P. M. A. de Bakker

On the methodology of the analysis of Mössbauer spectra

A review is presented of the direct fitting procedures which are used in the analysis of Mössbauer spectra. Direct lineshape fitting with alternative profiles as well as shape-dependent, shape-independent and quasi shape-independent distribution fitting methods all can easily be incorporated in one computer program scheme yielding a large versatility for modification and/or extension of the programs according to specific spectra.

Influence of nonstoichiometry and the presence of maghemite on the Mossbauer spectrum of magnetite

Several samples of large- and small-particle magnetite (Fe3O4), as well as its thermal decomposition products formed at different temperatures and atmospheres, have been studied extensively by Mössbauer spectroscopy (MS), both with and without an applied field of 6T. Synthetic mixtures of magnetite and poorly- or well-crystallized maghemite have also been studied. Large-particle magnetite (MCD > 200 nm), when heated in air for 12 hours at T < 400°C, transforms to a mixture of well-crystallized hematite and magnetite, the latter one remaining stoichiometric, according to the relative area-ratios obtained from MS. Thermal treatment at 1300°C in a controlled O2 partial pressure, produced a mixture of stoichiometric and nonstoichiometric magnetite, but the latter component seems to be composed of particles with different degrees of nonstoichiometry. The Mössbauer spectra of the decomposition products at T < 200°C in air of small-particle magnetite (MCD ~ 80 nm) could be successfully interpreted as a mixture of magnetite and maghemite, rather than nonstoichiometric magnetite. This suggestion is further supported by the experiments with the synthetic mixtures. It is clearly demonstrated that is not possible, even by applying a strong external field, to separate the contribution of the A-site of magnetite from that of maghemite.

Annealing behaviour of reactor pressure-vessel steels studied by positron-annihilation spectroscopy, Mössbauer spectroscopy and transmission electron microscopy

The annealing behaviour of commonly used reactor pressure-vessel steels was studied using positron-annihilation spectroscopy (PAS) (lifetime and Doppler broadening techniques), transmission Mossbauer spectroscopy (MS), integral low-energy electron MS (ILEEMS) and transmission electron microscopy (TEM). The results of these methods applied to different types of steels are discussed. Some significant differences in the experimental results are observed between the Russian (3 types) and Western Europe (5 types) steels and between individual specimens within these two groups. All specimens were annealed in vacuum and studied after this thermal treatment. It was confirmed that the heat affected zone (HAZ) is the most sensitive region for thermal and neutron irradiation-induced embrittlement in the reactor. Positron-annihilation lifetime measurements on HAZ specimens annealed at successively higher temperatures show the drastic increase in the vacancy-type defect formation between 525°C and 600°C. Therefore these specimens were selected for further detailed studies by TEM.

Mössbauer study of the thermal decomposition of lepidocrocite and characterization of the decomposition products

The lepidocrocite (γ-FeOOH) to maghemite (γ-Fe2O3), and the maghemite to hematite (α-Fe2O3) transition temperatures have been monitored by TGA and DSC measurements for four initial γ-FeOOH samples with different particle sizes. The transition temperature of γ-FeOOH to γ-Fe2O3 and the size of the resulting particles were not affected by the particle size of the parent lepidocrocite. In contrast, the γ-Fe2O3 to γ-Fe2O3 transition temperature seems to depend on the amount of excess water molecules present in the parent lepidocrocite. Thirteen products obtained by heating for one hour at selected temperatures, were considered. Powder X-ray diffraction was used to qualify their composition and to determine their mean crystallite diameters. Transmission electron micrographs revealed the particle morphology. The Mössbauer spectra at 80 K and room temperature of the mixed and pure decomposition products generally had to be analyzed with a distribution of hyperfine fields and, where appropriate, with an additional quadrupole-splitting distribution. The Mössbauer spectra at variable temperature between 4.2 and 400 K of two single-phase γ-Fe2O3 samples with extremely small particles show the effect of superparamagnetism over a very broad temperature range. Only at the lowest temperatures (T⩽55 K), two distributed components were resolved from the magnetically split spectra. In the external-field spectra the ΔmI=0 transitions have not vanished. This effect is an intrinsic property of the maghemite particles, indicating a strong spin canting with respect to the applied-field direction. The spectra are successfully reproduced using a bidimensional-distribution approach in which both the canting angle and the magnetic hyperfine field vary within certain intervals. The observed distributions are ascribed to the defect structure of the maghemites (unordered vacancy distribution on B-sites, large surface-to-bulk ratio, presence of OH- groups). An important new finding is the correlation between the magnitude of the hyperfine field and the average canting angle for A-site ferric ions, whereas the B-site spins show a more uniform canting. The Mössbauer parameters of the two hematite samples with MCD104 values of respectively 61.0 and 26.5 nm display a temperature variation which is very similar to that of small-particle hematites obtained from thermal decomposition of goethite. However, for a given MCD the Morin transition temperature for the latter samples is about 30 K lower. This has tentatively been ascribed to the different mechanisms of formation, presumably resulting in slightly larger lattice parameters for the hematite particles formed from goethite, thus shifting the Morin transition to lower temperatures.

Mössbauer study of small-particle maghemite

Two small-particle maghemite (λ-Fe2O3) samples have been investigated with the Mössbauer effect. From the results of the model-independent hyperfine-field distribution fits some characteristic temperature-dependent parameters have been obtained. The spectra at the lowest temperatures could be fitted with two strongly overlapping hyperfine-field distributions with different isomer shifts. Spectra in applied magnetic fields ranging from 40 to 60 kOe, and at 4.2 K showed non vanishing Δm1=0 absorption lines. The hyperfine-field distribution and canting-angle distribution method for fitting these spectra did not yield reasonable results. Therefore, a bi-dimensional hyperfine-field-canting-angle distribution has been applied, and was found to reproduce the experimental line shapes with remarkable adequacy. The resulting distribution profiles revealed a linear correlation between Hhf and the angle between the magnetic moments and the external field.

