High-performance Mössbauer spectroscopy: Criteria, possibilities, limitations

Increasing attention is being paid to non-conventional Mossbauer methods in view of the extension of Mossbauer Spectroscopy (MS) to a broadening field of applications. With such long-lasting experiments the shortening of the measuring time required for a given statistical significance is of major practical importance. It is shown that the statistical utility rateu allows one to determine which experimental parameters have a primary role, and it also enables sucessive optimization. It is pointed out for various MS measurements that the strategy for improving the experimental performance is strongly dependent on the given problem. As examples, time-differential Mossbauer measurements and conv…

The phase composition of the passive layer on iron

Determination of the Absolute Density of Fe3+ and Ni2+ Ions in Langmuir-Blodgett Films

By means of the Langmuir–Blodgett (LB) technique, mono- and multilayers of Ni2+ and Fe3+ containing fatty acid salts are transferred onto silicon wafers. After thermal treatment, oxidic layers can be produced. The absolute amounts of Fe3+ and Ni2+ ions per monolayer of LB film were measured and calculated by three different methods. In the case of nickel, the amount expected from theory and preparation conditions was obtained experimentally. In contrast, about twice the number of Fe3+ ions as expected is transferred. An explanation can be given by the presence of hydroxide groups bound to iron. The mean film thickness of the oxidic layers after thermal treatment was estimated where the thic…

Conversion electron Mössbauer study of low carbon steel polarized in aqueous sulfate and sulfite containing sulfate solutions

Abstract The passivation of low carbon steel was studied in aqueous solutions of 0.5 M Na 2 SO 4 (pH = 3.5 and 6.5) and of 0.5 M Na 2 SO 4 + 0.001 M NaHSO 3 (pH 3.5 and 6.5). The used conversion electron Mossbauer spectroscopy (CEMS) with the complementary electrochemical, microscopic and spectrophotometric investigations proved that the presence of sulfite ion induces pitting corrosion. The compositions and thichnesses of the passive films formed during the electrochemical treatments are determined from the conversion electron Mossbauer spectra. γ-FeOOH was found in each case as a major component. At pH = 3.5, the sextet belonging to Fe 3 C appears in the spectra in most cases, and also Fe…

The passivation of steel in sodium sulphate solution studied by CEMS and aes

The passive layer formed on standard steel by anodic oxidation in 0.5 M sodium sulphate solution was found to contain iron only in the trivalent state. The thickness of the layer increases with the applied potential as well as with the time the passivating potential is applied to the sample. These results, compared with the electrochemical data, lead to the suggestion that the passive behaviour is not due to the whole oxidic layer but due to a thin, low lying interfacial layer with a structural disorder.

Problems of electron detection in Depth-Selective Conversion Electron Mössbauer Spectroscopy

Applications of Depth-Selective Conversion Electron Mossbauer Spectroscopy (DCEMS) are limited by the long measuring times needed for collecting sufficient data statistics. To shorten the recording time, the background should be reduced and the detection efficiency for conversion electrons should be improved. For57Co/57Fe DCEMS, systematic studies were performed to investigate the origin, shape, and structure of the background components in DCEMS data distributions for various samples using channeltrons and low-noise scintillation counters as electron detectors.

Zerstörungsfreie Phasenanalyse dünner Oberflächenschichten mittels Konversionselektronen

By use of an appropriate gamma radiation, conversion electrons may be produced by Mossbauer effect also in a depth below the sample surface deeper than the free path for inelastic electron scattering. Because the Mossbauer spectrum of the conversion electrons reflects the local phase composition, the recording of all electrons escaping from the surface allows an integral phase analysis of a layer of some 10–100 nm thickness. If only electrons within a narrow range of energy are recorded, a depth selective phase analysis is possible. The applicability of these two techniques of conversion electron spectroscopy is demonstrated by a few examples concerning oxidation and passivation of steel. C…

Study of the phase composition of iron-containing Langmuir-Blodgett layers before and after thermal and chemical treatment

Iron-containing Langmuir–Blodgett mono- and multilayers were prepared by depositing ferric stearate onto silicon wafers. Particular care should be taken in order to avoid the presence of alkali ions, which may replace iron ions in the deposited film. By a subsequent heating in air, the fatty acid chains were thermodesorbed. This results in a rather homogeneous coating of the samples by an iron oxide, most probably in the form of crystalline and amorphous γ-FeOOH, as found by conversion electron Mossbauer, photoelectron and microprobe studies. By a subsequent heating in hydrogen gas or exposure to nascent hydrogen, a partial reduction of the iron oxide layer is possible up to the metallic st…

