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.     

The discovery of the Mössbauer effect

A historical outline is given of the discovery of recoilless nuclear resonance absorption of γ-radiation, also called the Mössbauer (M-) effect.     

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 temperature dependence of asymmetric line intensities in Mössbauer effect doublet spectra

Temperature dependent asymmetric line intensities in Mössbauer doublet spectra were observed in linear chain polymers of trimethyltin cyanide and triphenyltin hydroxide. The asymmetry is due to the characteristic anisotropic mean square displacement tensor found for such polymeric structures.     

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.     

A Mössbauer effect investigation of the crystalline electric field in thulium metal

The crystalline electric field parameters and the total splitting of the ³H₆ ground term in thulium metal have been determined above the Néel temperature by a Mössbauer effect investigation of the temperature dependence of the nuclear quadrupole splitting of the 8.42 keV gamma-transition of ¹⁶⁹Tm.     

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.     

A Mössbauer effect study of dilute CrFe alloys

A Mössbauer effect study of the hyperfine magnetic fields at ⁵⁷Fe nuclei in dilute CrFe alloys is reported using a ⁵⁷Co in Cr source and absorbers with Fe concentration from 0·2 to 10 at.%. In zero applied field the most probable hyperfine field for the 0·2 to 5 at.% alloys exhibits the same qualitative temperature dependence, becomeing zero at about the Néel temperature and tending to 35 kOe at 4·2°K. Spectra obtained at 4·2°K in applied fields up to 88 kOe show that the hyperfine field is negative. A value of 225 kOe for the exchange field produced on the Fe localized moments by the SDW's is obtained over the concentration range from 0·2 to 5 at.%. The exchange field is collinear with the local SDW polarization and not with the applied field. The results obtained in zero applied field are interpreted in terms of a spin-compensated magnetic moment partially destroyed by the SDW exchange field. For the 10 at.% alloy larger hyperfine fields are observed and the results indicate ferromagnetic FeFe interactions.