A CEMS/AES study of the passivation of iron

Summary The passivation of iron and steel (DIN 1623) was studied by integral and depth selective conversion electron Mössbauer spectroscopy and Auger electron spectroscopy. Thickness and phase composition of the passive layer formed in sulphate solution and in a phosphate buffer were determined in dependence on the anodic potential and the duration of the passivating procedure. The experimental results lead to the conclusion that not the whole oxidic layer is responsible for the passivity but only a very thin intermediate layer formed between the cubic substrate and the rhombic oxide (-FeOOH) cover.

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CEMS/AES-Analyse von Passivschichten auf Eisen

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In partial fulfillment of his thesis     

Conversion electron Mössbauer and XPS study on the effect of polishing of a stainless steel sample

Conversion electron Mössbauer spectroscopy (CEMS) and XPS has been used for the surface analysis of an X10CrNiTi 18/9 (DIN 1.7440)-type stainless steel in order to determine the supposed structural and/or chemical changes in the surface layer caused by polishing. Both, CEMS and XPS results can be associated with the appearance of Fe nitride in the outer layer of steel samples after polishing, while no sign of nitrogen was detected in the bulk material.     

Determination of thin surface layers in-situ by the conversion electron mössbauer spectroscopy /CEMS/, using a parallel plate avalanche counter /PPAC/

In the present paper we describe a technique for the determination of thin layer thicknesses by the conversion electron Mössbauer spectroscopy /CEMS/, using a new alternative method, a parallel plate avalanche counter /PPAC/, operating with the ketone gas in the ionization chamber. We determined the thickness of iron and magnetite on steel.     

Comparative study of the corrosion and surface chemical effects of the decontamination technologies

Decontamination technologies are generally developed to reduce the collective dose of the maintenance and operation personnel at nuclear power plants (NPP). The highest efficiency (i.e., the highest decontamination factors) available without detrimental modification of the treated surface of structural material is the most important goal in the course of the application of a decontamination technology. At the Paks NPP the AP-CITROX procedure has been utilized for the decontamination of the primary coolant circuit’s components (e.g., main circulating pump (MCP) and steam generators (SGs)). Our previous studies have revealed that a ‘hybrid’ structure of the amorphous and crystalline phases was formed in the outermost surface region of the austenitic stainless steel tubes of SGs as an undesired consequence of the industrial application of the AP-CITROX decontamination technology during the period of 1993–2001. In this paper, we report some comparative findings on the corrosion and surface chemical effects of the AP-CITROX procedure and the novel decontamination technology elaborated at our institution. On optimizing the operational parameters the latter technology may become suitable for the effective decontamination of both dismountable (e.g., MCP swivel) and separable (e.g., SGs) equipments. For this purpose experiments were performed. In this laboratory scale experiments, the passivity, morphology and chemical compositions of the treated surfaces of tube specimens were investigated by voltammetry, and SEM–EDX methods, respectively. The SEM–EDX results have revealed that the oxide removal is surprisingly uniform even after 2 or 3 consecutive cycles. The electrochemical studies have provided evidences that no unfavorable tendencies in the general corrosion state of the tube samples can be detected in the course of the chemical treatments.     

Characterization of tin coated Al alloy by 119Sn conversion electron Mössbauer spectrometry (CEMS)

Sn-plating of aluminum alloy before and after a post-molybdate treatment is characterized by ¹¹⁹Sn conversion electron Mössbauer spectrometry (CEMS). CEMS results gave the direct evidence that the oxidation resistance of Sn-coated aluminum alloy is improved by the post-molybdate treatment. Depth selective CEMS showed that the coating structures consist of SnO₂ on the top coating and the mixed Sn(0) and Sn(II) species in the intermediate layers. The Sn(II) oxide exists abundantly near the interface between the aluminum alloy and the Sn coating rather than beneath SnO₂ layer.     

Fundamental issues of the effective decontamination of the steam generators of Paks NPP</p> </p>

Summary During the period of 1993-2001 chemical decontaminations of 24 SGs in the units 1-3 of the Paks NPP were carried out by a non-regenerative version of AP-CITROX technology, even in two or three consecutive cycles. A comprehensive investigation of the above decontamination method have revealed that the fundamental issues of analytical chemistry and corrosion science were not taken into consideration during the elaboration of AP-CITROX procedure. Therefore, the non-regenerative version of the technology utilized at Paks NPP can be considered to be not an adequate method for the chemical decontamination of any reactor equipments having large steel surfaces (e.g., SGs). As a consequence of the lack of the appropriate decontamination method, initiation of a R&D project focused on the elaboration of the required technology should not be postponed. In this paper, we present a brief overview on the fundamental issues of the technology development. Selected findings obtained in our laboratory on the field of the improvement of the AP-CITROX technology are also reviewed in order to demonstrate the crucial role of some selection criteria.</p> </p>     

In situ M?ssbauer spectroscopic investigation of iron-oxide based water-gas shift catalysts

Iron oxide based catalysts have been studied under reaction conditions by Mössbauer spectroscopy. The parameters of the Mössbauer spectra and the phase composition have been determined in different reaction media and at various temperatures. These data are related to the cation distribution on the main phase-magnetite.     