CEMS/XPS study of iron stearate Langmuir-Blodgett layers

Langmuir-Blodgett mono- and multilayers of ferric stearate have been formed on oxidized silicon wafers. Thermodesorption of these layers was investigated by conversion electron Mossbauer 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 r…

Mößbauer- und ESCA-Untersuchungen zur Bildung oxidischer Eisenphasen in wäßrigen Medien unter der Einwirkung organischer Korrosionsinhibitoren

Korrosionsschichten auf Stahl nach Exposition in Wasser mit bestimmter Harte und Chloridgehalt wurden hinsichtlich der Wirksamkeit beigefugter organischer Inhibitoren mittels Mosbauer- und ESCA-Spektroskopie untersucht. Es entstehen relativ dicke Schichten mit einem unerwartet niedrigen Eisengehalt in Form von FeOOH. Die Schichten enthalten merkliche Mengen von Ionen aus der Testlosung und auch Abbauprodukte der Inhibitormolekule. Letztere werden anscheinend in dem korrosiven Medium zersetzt. Es ist anzunehmen, das das Gesamtmolekul zwar den Transport des Inhibitors zum Metall beeinflust, die eigentliche Inhibierung aber allein durch funktionelle Gruppen erfolgt. Mossbauer and ESCA investig…

Study of Fe−Ti and Fe−TiN interfaces by conversion electron Mössbauer spectroscopy

Titanium and titanium nitride-iron interfaces obtained by PVD coated thin films of Ti and TiN onto argon plasma etched iron substrates at various temperatures and negative bias were studied by use of CEMS. It was found that intermixing to Ti with Fe resulted in the appearance of an amorphous FeTi1−x phase. Furthermore, a comparison of CEM spectra of samples before and after heating in UHV has shown rather strong influence of thermal treatments on Fe/Ti as well as Fe/TiN interfaces.

CEMS of insulators by use of gas-flow counters

Gas-flow CEMS counters are usually designed in such a manner that the sample to be investigated is inserted into the counter and serves as the backing cathode. If the sample consists of an insulating material, serious problems are expected by charging-up effects similar to those appearing in Maze counters. These problems are discussed in detail. It could be shown by experiments with glass samples that their very low surface conductivity is sufficient to allow a defined operation of such gas-flow CEMS detectors. The electric field strength between the surface of the sample and the anode has to be equal or higher than that between the entrance window and the anode. This can be ensured by an a…

Mossbauer study on the distribution of iron in high coercivity chromium dioxide particles

/sup 57/Fe Mossbauer spectroscopy is applied to determine the level of iron doping in high-coercivity CrO/sub 2/ particles. It is found that, compared with the conventional preparation process, the particles contain an increased amount of Fe/sup 3+/ ions in the CrO/sub 2/ crystal lattice, giving rise to higher magnetocrystalline anisotropy. This is reflected in coercivities up to over 900 Oe. All samples contain as a secondary iron-containing phase some (Cr/sub 1-x/Fe/sub x/)/sub 2/O/sub 3/. The valence of the iron doping is predominantly +3; very weak signals in the Mossbauer spectra suggest the existence of Fe/sup 4+/ in an amount 2-3% of the total number of iron atoms. >

The influence of water and of alkali promotor on the carbon number distribution of fischer-tropsch products formed over iron catalysts

The carbon number distribution of Fischer-Tropsch products formed over an alkalized precipitated iron catalyst has been studied as a function of the water vapor pressure of the synthesis gas. The carbon number distribution of formed hydrocarbons is characterized by a bimodal Schulz-Flory distribution of growth probabilities P1 ≈ 0.6 and P2 ≈ 0.87 attributed to unpromoted and promoted (alkalized) sites on the catalyst surface. Promoted sites are more stable with respect to oxidation (deactivation) by water than unpromoted sites. The growth probability of unpromoted sites decreases with increasing ratio P/P — Studies using Mossbauer spectroscopy have shown that iron foils treated with water c…

Mößbauerspektroskopische Phasenanalyse eisenhaltiger Oberflächenschichten

Surface spectroscopic study of the corrosion of ultrathin57Fe-evaporated and Langmuir-Blodgett films in humid SO2 environments

Integral conversion electron Mossbauer spectroscopy (ICEMS), x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and scanning electron microscopy (SEM) have been used to carry out a comparative study of the corrosion resistance against humid SO2-aggressive environments of ultrathin 57Fe films. These films, having a thickness ≤ 2.5 nm, have been prepared by evaporation of 57Fe under vacuum and by 57Fe coating by a Langmuir–Blodgett (LB) technique on SiO2/Si wafers. The results have shown that the corrosion resistance of the evaporated films is similar to that of massive Fe. However, the LB films show a remarkably higher corrosion resistance. Thus, although the Fe films …

