EPMA and X-Ray Diffraction of the Degraded Fuel Bundle from the Phebus FPT1 Test

 The degraded fuel rod bundle from the second Phebus test (FPT1) was examined at ITU, Karlsruhe. Metallographic and microprobe analysis of the degraded fuel pieces were carried out. The fuel samples from the upper bundle and cavity edge were porous and had remnants of thick oxidised cladding adhering to them. Electron microprobe analysis line scans across the cladding-fuel interface showed interdiffusion of U and Zr, with U diffusing down the grain boundaries of the oxidised cladding, while point analyses revealed noticeable amounts of Zr (1.5–4.2 wt%) in the UO₂ fuel. EPMA oxygen measurements revealed in the upper part of the bundle a superstoichiometry of x = 0.3–0.4 in UO _2 + x , indicating that fuel fragments in this position had undergone considerable oxidation. X-ray diffraction of the corium pool disclosed a deformed cubic fluorite lattice of UO₂. The lattice parameter of a = 5.2984 ? was considerably reduced compared with pure, stoichiometric UO₂ and was consistent with a lattice containing approximately 45 mol% ZrO₂ that had undergone little oxidation. The corium’s nominal composition of (U_0.5Zr_0.5) O₂ also corresponded to its observed single phase microstructure.     

Energy Dispersive X-Ray Fluorescence Analysis and X-Ray Microanalysis of Medieval Silver Coins

 Austrian medieval silver/copper coins were investigated at their surfaces by energy dispersive X-ray fluorescence analysis (EDXRF) and at the cross-sections by X-ray microanalysis in the scanning electron microscope (SEM/EDX) in order to estimate the error occurring when corroded objects of art and archaeology are analyzed on the surface by non-destructive methods. Additionally, Ag/Cu-standards were treated in diluted sulphuric acid and the depletion of copper on the surface was measured by EDXRF. By calculating the ratio of the Ag-K/Ag-L intensity the process of blanching could be studied.     

X-Ray Emission from Thin Films on a Substrate – Calculation and Experiments

 Monte Carlo simulation of electron transport in solids is widely used in electron microscopy, spectroscopy and microanalysis. The reliability of physical models incorporated in a Monte Carlo code is usually checked by comparing with experimental results. Elastic or inelastic collisions are usually considered as the basic interactions of electrons with atoms. In our Monte Carlo code the single scattering model is employed for simulation of X-ray emission from thin films of Au on the Si substrate. The electron beam energy was in the range 10–30 keV, the take-off-angle was 40°. The simulated values of X-ray production were calculated in our Monte Carlo code using several models of ionisation cross-sections. For the emitted intensities the depths of inelastic collision and X-ray absorption were taken into account, then the k-ratios were calculated. These data were compared with experimental values of k-ratios calculated from X-ray intensities of Au M and Au L characteristic lines. We followed mainly the dependence of the k-ratios of the film element on film thickness. The film thickness was in the range 0.05–1 μm. Reasonably good agreement was found for dependences of X-ray intensity on film thickness in the whole energy range and for both lines, especially for Powell’s model of the ionisation cross-section.     

X-Ray Microanalysis of Thin Surface Films and Coatings

 The paper gives an overview of the present knowledge in the field of X-ray analysis of surface films and more generally stratified specimens. The aim of the paper is not to report the details and formulas of the available quantitative procedures, but to concentrate on the general ideas and orders of magnitude illustrating the capability and limits of the method, and on the optimal adaptation of the operating conditions to every particular problem. The various specific pitfalls which can be encountered are pointed out, in particular the fluorescence effects when using high-energy X-ray lines, or the anomalies due to chemical bonding, absorption uncertainties, and contamination effects when soft radiations are employed.     