Verwey Transition in Epitaxial Fe3O4 Films

Thin magnetite films grown on cleaved MgO (100) substrates were studied by in-situ conversion electron Mössbauer spectroscopy (CEMS) in the temperature range of 80 K–300 K. The film growth was monitored by low energy electron diffraction revealing a perfect epitaxy in the whole thickness range from 430 nm down to 3 nm. CEMS measurements proved an ideal magnetite stoichiometry of the 430 nm thick film reflected both in the hyperfine pattern and in the Verwey transition. The thinner films showed strong deviation from the bulk properties, which was attributed to the modification of composition at the MgO/Fe₃O₄ interface, at which a magnesium rich phase is supposed based on CEM spectra. This phase, which was not observed previously, could be detected thanks to highly sensitive low-temperature measurements.     

CEMS/XPS study of iron stearate Langmuir-Blodgett layers

Summary Langmuir-Blodgett mono- and multilayers of ferric stearate have been formed on oxidized silicon wafers. Thermodesorption of these layers was investigated by conversion electron Mössbauer and photoelectron spectroscopy and some complementary methods. Heating of samples in air up to 523 K leads to a desorption of the fatty acid chains, while the ferric ions are left on the substrate surface. These ions do not cluster laterally like it was found for Cd ions. They form a rather homogeneous, closed oxidic layer. This well defined layer may be used afterwards for further studies of surface reactions as well as interface and intra-layer interactions. The surface iron ions were found to exhibit a reasonably high recoilless fraction. Therefore, Mössbauer spectroscopy allows to follow chemical, structural, and magnetic changes of the iron ions even if the surface is covered by less than one monolayer.     

Application of MMS for the study of corrosion at the interface of organic coatings and iron substrate

A special Mössbauer technique, MMS has been used for the study of corrosion on the surface of⁵⁷Fe layers, under two types of organic coatings. The corrosion processes were followed by the Mössbauer spectra.     

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.     

57Fe Mössbauer spectroscopic characterisation of a ferromanganese nodule from the Central Indian Ocean

The iron bearing phases present in a ferromanganese nodule from the Central Indian Ocean have been determined using⁵⁷Fe Mössbauer spectroscopy. The Mössbauer results have been corroborated by XRD, IR and TG-DTA studies. The Mössbauer spectrum of a ferromanganese nodule shows a broad line width which indicates the presence of more than one iron bearing paramagnetic oxide or oxyhydroxide phases where iron is present as Fe³⁺. -FeOOH has been distinctly characterised as one of the iron bearing phases in the nodule. Other oxyhydroxide and oxide phases of iron in the nodule have been ruled out. A typical paramagnetic doublet persists even at very high temperature which has been proposed to be due to iron(III)phosphate. Formation of solid solution of Mn₂O₃–Fe₂O₃ has been observed in the heat treated nodule at 1073 K, which has been characterised by the Mössbauer technique.     

Iron-Iridium Mixed-Metal Carbonyl Clusters: A Mössbauer Study of the Structure and of the Adsorption of [Fe2Ir2(CO)12]2− on MgO

¹⁹³Ir and ⁵⁷Fe Mössbauer spectroscopy was used to investigate the structure of the [Fe₂Ir₂(CO)₁₂]^2- cluster compound and the adsorption of this cluster on hydrated MgO. Supported samples were prepared by impregnation of the magnesia with solutions of [Et₄N]₂[Fe₂Ir₂(CO)₁₂] in acetone. The Mössbauer and FT-IR spectra of the MgO-supported cluster confirm that the bimetallic carbonyl is molecularly physisorbed onto MgO without undergoing any transformation or decomposition. The easy solvent extraction of the intact cluster from the oxide surface excludes ion pairing between the cluster anion and the Mg²⁺ surface sites. Mössbauer spectra are in agreement with the refined structure of the molecular cluster and the temperature dependence of the ⁵⁷Fe Mössbauer spectra above 80 K is consistent with the low degree of interaction of the cluster with the support. This technique, therefore, appears to be promising in order to infer structural information when X-ray determination fails.     

Mössbauer study of hydrothermally-treated ferrosilica gels

Mössbauer spectroscopy and x-ray phase analysis have been used to examine the structural states and grain sizes of the iron-bearing phase in ferrosilica gels in the initial state and after hydrothermal treatment at 673 K. The component ratio has a substantial effect on the phase composition. The specific surface is also related to the phase composition.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 5, pp. 647–651, September–October, 1987.     