Formation, phase composition, and transformations of Langmuir-Blodgett multi- and monolayers containing Fe

Mono- and multilayers of ferric stearate were formed by the Langmuir-Blodgett technique. Thermodesorption of the hydrocarbon chains results in well defined thin oxidic films. Their reduction to Fe2+ and α-Fe was followed by conversion electron Mossbauer spectroscopy. Resonance lines can be observed even if the Fe coverage is less than one monolayer.

Investigation of structure, stability, phase composition and magnetic ordering in ultrathin iron/nickel films

By thermal and chemical treatment of Langmuir-Blodgett (LB) films, oxidic and metallic Fe and Ni layers can be prepared. The films are characterised, where differences e.g. in the lateral homogeneity are found. The metallic Fe containing samples show a higher corrosion stability as compared with films prepared by other coating techniques. Mixed Fe/Ni oxidic and metallic layers, respectively, are prepared, where the Ni concentration in the oxidic films can be determined as a function of the ratio of initially transferred numbers of LB layers. The phase composition of the metallic Fe changes systematically with the Ni concentration.

Icems and dcems study of Fe layers evaporated onto Al and Si

Thin layers of57Fe (2.5 nm, 10 nm and 70 nm thickness), vacuum evaporated onto Al and Si plates, have been investigated by conversion electron Mossbauer spectroscopy (CEMS). The measurements were performed employing both a proportional counter and a channeltron for conventional and ultrahigh-vacuum integral CEMS (UHV-ICEMS) studies, respectively, and a channeltron for depth-selective CEMS (DCEMS). The phase analysis of the layers on base of experimental results has indicated the presence of metallic iron and one or two iron compounds, ascribed to iron reaction products formed with the residual gas during evaporation. These products are most likely rather stable iron nitrides, are more or le…

A study of thin surface layers by multilayer Mössbauer spectroscopy /MMS/

A stacking Mossbauer technique, MMS has been applied for studying thin surface layers. The surface layers formed on the57Fe film in aqueous solutions of corrosion inhibitors, such as zinc phosphate and barium metaborate, and in distilled water was studied by this method. It has been found that the corrosion is much slower in the presence of zinc phosphate and barium metaborate. XPS analysis suggests the formation of a mixed iron zinc phosphate on the surface of the57Fe film after corrosion in a zinc phosphate solution.

Surface and thin film analysis: an introductory survey

Phase composition of Fe-containing Langmuir-Blodgett layers after thermal treatment in a reactive atmosphere

By the Langmuir-Blodgett technique, mono- and multilayers of ferric stearate were drawn onto silicon wafers. They were thermodesorbed in air at 250–300°C, and the layers formed in this way were found to consist of γ-FeOOH with defective stoichiometry. By heating in H2, the layers can be reduced to Fe2− and even to α-Fe. The latter is magnetically ordered and highly corrosion resistant. Chloride ions, however, induce fast corrosion. FeCl2, formed by this corrosion, is rather unstable and transforms to an Fe3+ phase. The high corrosion resistance of the metallic Fe layer is assumed to be due to its excellent homogeneity. The experiments were performed using XPS, AES, CEMS, and SEM.

Corrosion processes and their inhibition as studied by Mössbauer conversion and other electron spectroscopies

To study corrosion processes of iron and steel and measures of their inhibition, a detailed knowledge of the phase composition and of phase transformations in very thin layers close to the attacked surface of the material is necessary. The information depths of integral (ICEMS) and depth selective (DCEMS) conversion electron Mossbauer spectroscopy are well suited for such investigations, but some effort is necessary if technical samples, i.e. nonenriched in57Fe, are to be studied. In many cases of practical importance, full information on the corroded surfaces cannot be got from Mossbauer spectra only, and a combination with Auger and photoelectron spectroscopies, in-including scanning and …

The state of iron in andalusite

Iron in andalusite (Al2SiO5) with concentrations of 1.5 … 4.3 wt-% has been reported in the literature to occupy mainly Al1 sites as Fe3+, and only small portions occupy Al2 sites as Fe3+ and Fe2+. In no case a magnetic hyperfine splitting has been found at temperatures above 77 K.

