On the merits of conversion electron Mössbauer spectroscopy in geosciences

Described are some applications of conversion electron Mössbauer spectroscopy (CEMS) in geosciences. It is shown how easily this technique can be applied in existing Mössbauer laboratories to investigate natural samples. Some examples demonstrate the kind of information CEMS can give on the weathering history or mechanical properties of samples. The possible application of CEMS on Mars is discussed.     

Layer-by-layer epitaxial growth of polar FeO(111) thin films on MgO(111)

We report on the structural properties of epitaxial FeO layers grown by molecular beam epitaxy on MgO(111). The successful stabilization of polar FeO films as thick as 16 monolayers (ML), obtained by deposition and subsequent oxidation of single Fe layers, is presented. FeO/MgO(111) thin films were chemically and structurally characterized using low-energy electron diffraction, Auger electron spectroscopy and conversion electron Mössbauer spectroscopy (CEMS). Detailed in situ CEMS measurements as a function of the film thickness demonstrated a size-effect-induced evolution of the hyperfine parameters, with the thickest film exhibiting the bulk-wüstite hyperfine pattern. Ex situ CEMS investigation confirmed existence of magnetic ordering of the wüstite thin film phase at liquid nitrogen temperature.     

Mössbauer Study of Thin Iron Film Beryllization

Beryllium coating of the iron foil is made by means of magnetron sputtering. Mössbauer studies are performed by means of two registration techniques: conversion electron Mössbauer spectroscopy (CEMS) and the γ-ray technique in absorption geometry. Performed investigations confirm the original thermodynamic approach to creation of thermally stable multi-layer materials.

     

Effect of N 2 + ion implantation on the oxidation behaviour of Fe50Ni50 alloy

The high temperature oxidation behavior of Fe₅₀Ni₅₀ alloy foils implanted with 100 KeV N₂ ⁺ ions at a different dose values is studied by using the technique of conversion electron Mössbauer spectroscopy (CEMS). It has been shown that the implanted foils exhibit considerable adherence of scales and higher oxidation resistance as compared to the virgin foils. This excessive adherence of scales to the surface and higher resistance to oxidation of implanted samples is attributed to nickel enrichment in the surface layers. Various oxides of Fe, Ni and Fe?Ni are identified from the hyperfine interaction parameters of the corresponding CEMS spectra and also from x-ray diffraction measurements.     

Conversion electron Mossbauer spectra of very thin gold films

Conversion electron Mössbauer spectroscopy of the 77.3 keV transition in¹⁹⁷Au is shown to be three orders of magnitude more sensitive than the usual gamma-ray transmission technique. CEMS spectra of metallic gold films as thin as 10–100 μg/cm² (i.e. 5–50 nm) were measured.     

Depth sensitivity of X-e− coincidence Mössbauer scattering spectra

The performance of the X-ray — e⁻ coincidence technique for recording depth selective⁵⁷Fe CEMS spectra was investigated. The technique proved useful for selection of K-shell conversion electrons (7.3 keV) from a beam of back scattered electrons. This makes it possible to observe the depth sensitivity of CEMS spectra recorded with an He/CH₄ flow proportional counter.     

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 Mössbauer 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 less clustered and are distributed throughout the whole layer.     

A cems study of119Sn ion-implanted into Ni

Conversion electron Mössbauer spectroscopy (CEMS) was applied to study the behaviour of¹¹⁹Sn atoms implanted into Ni at the accelerating energy of 100–400KeV and doses of 5×10¹⁵–5×10¹⁶ ions/cm² at room temperature. All CEMS spectra were measured at room temperature and successfully analyzed by two components. The energy and dose dependence of CEMS spectra were well explained by the depth distribution of¹¹⁹Sn atoms.     

