Mössbauer spectroscopy as an analytical tool

Mössbauer spectroscopy is a powerful tool in qualitative and quantitative analysis of solid substances containing Mössbauer-active elements. Information either on the bulk sample or on its surface can be obtained.     

Coprecipitation of iron and platinum(IV) hydroxo complexes as probed by Mössbauer spectroscopy

Stabilization of ⁵⁷Fe compounds in matrices of solid solutions of platinum(IV) superoxo- and hydroxo complexes was probed by Mössbauer spectroscopy. The ratio Fe^III/Fe^IV in these matrices is 20/1.     

Mn doping on Mössbauer spectroscopy of maricite-NaFePO4 as cathode material

Journal of Radioanalytical and Nuclear Chemistry - Transition metal ion substitution in sodium phosphate is effective in enhancing the performance of a cathode material. The...     

Degradation of passive layers of iron studied by conversion electron Mössbauer spectroscopy

Integral electron Mössbauer spectroscopy (ICEMS) and additionally some electrochemical methods were used to characterize the passivation process of iron (low carbon steel) in sulfate, sulfate+sulfite (a possible model solution of acid rain) solutions and in phospate buffer. The phase compositions and thicknesses of the passive layers formed due to the electrochemical polarizations were analyzed in dependence on the duration of the anodic passivations and on the pH of the used electrolytes. The passive layer, as determined from the Mössbauer spectra, consists mainly of -FeOOH, however in sulfite containing sulfate aqueous solution at pH 3.5 Fe₃C and despite ex-situ circumstances FeSO₄·H₂O was detected after the shortest polarization time. The film thickness, which was found to grow nearly linearly with polarization time in pure sulfate solution and in phospate buffer, reached a maximum of 60–160 nm (depending on pH) in sulfate+sulfite solution after a passivation time of about 4 hours. It has been proved, that HSO₃ ^–-ion, which is contained by acid rain, initiate pit formation under acid conditions and so enforces the corrosion of iron. The experimental results furthermore suggest, that not the whole oxidic layer is responsible for the passivity but only a very thin intermediate layer formed between an inner oxide layer of a cubic structure and the rhombic oxide (-FeOOH) cover.     

Local structure and valence of impurity ions in oxides by TDPAC and Mössbauer emission spectroscopy

The features of time-differential perturbed angular correlation (TDPAC) in studies on local chemical structures around impurity atoms are described in comparison with those of Mössbauer emission spectroscopy with four typical examples of recent applications to metal oxide systems, namely,⁹⁹Rh⁹⁹Ru in -Fe₂O₃ and YBa₂Cu₃O_7– and¹¹⁷Cd¹¹⁷In in MO (M=Mn, Co, Ni) and BaRu_2/3Cd_1/3O₃.     

A study of carbonic anhydrase using Mössbauer spectroscopy

The preparation and characterization of an Fe(II) bovine carbonic and human carbonic anhydrase are presented. Results of Mössbauer spectroscopy measurements indicate that the Fe(II) (low spin) is bound at the enzymatically active site. The results are compared with previous studies which had used the technique of perturbed angular correlations of γ-radiation.     

Development and application of parallel-plate avalanche counter for in-beam Mössbauer spectroscopy

For Mössbauer -rays in the in-beam Mössbauer experiments using various beams such as heavy ion, secondary short-lived isotope, and neutron beams, it is important to develop a detector. A parallel-plate avalanche counter (PPAC) is the most suitable gas counter for on-line measurements, because PPAC collects the internal conversion electrons emitted by the Mössbauer effect even under high -background. We evaluated the influences of the pressure and flow rate of the counter gas against the counting efficiency of PPAC, and determined the optimum conditions for use in the in-beam Mössbauer experiments.     

Visible light activated catalytic effect of iron containing soda-lime silicate glass characterized by 57Fe-Mössbauer spectroscopy

A relationship between local structure and visible light activated catalytic effect of iron containing soda lime silicate glass with the composition of 15Na₂O·15CaO·xFe₂O₃·(70-x)SiO₂, x = 5–50 mass %, abbreviated as NCFSx was investigated by means of ⁵⁷Fe-Mössbauer spectroscopy, X-ray diffractometry (XRD), small angle X-ray scattering (SAXS), electrospray ionization mass spectrometry (ESI–MS) and ultraviolet–visible light absorption spectroscopy (UV–Vis). Mössbauer spectra of NCFSx glass with ‘x’ being equal to or larger than 30 after isothermal annealing at 1,000 °C for 100 min consisted of a paramagnetic doublet and a magnetic sextet. The former had isomer shift (δ) of 0.24 mm s^?1 and quadrupole splitting (Δ) of 0.99 mm s^?1 due to distorted Fe^IIIO₄ tetrahedra, and the latter had δ of 0.36 mm s^?1 and internal magnetic field (H _int) of 51.8 T due to hematite (α-Fe₂O₃). The absorption area (A) of α-Fe₂O₃ varied from 47.2 to 75.9, 93.1, 64.8 and 47.9 % with ‘x’ from 30 to 35, 40, 45 and 50, indicating that the amount of precipitated α-Fe₂O₃ varied with the Fe₂O₃ content of NCFSx glass. The precipitation of α-Fe₂O₃ was also confirmed by XRD study of annealed NCFS glass with ‘x’ larger than 30. A relaxed sexted with δ, H _int and Γ of 0.34 mm s^?1 and 37.9 T and 1.32 mm s^?1 was observed from the Mössbauer spectra of annealed NCFSx glass with ‘x’ of 45 and 50, implying that the precipitation of non-stoichiometric iron hydroxide oxide with the composition of Fe_1.833(OH)_0.5O_2.5 having the similar structure of α-Fe₂O₃ and α-FeOOH. A remarkable decrease in the concentration of methylene blue (MB) from 10 to 0.0 μmol L^?1 with the first-order rate constant (k) of 2.87 × 10^?2 h^?1 was observed for 10-day leaching test using annealed NCFS50 glass under visible light irradiation. ESI–MS study indicated that existence of fragments with m/z value of 129, 117 and 207 etc. originating from MB having m/z of 284. This result evidently showed that the MB concentration decreased due to visible light induced decomposition caused by the visible light activated catalytic effect of α-Fe₂O₃ and/or Fe_1.833(OH)_0.5O_2.5 precipitated in soda-lime silicate glass matrix.     