An ESCA and Mössbauer study of the oxide layer formed on steel in water containing chromate and chloride ions

Abstract The formation of oxidic layers on steel in chromate solutions was studied by photo-electron and Mossbauer spectroscopy. To simulate more aggressive realistic systems, some chloride ions were added to the solution. The layers formed under these conditions were found to be thicker by an order of magnitude than those formed in the absence of chloride ions. They probably consist of ferric and chromic oxides of the corundum type (Fe 1−2 Cr x ) 2 O 3 , with the Cr : Fe ratio being depth dependent. The oxide layer is subdivided into small regions behaving superparamagnetically. This heterogeneity of the layer is ascribed to the attack by the chloride ions. The structure of the oxides foun…

XPS study of leached glass surfaces

Abstract By use of a special deconvolution algorithm, it was possible to decompose the XPS O 1s signal into several components reflecting different oxygen bonds. The influence of exposure in vacuo, environmental atmosphere, distilled water, and in a polish solution as corrosive media on the surface of different glasses has been studied. The O 1s signals of fused silica, Na 2 O· n SiO 2 glasses, a BaO·SiO 2 and a BaOB 2 O 3 SiO 2 glass (Schott SK 16) were analyzed. On the glass surfaces, leached layers were formed and analyzed qualitatively and semiquantitatively by XPS and optical and infrared methods. As a reference, virgin surfaces of samples broken in ultrahigh vacuum have been used. T…

Studies of the Phosphatization of Steel and its Corrosion Products

The reaction of phosphoric acid with steel is a basic process in many technological procedures. A typical example is the pretreatment of steel surfaces for the application of coatings. The aim of the treatment is to clean the surface, to produce a homogeneousr tight, and smooth cover and to provide a reliable adhesion between the steel substrate and the coating. This example points out that the phase composition of the layer formed is of great interest, and that reactions with residues on the surface, such as oxides and corrosion products, have to be considered, too. The same holds for phosphate layers formed in order to modify the mechanical or corrosion behavior of steel surfaces. Because…

Quantitative XPS analysis of leached layers on optical glasses

The corrosion of optical glasses often reduces the utility of uncoated glasses as well as the adhesion of resistive coatings deposited onto corroded glasses. Photoelectron spectroscopy (XPS) was applied to study glass surfaces with respect to their surface corrosion. In particular, leaching by the influence of polish slurries, pure water, air and even residual gases inside a vacuum device was studied in detail. Pure quartz glass and different sodium and barium silicate glasses were broken in ultrahigh vacuum (4 × 10−10 mbar) for the determination of sensitivity factors of the different XPS signals. It was found that a quantitative determination of the surface composition of corroded and lea…

Study of very thin oxide layers by conversion and Auger electrons

Oxidic layers as thin as 20–30 A on α-Fe and stainless steel are studied by57Fe-DCEMS with K-conversion electrons and ICEMS. No indication of a vanishingf-factor could be found. Mossbauer spectra, recorded by use of LMM-Auger electrons (AEMS) and by electrons emitted with energies below 15 eV (LEEMS), contain information on the surface layer as well as on the bulk material, showing that part of these electrons are due to secondary effects and the high escape depths of K-conversion electrons.

A Mössbauer study of the crystalline structure of the passive film formed on iron in aqueous sulfate solution containing sulfite in low concentration

Electrochemically induced passivation of evaporated, enriched 57Fe in 0.5 mol dm−3 Na2SO4 + 0.001 mol dm−3 NaHSO3 aqueous solution (pH 6.5) was followed by conversion electron Mossbauer spectroscopy. The transformation of amorphous iron oxide or hydroxide into crystalline γ-FeOOH could be observed with the increase of the polarization time. The comparison of the original quantity of evaporated, enriched 57Fe layer on the surface of the samples with the dissolved iron, measured in the solutions after the polarization, proved the existence of pitting corrosion at this pH.

Changes of lead silicate glasses induced by leaching

Abstract The structural differences in the surface region between freshly fractured and leached silicate glasses containing 16.7, 18.8 and 44.4 mol% PbO, respectively, were investigated by photoelectron spectroscopy (XPS). The optical properties and the thicknesses of leached layers were determined by reflection measurements. The binding energies of the O1s signal components for untreated samples can be ascribed to non-bridging (NBO) and bridging (BO) oxygen and oxygen associated with lead as network former (OPb). The binding energy of OPb was found to be 529.1 ± 0.2 eV. For quantitative conclusions, relative XPS sensitivity factors were determined for oxygen, silicon and lead in these glas…

In-situ radiotracer studies of sorption processes in solutions containing (bi)sulfite ions—II. Low carbon steel

