Corrosion studies of iron and its alloys by means of57Fe Mössbauer spectroscopy

Some of the advantages and limitations of Mössbauer spectroscopy when used in corrosion research are shown by using three examples taken from the work of the authors on (i) the passive layer of iron, (ii) the corrosion of weathering steels by SO₂-polluted atmospheres and (iii) the performance of rust converters.     

Mössbauer investigation of temperature transformations in bacterial ferrihydrite

Ferrihydrite nanoparticles formed as a result of the microorganism activity have been studied using Mössbauer spectroscopy, X-ray powder diffraction analysis, and X-ray fluorescence analysis. Three positions of trivalent iron with nonoverlapping ranges of quadrupole splittings have been revealed in bacterial ferrihydrite: QS{Fe³⁺(1)} = 0.49–0.83 mm/s, QS{Fe³⁺(2)} = 0.84–1.10 mm/s, and QS{Fe³⁺(3)} = 1.25–1.73 mm/s. It has been experimentally demonstrated that the Fe³⁺(3) positions are the centers of nucleation of the hematite phase in the course of heat treatment.     

Mössbauer effect study of the magnetic structure in δ-FeOOH

Two samples of-FeOOH with different particle sizes have been studied in an external field of 4 T and as a function of temperature. They were found to have a ferrimagnetic structure due to an unequal occupancy of antiferromagnetically coupled octahedral ferric ions. The large surface contribution, which is characterized by a canted spin structure and by highly deformed Fe³⁺ co-ordinations, strongly influences the magnetic properties observed with Mössbauer spectroscopy.     

The Mössbauer effect in the points of phase transitions

The temperature dependence of the intensity of the Mössbauer line and the shift of its centre on passing through the points of phase transitions was studied. Both quantities exhibit discontinuity at transitions of the first kind while only the shift of the line centre does so at transitions of the second kind. The possibility of using the Mössbauer effect for the exact localization or even classification of phase transitions is shown.     

The Mössbauer effect and magnetism

The Mössbauer effect enabled the magnetic hyperfine splitting (hfs) in ferromagnetic solids to be observed directly for the first time. It was quickly extended to measurements on antiferromagnets, ferrimagnets and paramagnets, and is now well established as a probe for the study of magnetic materials. Applications have ranged from the old problem of the state of the iron atoms in ferromagnetic alloys to the new magnetic materials, e.g. amorphous magnets, spin glasses, fine particle magnets and multilayers. Some examples where the Mössbauer effect has made an important contribution are described.     

Mössbauer effect and XRD studies of iron-zinc binary alloys

Mössbauer spectroscopy and XRD were employed to characterize the microstructural properties of iron-zinc binary alloys between 0–31 at.% Fe. Samples were prepared with accuracies of ±0.5 at.% Fe, and the Mössbauer and lattice parameters were monitored as a function of iron concentration across each phase. Two iron sites were observed in the phase (18–31 at.% Fe), whose occupancies and isomer shifts varied continuously with iron content. However, the quadrupole splitting of each site remained constant. Within the ₁ phase (19–24 at.% Fe), three iron sites were observed whose isomer shifts and quadrupole splittings remained constant, while their occupancies varied with iron concentration. For the first time, a third iron site was observed in the phase (8–13 at.% Fe), whose occupancy increases with iron content. Also, the site occupancies of the two other sites appear to remain constant, while other Mössbauer parameters vary continuously with iron content. Analysis of the phase (6–7 at.% Fe) showed the presence of one iron site, whose parameters were not observed to change due to the small variance in iron concentration. XRD studies indicate the lattice parameters across the and phases vary continuously with iron concentration. Moreover, a better understanding of these phases, as formed in galvanneal steel coatings, was obtained.Research supported by the International Lead Zinc Research Organization, Inc., Grant No. ZM-403 and Virginia's Center for Innovative Technology, Grant No. MAT-92-007-01.     