Basics, Possibilities and Limitations of the Microscopic X-Ray Fluorescence Analysis

 Microscopic X-ray fluorescence (MXRF) analysis was used to investigate different samples: meteorites, Jasper, coated glas and, reference materials. The element distribution within sections of two different meteorites have been determined – one metal rich and one oxide rich. The metal rich showed a matrix of Fe with Ni-, Ti-, and Si-enriched regions. The oxide rich also showed a Fe rich matrix and regions with different concentrations of other elements. A reference sample with a flat and polished but systematically tilted surface was used to assure, that roughness of the sections of the meteorites has only negligible influence. Nondestructive investigations in Jasper with included Stromatolithes, which were fossilized more than 2 billion years ago, showed the Stromatolithes to have Fe as main element instead of Si in the Jasper matrix. The thickness of Yb-layers on glas was determined from the intensity of the Yb fluorescence peak. Calibration was done by using a sample without coating and a reference sample whose thickness of the layer was determined by XRD reflectometry. Futhermore it has been shown that materials can be analysed even if mounted in glas capillaries or covered by plastic foils. By using Mark capillaries the elements from S to U may be detected instead of Na to U while working in vacuum mode.     

Indirect Measurement of Biologically Important Compounds by Means of X-Ray Microanalysis

 The main objective of our work was to investigate the possibility and usefulness of indirect methods in X-ray microanalysis for the quantification of biologically important compounds. Metallothionein-like proteins (MT-like proteins) from kidney and liver, rich in sulfur were chosen as an indicator of heavy metal presence in cells and their environment. Tissues from goldfish (Carassius auratus gibelio) were sampled after short and prolonged periods of exposure to Co⁺², CrO₄ ⁻², Pb⁺², Cu⁺² and control treatment and prepared for histochemical staining for peroxidated thiolate groups. Commonly used –S–S– bonds dye (Nitro Red) was replaced with iodine atoms and they were quantified at L line by means of X-ray microanalysis combined with SEM. After fish treatments with heavy metal solutions changes in MT-like proteins and in I atom contents were expected. There was statistically significant decrease in MT-like proteins level in kidney after lead treatment (Pb/C = 0.62). In liver a statistically significant increase in MT-like proteins concentration was observed after chromium, cobalt and lead ions treatment in comparison to control animals. The following ratios were noted: 3.04 for Cr/C, 2.18 for Co/C and 2.10 for Pb/C. Our finding indicates that the method of indirect measurement of MT-like proteins in fish and other animal tissues is possible. The concentration of iodine atoms is above their detection level by EDS and their changes are possible to identify. During histochemical procedures it is worth taking into account sample preparation methods which might disturb the quality and quantity of the analysed material.     

Identification of Composite Cement Hydration Products by Means of X-Ray Diffraction

 In this paper the effect of limestone, fly ash, slag and natural pozzolana on the cement hydration products is studied. Four composite cements containing limestone, natural pozzolana from the Milos Island, slag and fly ash have been produced by intergrinding clinker (85%), the above main constituent (15%) and gypsum. The grinding process was designed in order to produce cements of the same 28d compressive strength. The hydrated products, formed after 1–28 days, were studied by means of X-ray diffraction. Unhydrated calcium silicate compounds of clinker and hydration products such as C*H, C*S*H and ettringite are clearly observed. Although there is not significant differentiation among samples hydrated for the same period of time, modifications of calcium aluminate hydrates as well as sulfoaluminate hydrates, are indicated by the XRD patterns. In samples of limestone cement, monocarboaluminate is formed in the first 24 hours and is still present after 28 days.     

Microanalytical Techniques Applied to Phase Identification and Measurement of Solute Redistribution at the Solid/Liquid Interface of Frozen Fe-4.3Ni Doublets