Abstract In this paper, time, potential and pH dependence of SO42− and HSO3− accumulations measured by an in-situ radiotracer method on surface oxide layers of low carbon steel are presented and discussed. This work is a continuation of a research program[1–5] and deals with the characterization of the sorption behaviour of low carbon steel in solutions containing sulfate and bisulfite ions (as a possible model of acid rain). From the experimental results it can be stated that 1. (i) the presence of bisulfite ions in the solution phase accelerates the corrosion of low carbon steel; 2. (ii) at E > 0.40 V the electrooxidation of HSO3− ions presumably proceeds to yield a steel surface covered …

Conversion electron Mössbauer study of vacuum and thermally treated vivianite

Natural vivianite samples were studied by Mossbauer transmission and conversion electron spectroscopy. The intensities of ferrous doublets in vivianite and the widths of the resonance lines depend strongly on the origin of the samples, on their preparation history, and on exposures in vacuo as well as on thermal treatments. An additional ferrous doublet appearing in samples after vacuum treatment can be ascribed to a tetrahydrate phosphate phase appearing at the surface due to dehydration. Heating at 413 K in dry air for periods of 15–240 min causes a higher oxidation and decomposition rate at the surface region than in the bulk of vivianite. All results do not confirm the assumption publis…

Influence of sulphite on the passivation of iron

Abstract Mossbauer spectroscopy and electrochemical measurements were used to study the passivation of iron and steels in a sulphite containing solution. The potentiodynamic curves show that passivation occurs at −140 mV potential vs saturated calomel electrode ( sce ). The main phase of the passive layer was found to be γ-FeOOH, while FeSO 4 ·H 2 O on the surface and FeSO 3 ·3H 2 O inside the layer were identified as minor phases in the case of polarization in a solution of pH 3.37. Only γ-FeOOH was observed on the surface of samples polarized at pH 6.6.

Investigation of ultrathin iron and iron/nickel layers prepared from Langmuir-Blodgett films

Oxidic and metallic iron and iron/nickel multilayers, formed after thermal and chemical treatment of Langmuir-Blodgett films, were investigated. Reduced iron-stearate multilayers were compared with evaporated films concerning their phase composition and their lateral homogeneity. The sequence of metallic and oxidic iron in the films after reduction was determined. Oxidic iron/nickel mixed layers can be prepared from Langmuir-Blodgett films, in which a magnetically non-ordered Fe3+ phase exhibiting a distribution of the quadrupole splitting is observed. After reduction of such layers, two metallic iron phases appear dependent on the nickel concentration. The hyperfine field distribution of t…

Low noise scintillation detectors with a P-47 thin layer screen for electrons of several keV

Abstract The applicability of a low-noise scintillation detector (ScD) for the registration of electrons of several keV energy has been studied employing photomultipliers (PM) of different types and sizes. With the application of a sedimented P-47 scintillation screen, the values of the low-energy sensitivity limit and those of the light conversion coefficient were determined as about 2.7–4.7 keV and 2.8–6.6 photoelectrons/keV, respectively, for the set of PM's (Philips-Valvo XP 2020, Philips-Valvo XP 2052, Philips-Valvo XP 2972, EMI 9124a) studied. It is concluded that such scintillation detectors might be used advantageously as electron counters in the range of E > 5 keV. Applications bel…

Mössbauer and TEM studies of the perovskite system (1-y)La2/3 $$A$$ 1/3TiO3·yLaFeO3

The microscopic nature of the Mossbauer phase analysis has been found as being particularly valuable in testing assumptions suggested by TEM results regarding the microdomain structure and the population of different lattice sites by iron ions in the perovskite system (1-y)La2/3\(A\)1/3TiO3·yLaFeO3 with 0.04<y < 0.25 (\(A\) is an A-site vacancy). This system was found to contain only Fe3+-phases which are stable under normal conditions, but moderate heating in vacuo causes a partial reduction of ferric ions to ferrous ions.