基于S7-200PLC的CEMS系统程序设计及优化研究

以某电厂4×600 MW机组脱硫烟气连续排放监测系统(CEMS)为背景,本文介绍了下位机S7-200 PLC及上位机Fame View组态软件在CEMS数据采集与处理子系统中的应用。重点阐述了CEMS下位程序的设计及上位机组态功能实现原理,针对现场实际情况进行分析,提出了程序优化方案。实践证明优化后的程序,可提高CEMS数据可靠性和有效性。本文所优化设计的CEMS系统程序已在某电厂长周期运行,系统各项功能正常,运行特性良好,达到了预期目的。     

Conversion electron Mössbauer spectroscopy study of growth and nature of corrosion products on mild steel exposed to different environments

In this study, conversion electron Mössbauer spectroscopy (CEMS) has been utilized for identifying the nature of initial corrosion products formed on the surface of steel under different environments and measurement of relative thickness of corrosion products formed. CEMS studies on mild steel exposed under different environments, viz. mild steel sprayed with (1) distilled water (2) 3% NaCl and (3) mild steel exposed to SO₂ were carried out. The initial stable product of corrosion is found to be γ-FeOOH, which will transform into other oxyhydroxides and oxides, depending on environments. The mechanisms for the corrosion processes occurring under different conditions are also discussed.     

Preparation and characterisation of electrodeposited amorphous Sn-Co-Fe ternary alloys

Electrochemical deposition was investigated as a process to obtain alloys of Sn-Co-Fe, which to date have not been reported in the literature. A constant current technique was used to electrochemically deposit tin-cobalt-iron alloys from a gluconate electrolyte. The gluconate system was chosen as an electrolyte, which could potentially provide an environmentally safe process. The effect of plating parameters such as current density, deposition time, temperature and pH are discussed. Results are reported for current density and plating time using an electrolyte temperature of 20-60 °C and pH of 7.0 in relation to phase composition, crystal structure and magnetic anisotropy of the deposited alloys.Investigations were conducted using ⁵⁷Fe conversion electron Mössbauer spectroscopy (CEMS), ¹¹⁹Sn CEMS, transmission Mössbauer Spectroscopy and XRD. The ⁵⁷Fe and ¹¹⁹Sn CEMS spectra and XRD showed that the dominant phase in the deposits was amorphous Sn-Co-Fe. The relative area of the 2nd and 5th lines of the sextets representing the magnetic iron containing phases was found to decrease continuously with increasing current density while at the same time no significant changes in the magnetic anisotropy was found with plating time. Magnetically split ¹¹⁹Sn spectra reflecting a transferred hyperfine field were also observed.A range of good quality amorphous Sn-Co-Fe ternary alloys was obtained over a range of operating conditions from an environmentally acceptable gluconate electrolyte.     

Conversion Electron Moessbauer Spectroscopie Studies on Ion Implanted Iron Layers

Conversion electron Moessbauer spectroscopy (CEMS) is a method very suitable for the study of ion implanted iron. It is demonstrated on nitrogen and phosphorus implanted iron layers. Using this technique not the 14.4-keV-gamma-rays as in the case of the conventional Moessbauer transmission experiments but the conversion and Auger electrons are detected. These electrons have a maximum energy of 7.3 keV. The Moessbauer signal can be obtained from a surface layer of about 300 nm. But the main fraction of the signal, namely 65%, comes from the first 50 nm. This range is just interesting for ion implantation. Depending on the test conditions different iron nitrides are formed by the nitrogen implantation and the phosphorus implantation can result in both amorphization and compound formation in the implanted layer.     

Titanium and carbon implantation of iron

Pure iron foils have been implanted with Ti and with Ti plus C and characterized by conversion electron Mössbauer spectroscopy (CEMS) and Auger electron spectroscopy (AES). Both paramagnetic and magnetic phases are observed and attributed to amorphous Fe?Ti?C alloys of differing Ti and C contents. Estimates of the thicknesses of the amorphous layers based on the CEMS data are in good agreement with the AES concentration depth profiles.     

Is a coating part of the substrate? The case of vanadium carbide on steel

Metallic surfaces, especially that of steel, are generally protected by various types of coatings. This paper presents some of the results of CEMS studies currently being made on mild steel substrate coated with a thin layer of vanadium carbide (VC). CEMS studies were done before and after coating. The internal magnetic field was found to be oriented at an angle of 48 degrees with respect to the transverse surface of the steel sample. After coating with VC at 950 °C, this value was reduced to 39 degrees. Molecular orbital calculations indicated that the electron density along the surface of the steel is significantly changed when the VC layer is formed, which leads to the changes in the magnetic field directions that are observed. The experimental data therefore reveal that vanadium from the coating diffuses into the iron substrate.     