An improved, two-parameter distribution method for the description of the Mossbauer spectra of magnetic small particles in an applied field

An improved method for computer analysis of Mossbauer spectra of small-particle magnetic materials obtained at 4.2 K and in varying external magnetic fields applied parallel to the gamma -ray direction, is presented. The method is based on the simultaneous distribution of the intrinsic hyperfine field Hhf and the canting angle theta between Hhf and the applied magnetic field Hext. The smoothing Lagrange multipliers for both distributed parameters can be chosen independently. The matrix inversion has been solved under the constraint that only positive values are allowed for the resulting probability profile. This matrix inversion is combined with an iteration procedure. The applicability of this model-independent distribution method is illustrated by means of the results obtained for two small-crystallite iron oxyhydroxides, namely ferrimagnetic delta -FeOOH and antiferromagnetic aluminium-substituted goethite ( alpha -AlcFe1-cOOH).

Variable-temperature Mössbauer spectroscopy of nano-sized maghemite and Al-substituted maghemites

Synthetic aluminum-substituted maghemite samples, γ-(Fe1-xAlx)2O3, have been prepared by thermal decomposition of Al-lepidocrocite (γ-Fe1-xAlxOOH), with × = 0, 0.04, 0.06, 0.14 and 0.18. The particles are needle-shaped and the mean crystallite diameter along the [311] crystallographic direction was found to be between 2.0 and 5.0 nm. Mössbauer spectra were collected at 6 K and from 80 K up to 475 K at steps of 25 K. In a wide range of temperatures the spectra of the non-substituted sample consist of a superposition of a broad sextet and a superparamagnetic doublet, whereas for the Al-maghemites this range is much smaller. From the temperature variation of the fractional doublet area two different parameters were defined: the temperature corresponding to a 50/50 doublet-sextet spectrum (T1/2), and the temperature below which the doublet ceases to exist (T0). These two parameters (T1/2 and T0) decrease from 390 K and 92 K (Al-free sample), to 118 K and 64 K (4 mole % Al) and to 100 K and 48 K (18 mole % Al), respectively. The average hyperfine fields at 6 K undergo a steep drop in going from the Al-free sample (Hhf = 506 kOe) to the sample with 4 mole % Al (Hhf = 498 kOe), but for higher substitutions the effect is much smaller. The A- and B-site quadrupole splittings, obtained from the data between 220 K and 475 K, were found as: ΔEQ,A = 0.86 ± 0.04 mm/s and ΔEQ,B = 0.65 ± 0.04 mm/s for the 4 mole % Al sample. The characteristic Mössbauer temperature, determined from the temperature dependence of the average isomer shift, was found to be in the range of 500–600 K.

Mössbauer effect study of natural greigite

The hyperline parameters of relatively well crystallized grelgite (Fe3S4) have been determined by Mössbauer spectroscopy on a natural greigite-smythite sample. Applied-field measurements confirm the ferrimagnetic behavior. Saturation values of the magnetic hyperfine fields are 31.8 and 33.0 T for the tetrahedral and octahedral Fe respectively. The temperature dependence implies a Curle temperature of at least 800K. In addition, the analyses of the spectra provide some information about smythite for which the spectra seem to be composed of at least three sextets.

Temperature dependence of the hyperfine parameters of maghemite and al-substituted maghemites

Synthetic aluminum-substituted maghemite samples, γ-(AlyFe1-y)2O3 with y=0, 0.032, 0.058, 0.084, 0.106 and 0.151 have been studied by Mössbauer spectroscopy at 8 K and in the range 80 K to 475 K at steps of 25 K. The spectra have been analysed as a superposition of two sextets composed of asymmetrical Lorentzians. The A- and B-site isomer shifts were constrained as: δA=δB-0.12 mm/s. From the temperature dependence of δB it was possible to determine the characteristic Mössbauer temperature and the intrinsic shift. Both quantities clearly increase with increasing Al content, at least up to 10 mole%. The temperature dependence of the A-and B-sites hyperfine fields could be satisfactorily reproduced using the molecular-field theory assuming an antiparallel spin configuration. The exchange integrals were found as: JAB=-25 K; JAA=-18 K and JBB= -3 K. The hyperfine fields show a crossing in the vicinity of 300 K as a result of the relatively strong A-A interaction. The Curie temperature for the non-substituted sample was calculated to be 930 K and decreases to 765 K for the sample with 15 mol% Al. The gradual decrease of the saturation value of the A-site hyperfine field with increasing Al substitution and the constancy of this quantity for the B sites, suggest that the Al cations occupy the B sites.

TEMPERATURE-DEPENDENCE OF THE MOSSBAUER PARAMETERS OF THE FE-NI PHASES IN THE SANTA CATHARINA METEORITE.

The temperature variation in the range 8–760K of the hyperfine parameters of the Fe−Ni phases in the Santa Catharina meteorite has been determined. It is suggested that the disordered 50–50 Fe−Ni phase actually consists of two distinct fractions, i.e. a completely disordered phase and one with intermediate long-range ordering parameter. The single-line subspectrum of the 28%-Ni phase was found to display magnetic ordering below approximately 25K.