Mössbauer study of carbon-supported α-Fe catalysts

Mössbauer spectra of carefully reduced carbon-supported iron catalysts show superparamagnetic -Fe at 80 K. The results indicate that the particle size depends on the reduction temperature. Effects of evacuation and CO chemisorption are discussed.     

The influence of pressure on the Mössbauer effect

A study was made of the pressure dependence of the intensity of the Mössbauer line, and the dependence of this quantity on the specific volume of the crystal, which has the same form for all these crystals in the first approximation, was derived for regular atomic crystals in the Grüneisen approximation. The change in intensity of the Mössbauer line due to pressure can be converted, except for a multiplication factor, to a change in intensity of this line caused by a change in temperature.     

Study of the structure and electronic state of thiolate-protected gold clusters by means of 197Au Mössbauer spectroscopy

We have investigated the structures and electronic states of a series of glutathionate-protected Au clusters, Au _n (SG) _m with n = 10 ? ～55, using ¹⁹⁷Au Mössbauer spectroscopy, which allows us to probe the local environment of the constituent Au atoms via isomer shift (IS) and quadrupole splitting (QS). The spectral profile abruptly changes on going from Au₂₂(SG)₁₇ to Au₂₅(SG)₁₈, then it smoothly changes to that of Au～₅₅(SG)_m. However, the spectral profile dramatically changes on going from Au～₅₅(SG)_m to the dodecanethiolate-protected Au cluster with average diameter of 2 nm. The ¹⁹⁷Au Mössbauer spectra of glutathionate-protected Au clusters and dodecanethiolate-protected Au clusters were successfully analyzed on the basis of the structure and electronic state of Au₂₅(SG)₁₈.     

Surface and bulk Mössbauer effect studies of annealed NANOPERM-type alloys

Structure, hyperfine interactions, and magnetic behaviour of Fe₈₀M₇Cu₁B₁₂ (M=Mo, Nb, Ti) nanocrystalline alloys are studied by Mössbauer spectrometry. As-quenched and heat-treated specimens are investigated. Transmission and Conversion Electron Mössbauer effect techniques are used to compare surface and bulk crystallization as a function of annealing temperature with the aim to unveil the crystallization onset. In addition, magnetic structure comprising distributions of hyperfine fields is discussed as a function of composition and annealing temperature. Hyperfine field distributions are obtained separately for the amorphous residual phase and for interface regions. Crystalline phases are represented by discrete components.     

Mössbauer and magnetic characterization of TbRhSn

The intermetallic compound TbRhSn was investigated in detail by X-ray, magnetic susceptibility measurements and ¹¹⁹Sn Mössbauer spectroscopy. This compound undergoes a transition from a paramagnetic to an antiferromagnetic state at T _N = 20.8(2) K. The ¹¹⁹Sn Mössbauer spectrum recorded at 4.2 K can be well fitted as a composition of three subspectra with the same intensities, magnitudes of H _hf, ΔE _Q, and δ _is, in agreement with the model of triangular-like antiferromagnetic arrangements of equal magnetic Tb moments lying in the basal ab-plane deduced from neutron diffraction studies (Szytu?a et al., J Alloys Compd 244:94–98, 1996).     

Use of Mössbauer effect for ion-exchange resins investigation

Results of gamma-resonance spectroscopy investigation of iron ions sorption by aminocarboxylic ampholytes ANKB-2 and ANKB-50 are presented. Conclusions on the forms of the complexes produced in the phase of hydrated ion-exchangers are drawn.     

Mössbauer effect study of the Β-FeOOH to α-Fe2O3 phase transformation

-FeOOH was precipitated from a chloride solution. Mössbauer spectra were taken at room temperature (RT) and at 4.2 K in zero field and in external magnetic fields. Samples aged for successively longer time periods were studied. They contain -FeOOH and -Fe₂O₃, the Mössbauer spectra of which show superparamagnetic behavior. The transformation into -Fe₂O₃ is already induced by aging in the mother solution at 100 C. A final heat treatment at 350 C leads to the complete transformation into -Fe₂O₃ and to an increase of the crystallite size.     