Cems in non conducting surfaces with a parallel plate avalanche counter

The counter operation of a parallel-plate avalanche counter (PPAC) and the preparation of non conducting samples for conversion electron Mössbauer spectroscopy (CEMS) are described. Spectra of glass-ceramic materials and archaeological ceramics are shown.     

Interface study of Ag/57Fe/Ag trilayer using Mössbauer and X-ray standing wave analysis

Interface of Ag/⁵⁷Fe/Ag trilayer has been studied with a depth resolution of a fraction of a nanometer using x-ray standing waves generated by a W/Si multilayer mirror used as a substrate. Two interfaces of 38 Å thick Fe layer in Ag/⁵⁷Fe/Ag trilayer are clearly resolved. It is found that the rms roughness of the two interfaces Fe-on-Ag and Ag-on-Fe are 10 ± 1.0 and 6 ± 1.0 Å, respectively. Conversion electron Mössbauer spectroscopy (CEMS) has been used to get information about the volume fraction of the intermixed region and the estimated roughness from the relative area of the two sextets of CEMS spectra is found to be 7.0 Å which is consistent with the average roughness obtained by X-ray fluorescence measurements. However, the asymmetry of the interfaces can not be inferred from CEMS measurements.     

CEMS characterisation of Fe/high-κ oxide interfaces

The interfaces between Fe and different high-κ oxides are investigated by means of conversion electron Mössbauer spectroscopy (CEMS). Information on the magnetic ordering at the interface is obtained from the magnetic hyperfine splitting of the Mössbauer spectra. The reactivity of the Fe atoms at the interface (intermixing) is also estimated by CEMS. X-ray diffraction (XRD) and X-ray reflectivity (XRR) provide additional information on the intermixing and different phases present at the interface. CEM-spectra show the presence of both ferromagnetic and paramagnetic phases. CEMS and XRD results show that the Fe/HfO₂ and Fe/Al₂O₃ interfaces are the least reactive. The degree of intermixing between Fe and the high-κ oxide is determined by the oxide surface roughness.     

Chemical reactions induced by 40 keV He+ ions in Fe3O4 and α-Fe2O3

The chemical reactions induced by 40 keV He⁺ ions in α-Fe₂O₃ and Fe₃O₄ were investigated by the conversion electron Mössbauer spectroscopy(CEMS). Magnetite(Fe₃O₄) was formed upon the bombardment of α-Fe₂O₃, whereas no change was observed in Fe₃O₄. The initial G value for Fe₃O₄ formation is estimated to be 3.5×10^?4 for 100 nm depth from the surface. The application of CEMS and sputtering technique to ion bombardment chemistry is discussed.     

119Sn conversion electron Mössbauer spectrometric (CEMS) study on transparent conductive ITO and tin oxide films

Indium-tin oxides (ITO) films were prepared on glass by Ar ion sputtering, ion plating and electron beam melting in vacuum, and tin oxide films were prepared by chemical vapour deposition (CVD) of SnCl₄ in methanol containing HF. The chemical state of samples prepared was analyzed by CEMS. ITO films, produced from ITO source materials with higher solubility of tin oxide, showed lower electric resistivity. Amorphous ITO films had larger quadrupole splitting than crystalline ones. The tin oxide films were exposed in hydrogen plasma and hydrogen gas and the change of these films was also assessed by CEMS.     

The characterisation of iron-containing intermetallic phases within industrially cast aluminium

⁵⁷Fe conversion electron Mössbauer spectroscopy has been used to investigate the intermetallic phases near the surface of a D.C. cast aluminium ingot. The CEMS data is used with SAAES (selected area Auger electron spectroscopy) and SAXPS (selected area X-ray photoelectron spectroscopy) data to propose a model of the surface region above the grain boundaries.