Electrochemical and conversion electron mössbauer study of corrosion induced by acid rain

Abstract The passivation of low carbon steel was studied in aqueous solution of 0.5M Na2SO4 +0.001M NaHSO3 (pH 3.5, 6.5 and 8.5) which can be considered as a model of acid rain. The used conversion electron Mossbauer spectroscopy (CEMS) with the complementary electrochemical investigations proved that the sulfite ions induce pitting corrosion at pH 3.5 and 6 5 while the measurements showed much weaker pitting at pH 8.5. The compositions and thicknesses of the passive films formed during the electrochemical treatments are determined from the CEM spectra. Only γ-FeOOH was found on the surface of the samples at pH 6.5 and 8.5. Nevertheless, at pH 3.5 the sextet belonging to Fe3C appears in the…

M�ssbauer study of the spatial distribution of the active species in Cs doped Fe2O3-V2O5 catalysts

From a Cs doped Fe2O3-V2O5 (Fe:V=1.4) catalyst exhibiting an inhomogeneous composition after calcination, three different fractions have been separated by visual inspection. One fraction has been found to consist of mainly α-Fe2O3, another one of mainly FeVO4. The third fraction (S1 in the text) is the catalytically most active fraction containing besides both of the former components an amorphous phase of FexVyOz and also the dopant. By combining the results from transmission and conversion electron Mossbauer spectra it has been concluded that the amorphous component is enriched in the surface region of the crystallites of the catalyst. In addition, the formation of a thin surface layer of…

Untersuchungen zur Reaktion von konzentrierter Phosphors�ure mit reinen und korrodierten Stahloberfl�chen

Mittels Mosbauerspektroskopie wurde gefunden, das sich aus Rostkomponenten neben den normalen Eisen (III)- und Eisen (II)-phosphaten auch ein saures Eisen (III)-phosphat bilden kann, wenn sie mit konzentrierter Phosphorsaure behandelt werden. Voraussetzung hierfur ist, das die Ausgangsphase eine reine Fe3+-Verbindung ist. Das saure Eisen(III)-phosphat, wahrscheinlich FeH3(PO4)2 · 2,5 H2O, enthalt Fe3+ in nahezu kubischer Umgebung, die Kristallstruktur hat jedoch niedrigere Symmetrie. Unterhalb von 28 K setzt eine magnetische Ordnung ein. Es sind zwei Falle mit verschiedener Spinstruktur und Verkantungen zu unterscheiden.

Optimization of a conversion electron Mössbauer spectroscopy gas flow He/CH4 proportional counter

A new detector for CEMS has been built and optimized with respect to the statistical quality of spectra obtained. The optimization has been performed by measuring Mosbauer and pulse height spectra at in- and off-resonance. Single channel analyzer settings were calculated by a new optimization routine. A comparison of different detector designs has been performed using the statistical utility rate of spectra obtained from a stainless steel foil. A procedure for determining optimal operating parameters for ICEMS gas flow proportional counters is proposed.

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

Integral electron Mossbauer 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 phosphate 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 Mossbauer spectra, consists mainly of γ-FeOOH, however in sulfite confining sulfate aqueous solution at pH 3.5 Fe 3 C and despite ex-situ circumstances FeSO 4 .H…

AES and CEMS analysis of the formation of layers on Si steel under thermal treatment in a flux of H2/water vapour

The near surface diffusion and reaction processes in iron-silicon steel (3.1 wt.%Si) during 10 min decarburization in water vapour/hydrogen have been studied. The decarburization temperature has been varied between 506 and 714°C for the fixed partial pressure ratio pH2O/pH2=0.017. An outer layer of SiO2 forms on the surface with its thickness increasing with temperature. From 600°C upwards, the decarburization process is hindered and a cementite layer is formed below the SiO2 layer. The formation of fayalite at the surface has been studied at a fixed decarburization temperature with pH2O/pH2 ranging from 0.017 to 0.49. The scale thickness reduces abruptly just before the ratio pH2O/pH2 nece…

Study of interface diffusion of Ti and TiN PVD layers by Bremsstrahlung-induced AES

The influence of heat treatment in ultrahigh vacuum (UHV) on Ti and TiN layers coated by physical vapour deposition (PVD) has been studied by AES, XPS and bremsstrahlung-induced AES. It could be concluded that up to 500 o C (1 h) the Ti layer does not change significantly. At the TiN/steel substrate interface, however, a counter-diffusion of nitrogen and adventitious oxygen takes place, resulting in partial nitridation of the steel substrate and oxidation of the coating

Conversion-electron M�ssbauer spectroscopy using 121Sb and a study of powdered ?-Sb2O3

It is shown that 121Sb Conversion-Electron Mossbauer Spectroscopy (CEMS) is possible even at room temperature. The parameters and peculiarities of 121Sb CEMS are summarized. An application to powdered Sb(III) oxide shows that the material on the surface of the grains is not oxidized to Sb(V) but has changed its crystal symmetry, while the bulk of the grains still exhibits the initial cubic-crystal phase.