SCA window optimization in Mössbauer spectroscopy: The case of constant background

The optimum condition for setting the single channel analyzer /SCA/ has been studied with respect to the time required for data acquisition in Mössbauer spectroscopy. It has been found that, regardless what the peak height to background ratio may be, for most practical purposes the best point to cut off the constant background is where the intensity of the Mössbauer peak drops to about 20% of its full height.     

Mössbauer study of Al6 (Fe,Mn) formation in Al-rich Al−Fe−Mn alloys

Al–Fe–Mn alloys containing 0.5 wt. % iron and 0–3.0 wt. % manganese were prepared at different cooling rates from 0.1 to 500 K/s and studied by Mössbauer spectroscopy. Beyond the usual phase analysis, it was found that the presence of manganese is responsible for the decrease of the quadrupole splitting and isomer shift of the Al₆(Fe,Mn) phase, compared to those of Al₆Fe. It was also shown that the Mössbauer parameters are characteristic of the average manganese content of Al₆(Fe,Mn) only if there are no substantial fluctuations of the Fe/Mn ratio in the Al₆(Fe,Mn) phase. Accurate Mössbauer parameters for the Al₆Fe phase were also determined.     

Nuclear Techniques in the Elucidation of Chemical Structure

The paper offers three applications of nuclear methods in the research of chemical structure. First, progress in positron annihilation spectroscopy is illustrated by a positron beamline study, which obtained results that are not available through conventional experiments. The positron beam was used for the study of Langmuir-Blodgett (LB) films containing 4-58 layers of arachidic acid and its salts. These measurements have shown that this emerging technique is capable of characterizing even such elusive systems. Second, the potential of Mössbauer spectroscopy to answer current challenges of solid state chemistry are shown in a study on perovskites of recent interest. ¹⁵¹Eu Mössbauer spectroscopy was used to study the effect of Pr substitution in EuBa₂Cu₃O_7-. It was shown that the introduction of Pr into the rare earth site as well as into the Ba site results in the appearance of extra electrons both in the copper oxide planes and at the 4f shell of Eu cations. The observed effects were explained by the hole filling effect of Pr. Finally, a survey is presented on the recently developed techniques for nuclear resonant scattering of synchrotron radiation, an exciting and very rapidly developing extension to conventional Mössbauer spectroscopy. An interesting new result is that nuclear inelastic scattering experiments performed on solutions of ⁵⁷Fe complexes show contribution from vibrations rather than from diffusion to the inelastic spectra.     

Determination of the Mössbauer parameters of rare-earth nitroprussides: Evidence for new light-induced magnetic excited state (LIMES) in nitroprussides

Nitroprussides of the rare-earth elements and some mixed rare-earth-sodium nitroprussides are studied by Mössbauer spectroscopy at ambient and lower temperatures. The high precision Mössbauer measurements reveal fine changes in the electronic configurations of the nitroprusside anions. A small increase of the quadrupole splitting reveals charge polarization effects in the nitroprusside anion caused by the oblate or prolate shape of the rare-earth ion and the lanthanide contraction. Despite the very large magnetic moment of holmium a magnetic phase transition is not observed down to 300 mK. The population of the metastable states SI and SII are evidenced in europium and scandium nitroprussides, and most likely they can be populated in all rare-earth nitroprussides. No distinct correlation between the Mössbauer parameters and the decay temperatures T_c of the metastable states are found. In a very thin surface layer strong color change, which remains stable at room temperature, is detected. A quadrupole doublet with Mössbauer parameters typical for Fe(III), low spin S=1/2 state is related to a new colored photoproduct. The photoproduct is called light-induced magnetic excited state (LIMES) and explained with a photochemical redox reaction, which changes the valence, spin, and magnetic state of 4f-3d bimetallic complexes.     

Mössbauer and X-ray Investigation of Clay Minerals Originated from Libya

⁵⁷Fe transmission Mössbauer spectroscopy and X-ray diffractometry were used to study clay mineral samples originated from two different regions (Um-arrazm and Alkawasim) of Libya in order to get information about their mineralogical composition to assess their potential for use in the Libyan oil industry. In the samples originated from Um-arrazm calcite, akaganeite and nontronite while in the samples originated from Alkawasim quartz, akaganeite, montmorillonite, kaolinite, illite, mica and hematite were identified with different ratios by using diffraction method. The differences in the phase composition of iron-containing phases of samples from different localities have reflected in the complex Mössbauer spectra at both 300 K and 80 K. For the samples originated from Um-arrazm the Mössbauer parameters of subspectra were identified as nontronite and akaganeite.