recoilfree fractions of dilute Au impurities in Zn and Cd single crystals at 4 K. Mössbauer sources were prepared by ion implantation of^197mHg/¹⁹⁷Hg at ambient temperature. From the quadrupole splittings the electric field gradients $$\begin{gathered} eq(Au\underline {Cd} ) = + 11.7(6) \times 10^{17} v/cm^2 and \hfill \\ eq(Au\underline {Zn} ) = ( + )15.0(2.5) \times 10^{17} v/cm \hfill \\ \end{gathered} $$ were determined. The electric field gradients as well as the isomer shifts are in good agreement with the systematics of other impurity host systems. The recoilfree fractions agree with estimates using the mass corrected Debye temperatures of the host lattice.     

Mössbauer study of bacterial iron-reduction processes in natural glauconite and biotite

Interaction between a bacterial monoculture of alkaliphylic G. ferrihydriticus along with binary cultures of G. ferrihydriticus and cellulolytic C. alkalicellulosi and natural biotite and glauconite under alkaliphylic conditions is investigated by means of Mössbauer spectroscopy. Measurements were performed over a range of temperatures from T = 4.8 K to T = 300 K. It was found that a new magnetically ordered phase was formed during culture growth. This new phase was a mixture of nonstoichiometric magnetite and maghemite. The relative amount of the magnetically ordered phase in the monoculture of G. ferrihydriticus when interacting with glauconite is less than in the case of the binary culture. Iron reduction glauconite is also more intense than in biotite.