A CEMS/AES study of the passivation of iron

The passivation of iron and steel (DIN 1623) was studied by integral and depth selective conversion electron Mossbauer 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 (γ-FeOOH) cover.

conversion electron Mössbauer study of low carbon steel polarized in aqueous sulfate solution containing sulfite in low concentration

The passivation of low carbon steel was studied in aqueous solution of 0.5 M Na2SO4+0.001 M NaHSO3 at pH=3.5 and 6.5. The found major components at pH-3.5 were: γ-FeOOH and Fe3C, and also FeSO4.H2O could be identified on the surface of the low carbon steel as a minor component. At pH-6.5, the passive film contained only amorphous iron(III)-oxide or oxyhydroxide.

Phasenumwandlungen in Korrosionsschichten auf Eisen: Mößbauerspektroskopische Untersuchungen

Zur Untersuchung der Korrosion von Stahlblechen wurde die mosbauerspektroskopische Phasenanalyse in Transmissions- und Streugeometrie eingesetzt. Die Korrosion von Stahlblechen fuhrt in einer Atmosphare von geringer Korrosivitat nach langen Expositionszeiten vorwiegend zu den relativ stabilen β-Phasen der moglichen Fe-Korrosionsprodukte. Bei durch HCl-Zusatz erhohter Korrosivitat ergibt sich eine Bevorzugung der Bildung von β-FeOOH und kein Auftreten der α-Phasen. Auch der Einflus von. Beschichtungen auf die Phasenzusammensetzung wird behandelt. Die Entstehung und Umwandlung der verschiedenen Fe-haltigen Phasen im Rost last sich anhand eines Stabilitatsdiagramms verstehen. Auch die Wirkung …

Quantitative determination of fayalite layers on iron by CEMS

In the processing of silicon iron (Fe-3%) Si), so-called ‘fayalite layers’ are formed. By CEMS, they were found to consist of an outer Fe3+-oxide layer and an inner Fe2SiO4 (fayalite) layer. Sometimes an additional wustite contribution was found. Thef-factor of fayalite was determined experimentally (ffayalite/fα-Fe=0.47±0.04) and, by use of it, the thicknesses of the layers on some silicon iron samples could be calculated from CEMS data.

Layer formation on silicon steel by processing in H2/H2O at elevated temperatures

Silicon steel (Fe-3wt%Si), as used for transformers and generators, has been annealed in wet hydrogen at elevated temperatures. The composition, sequence, and thicknesses of the layers found by conversion electron Mossbauer spectroscopy (CEMS) and Auger electron spectroscopy (AES) depth profiling for a 10 minutes anneal in different atmospheres are reported. In the range from 500°C to 720°C we observed carbide formation, indicating that the decarburization is hindered. Above 800°C, the layers consist of fayalite or of fayalite and iron oxides, depending on the oxygen potentialaO. At 843°C, the onset of iron oxide formation was found ataO=0.33.

Surface and Thin Film Analysis by Mössbauer Spectroscopy and Related Techniques

The main trend in current high-tech development is miniaturization. This holds for complex electronic devices, such as microprocessors, as well as for coatings, such as Langmuir-Blodgett coatings, optical components, such as fiber couplers, chemical devices, such as microreactors, mechanical components, such as micromotors, and many others. Development and production of components with dimensions in the micron and submicron range require the availability of appropriate analytical tools for chemical, physical, and morphological analyses. In close interaction with the development of microcomponents, many, more and more efficient, analytical methods have been developed, many of which are “surf…

Poster contributions

Surface versus bulk composition of a phosphate glass

Transmission and conversion electron Mossbauer spectroscopy as well as photoelectron spectroscopy were applied to study alterations of the surface layer of an iron containing industrial phosphate glass as compared with its bulk. In the surface layer, after polishing and exposure to ambient atmosphere, Fe 2+ is partially oxidized to Fe 3+ . This oxidation, however, does not increase the O/P ratio in this layer, because it goes along with a strong leaching of network modifiers. This leaching leads to a net decrease of the O/P ratio because it overcompensates the relative oxygen increase by Fe 2+ oxidation and by uptake of water

A CEMS-study of the passive layer on iron and steel

From AES, ICEMS, and DCEMS experiments it was concluded that the passive layer formed on steel in a phosphate buffer consists of γ-FeOOH. Its thickness increases from 0.5 to 3.5 nm throughout the passive region. It is covered by noncorrelated layers of a precipitate and an adsorbate.

The EFG in oxonium ferric orthophosphate hydrate and related compounds

The point cherge model was used to interpret the small quadrupole spilting of Fe3H15(PO4)8·5H2O by comparing it with related phosphates of known structure. The approximation is sufficient as long as octahedrally coordinated compounds are compared for which Vzz and η do not change their signs.