Influence of the soliton in anharmonic molecular crystals with temperature on Mössbauer effect

The influence of a soliton on the properties of the M?ssbauer effect resulting from the gamma-active nuclei situated at lattice sites in quasi-one-dimensional anharmonically organic molecular chains, in which the active nuclei emit gamma-photons, has been theoretically studied by a quantum vibrational model. An expression for the gamma-radiated M?ssbauer transition probability as a function of the temperature and non-linear interaction has been obtained. Finally we give some new properties of this effect from numerical calculation in such a case, which present a way to experimentally confirm the soliton existence in molecular crystals. Received 9 April 1998 and Received in final form 11 December 1998     

New applications of the Mössbauer effect

Results from a Mössbauer experiment to observe acoustic oscillations induced by pulsed laser excitation in MgO:⁵⁷Fe²⁺ crystal are presented. Time-domain spectra are satsifacorily described by the theory of the frequency modulation of Mössbauer radiation transmitted through a vibrating resonance medium. It is proposed that the D _4Ω/D _2Ω ratio of the fourth and second Fourier harmonics of the modulated radiation be used to measure the amplitude of nuclear oscillations.     

Mössbauer investigation of non-aggregated γ-Fe2O3 particles

Investigation by Mössbauer spectroscopy of non-aggregated nanometric -Fe₂O₃ particles dispersed in polymer is reported. Magnetic interactions between the particles were controlled by varying the particle concentration in the polymer. The results show that over the investigated range, the interactions make the relaxation time shorter. Infield experiments show spin canting which increases with decreasing particle size.     

155Gd Mössbauer investigation of the magnetic order and spin-reorientation in Gd3Ag4Sn4

In a recent study of the magnetic order in Gd₃Ag₄Sn₄ by neutron powder diffraction and ¹¹⁹Sn Mössbauer Spectroscopy we showed that both the Gd(2d) and Gd(4e) sublattices order antiferromagnetically at 28.8(2) K. We also demonstrated that the ‘magnetic event’ around 8 K is in fact a ‘plane to axis’ spin-reorientation of the Gd magnetic structure. Here, we extend our study with ¹⁵⁵Gd Mössbauer Spectroscopy. The initial magnetic ordering at 30(2) K is clear for both sites and substantial changes in the hyperfine fields are observed at 8 K when the magnetic structure reorients.     

Determination of relative force constant inβ-Ti (Fe) alloys by means of the Mössbauer second-order Doppler shift

In the present work we have used the Mössbauer effect to investigate the dependence of the second-order Doppler shift on temperature for one sample of-Ti (Fe) alloy with 9.3 at.% Fe. The experimental data of total shift of the Mössbauer line in a temperature interval between 4K and 975 K were fitted to theoretical expressions obtained by assuming the Debye approximation to describe the lattice and a more general approximation for high temperature, which take into account the difference in mass of the impurity atom and that of the host lattice. From the fitting we have obtained that the Ti-Fe interatomic forces are larger than that of Ti-Ti.At the time this work was done E. Galvão da Silva was with the Universität des Saarlandes, Angewandte Physik, D-6600 Saarbrücken, F. R. Germany, as a Fellow on Training Program of the IAEA/Vienna and CNEN/Brazil     

Mössbauer effect and X-ray diffraction investigation of Si–Fe thin films

An X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy investigation of Si_{100– x} Fe _x (0?<?x?<?80) thin films prepared by combinatorial sputtering methods is reported. Resulting Mössbauer spectra were fit to Voigt-based distributions of quadrupole doublets for paramagnetic spectral components and Zeeman split sextets for ferromagnetic spectral components. In conjunction with the X-ray measurements, these results show that the Si-rich films are a mixture of dilute Fe in amorphous Si and an approximately equiatomic amorphous SiFe phase. Fe-rich films show the presence of a ferromagnetically ordered phase. For x?<?73, this ferromagnetic phase is amorphous or nanostructured and for x?≥?73, the phase is shown to be a crystalline bcc phase. Results are discussed in terms of short-range structural ordering in these alloys.