M?ssbauer spectroscopy and structural analysis of solids

Mössbauer spectroscopy is reviewed as a method of analysis of hyperfine interactions in the solid state. It is sensitive both to the atomic scale and to phase structures. It utilizes the interactions between the hyperfine fields and nuclei in solids measured by a nuclear technique. The importance of various Mössbauer isotopes is discussed, the ⁵⁷Fe being still the most important. Principles of the qualitative determination of the structure sites and/or phase attachment are explained on the basis of the measurement of hyperfine structure parameters (i.e. the isomer (chemical) shift, the quadrupole and magnetic splittings). The role of the hyperfine field distribution determination is stressed, especially the magnetic hyperfine induction distribution in magnetically ordered solids. Conditions are explained for the feasibility of quantitative estimations of site occupancy and phase abundance. With respect to the predominant role of the magnetic hyperfine structure predestinating Mössbauer spectroscopy to be considered simultaneously as a special magnetic measuring technique, examples are chosen from the field of new magnetic materials. For the substituted hexagonal (M-type) ferrites (aimed, e.g., for the perpendicular magnetic recording), Mössbauer determination of the cation site occupancy is discussed. Structural changes in ion implanted Fe-B-based amorphous alloys detected by the hyperfine field distribution are shown. For the magnetically extremely soft FeCuNbSiB alloys, produced by the controlled crystallization of an amorphous ribbon, the estimation of their rather complicated phase composition by the Mössbauer phase analysis is demonstrated.Common enterprise of the Department of Low Temperature Physics with the Institute of Physics and Institute of Inorganic Chemistry, Czech Academy of Sciences, Prague     

Applications of Mössbauer spectroscopy to the study of electronic materials

A brief introduction to the methodology of the Mössbauer spectroscopy will be given. The main applications to the study of the intrinsic properties of the materials employed in the electronic technology are reviewed.The reported examples prove the effectiveness of this techniques in the study of semiconducting and magnetic materials.Evidence will be given also to the studies of preparation processes of crystalline and amorphous compound.     

Mechanism of crystal modification of ferrihydrite by polymer hydrogels according to data of Mössbauer spectroscopy

The effect of a polymer hydrogel matrix and an ultrasonic field on the formation of a phase of iron(III) hydroxide is studied by means of Mössbauer spectroscopy. Polyacryl amide (PAA) and gelatin are chosen as polymer matrices for hydrogels. The transformation of iron hydroxide is interpreted as the formation of ferrihydrite with two different forms of iron relative to imperfect and relatively perfect fragments of the structure of crystallites. It is shown that the ultrasonic field and (in some cases) the polymer matrix have a substantial effect on the processes of crystallization of the dispersed phase.     

Fe- and Cr-substituted mullites: Mössbauer spectroscopy and rietveld structure refinement

Fe-substituted mullite samples Al_4.5-yFe_ySi_1.5O_9.75 (y = 0.25 and 0.50) have been prepared using a sol-gel route involving Si and Al alkoxides and iron nitrate as precursors. Mössbauer spectroscopy reveals the presence of three different Fe(III) sites but does not allow to conclude concerning the ion environments, tetrahedral or octahedral. Rietveld refinements reveal that Fe ions are distributed between octahedral and tetrahedral positions, the proportion of octahedral iron increasing from y = 0.25 to y = 0.50. On the other hand, for Cr-substituted mullite, Cr ions arc mainly located on octahedral positions. This difference between Fe and Cr has been attributed to the fact that Cr shows a clear trend to occupy octahedral sites compared to Fc and that it is incorporated inside the mullite structure only at high temperature.     

119Sn Mössbauer spectroscopy of Sn–O nanoparticles prepared by levitation-jet aerosol synthesis

Sn–O nanoparticles were prepared by levitation-jet aerosol synthesis and found to exhibit ferromagnetic behavior. X-ray powder diffraction analysis and ¹¹⁹Sn Mössbauer spectroscopy confirmed these nanoparticles consist of β-Sn, SnO and SnO₂ phases. The maximum specific magnetization was observed for nanoparticles containing the SnO/SnO₂ interface.     

Lithium-induced conversion reaction in wüstite Fe1−xO studied by 57Fe Mössbauer spectroscopy

Fe_1−xO wüstite as negative electrode material for Li-ion batteries has been studied. The aim of this work is to get a better understanding of the insertion mechanism involved during reduction/oxidation processes. Electrochemical tests have been done in Swagelock™ cells and shown a high specific capacity of 800 A h/kg for the first discharge. X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy provide us valuable information on both local and long range order. Hence, Li reaction with wüstite induces formation of highly divided metallic iron (α-Fe and nano-Fe) and Li₂O with a small amount of Fe₂O₃ occurring in a diffusion layer at the surface of the primary particles. Based on the X-ray and Mössbauer spectroscopic analyses, a core–shell model is proposed in order to explain the irreversible capacity of about 1 Li observed at the first cycle. It involves cation diffusion induced by lithium acting as an ‘electronic pressure’.