Technical Note:Study of the Cl−-Induced Breakdown of the Passive Layer on Steel

Abstract The Cl−-induced breakdown of the passive layer on a standard steel has an induction time that increases in a nearly linear fashion with the previous holding time (at the passivation potent...

The influence of phosphoric acid on steel and on its corrosion products: a Mössbauer spectroscopic approach

Mossbauer spectroscopy was used to study corroded iron after treatment with phosphoric acid or commercial rust transformers. It was found that treatment produced normal iron phosphates from metallic iron, hematite and FeO, and acid ferric phosphate FeH 3 (POI4I)I2I. 2.5H 2 O from alphaand gamma Fe 2 O 3 and alpha, beta, and gammaFeOOH. When these last are present, phosph oric acid treatment does not produce a protective, inhibiting layer. See also AATA 19-702. -- AATA

A study of electrochemically-induced corrosion of low carbon steel in a medium modelling acid rain

Complementary electrochemical, spectrophotometric and electron microsopic investigations were made in addition to the conversion electron Mossbauer spectroscopic (CEMS) measurements to learn more about the mechanism of corrosion of low carbon steel samples in aqueous sulfate and sulfite containing sulfate solutions (pH 3.5, 6.5 and 8.5). Passivation of iron in pure sulfate solution was studied in detail in earlier papers. In the present work, we used a solution containing both sulfate and sulfite anions to obtain more information about the effect of acid rain on low carbon steel samples. The compositions and thicknesses of the passive films formed due to the electrochemical treatments were …

Anodic layers formed on steel in phosphate buffer solution

In-situ gamma scattering and ex-situ conversion electron Mossbauer, and Auger spectroscopy were applied to investigate anodic layers on steel. Samples treated in the active potential range in phosphate buffer solution show a Fe(II)-phosphate deposit on the surface. After treatment in the passive potential region, only Fe3+was found to exist in the oxide layer. The passive layer does not consist of stoichiometric oxidic phases.

Ultrathin metal films and inorganic clusters via thermodesorption of LB films

Langmuir-Blodgett multilayers of cadmium arachidate and ferric stearate were investigated during heating in order to derive information on processes involved in thermodesorption and on the inorganic microstructures left on the substrate after thermodesorption. We studied these processes by X-ray induced photoelectron spectroscopy (XPS), interference enhanced reflection (IeR), Nomarsky microscopy, electron microprobe analysis and in the case of Fe57-ions by conversion electron Mossbauer spectroscopy (CEMS). Two different mechanisms of desorption were observed. In the case of cadmium arachidate multilayers it is shown that before desorption the film ruptures laterally and then forms droplets.…

Cluster formation during desorption of multilayers of fatty acid salts

Discrete bond model (DBM) of sodium silicate glasses derived from XPS, Raman and NMR measurements

In sodium silicate glasses, the fraction of differently bound Si species Q[i] (i = 0−4), depending on the number i of bridging oxygens bound to the quarternary silicon, is a function of stoichiometry and the Na/Si ratio. Sodium silicate glasses were investigated by high resolution X-ray photoelectron spectroscopy. To explain the differences in chemical shifts and linewidths of the O 1s signal of the bridging and the non-bridging oxygen as a function of alkali concentration, and extended glass model was developed. This new model takes into account the influence of the alkali concentration on the Q[i] distribution and on the appearance and concentrations of differently bound bridging oxygens …

Formation and characterization of oxidic and metallic Fe/Ni multilayers prepared from Langmuir-Blodgett films

Oxidic and metallic iron, nickel, and mixed iron/nickel mono- and multilayers were prepared by some treatments of iron- and nickel-containing Langmuir-Blodgett films. The layers were characterized by several surface-sensitive methods. Interactions between the iron and the nickel could be observed. The results are different to those obtained from disordered bulk alloys and from simple diffusion calculations.

The effect of energy-dependent detector efficiency in electron spectroscopic methods: XPS, AES and DCEMS

Systematic studies were performed to investigate the distorting effect of the electron energy dependence of the channeltron detector efficiency on the shape of data distributions in electron spectroscopy. In agreement with earlier results for electron energies up to 3 keV, it was found that a virtually energy-independent shape of the electron distribution might be achieved even in a very broad range of electgron energies (up to 15 keV) by appropriate selection of the operational high voltage of a channeltron. However, the efficieny of channeltrons was also found to depend on count rates, indicating one of the principal difficulties in comparing distribution recorded under different experime…