 A Fe-4.3Ni alloy has been solidified directionally by using the Bridgman system. The solidification conditions were chosen to obtain an oriented cellular structure of δ-ferrite. These are: a positive temperature gradient of about 60 K/cm and a growth rate of 6.6 μm/s. A change in these conditions can lead either to the formation of austenite or to the competitive growth of δ-ferrite/γ-austenite. The solid/liquid interface of δ-ferrite cells has been frozen and double instability has been revealed at the tip of the cells. The instability is described as the first harmonic wave of fundamental undulation, which appeared at the formerly planar solid/liquid interface. This means that a doublet structure is formed only with the imposed specific conditions of solidification. The Ni-solute redistribution after back-diffusion has been measured across the δ-ferrite doublet. Results of energy dispersive X-ray (EDX) measurements on the distribution of Ni and Fe correspond well to the theoretical prediction for redistribution developed especially for oriented structure formation (two dimensional solidification). Additionally, electron backscattered diffraction from the bulk Fe-4.3Ni alloy sample allowed us to determine the local structure, i.e. the distribution of single crystallite orientations in the microstructure. A unique correlation between fluctuations of the Ni-solute redistribution and crystalline orientations in the δ-ferrite doublets has been demonstrated. Moreover, a relationship between geometrical asymmetry of the doublets and solute redistribution has also been found.     

High-Spatial-Resolution Low-Energy Electron Beam X-Ray Microanalysis

 Performing X-ray microanalysis at beam energies lower than those conventionally used (< 10 keV) is known to significantly improve the spatial resolution for compositional analysis. However, the reduction in the beam energy which reduces the X-ray interaction diameter also introduces analytical difficulties and constraints which can diminish the overall analytical performance. This paper critically assesses the capabilities and limitations of performing low beam energy, high spatial resolution X-ray microanalysis. The actual improvement in the spatial resolution and the reduction in the X-ray yield are explored as the beam energy is reduced. The consequences for spectral interpretation, quantitative analysis and imaging due to the lower X-ray yield and the increased occurrence of X-ray line overlaps are discussed in the context of currently available instrumentation.     

Energy Dispersive X-Ray Spectrometry by Microcalorimetry for the SEM

 Analytical X-ray spectrometry for electron beam instruments has advanced significantly with the development of the microcalorimeter energy dispersive X-ray spectrometer (μcal EDS). The μcal EDS operates by measuring the temperature rise when a single photon is absorbed in a metal target. A cryoelectronic circuit with electrothermal feedback and a superconducting transition edge sensor serves as the thermometer. Spectral resolution approaching 4.5 eV for high energy photons (6000 eV) and 2 eV for low energy photons below 2000 eV has been demonstrated in energy dispersive operation across a photon energy range from 250 eV to 8 keV. Spectra of a variety of materials demonstrate the power of the μcal EDS to solve practical problems while operating on a scanning electron microscope platform.     

Trace Analysis by Heavy Ion Induced X-Ray Emission

 Various K-, L- and M-shell X-ray production cross sections are measured for heavy ion impact on elements in the range Z ₂ = 13 to 83. The ion species range from Z ₁ = 10 to 36, and ion energies from 1 to 16 MeV are used. Enhanced cross sections are observed when the projectile K- or L- binding energy is similar to the energy of the target K-, L- or M-shell. This effect is used to improve the analysis sensitivity for selected elements. As an example trace analysis of Fe in glass with V, Mn, Co and Ni ions is investigated. Results are compared with proton induced X-ray emission analysis on the same samples. In these samples Fe-K_α X-ray production is similar for irradiation with 3 MeV protons and 14 MeV Ni ions. However the signal to background ratio is four times higher for the irradiation with Ni ions as compared to irradiation with protons. Advantages and drawbacks of heavy ion induced X-ray emission for quantitative analysis compared to proton induced X-ray emission analysis are discussed.     

Microspectrometric Investigation of Petrified Wood from South-Eastern Poland

 The investigation of the interesting collection of the petrified wood from Bondyrz, Roztocze, south-eastern Poland, has been continued. Two kinds of microprobes such as electron microprobe from the Catholic University of Lublin and synchrotron-based X-ray microprobe from LURE, Orsay, were applied to detect the elements associated with the main component – silica and their spatial distribution and interrelations. The distribution of carbon in the petrified material has been established, which is important since that element is the main remains from the history of the trees. The carbon distribution was characteristic – it concentrated on a place of primordial dark wood. The distribution patterns of the other elements were either similar to that of carbon (Cu, Pb) or they concentrated in separate inclusions (Fe, Al, K, Na, Ca). The replicating mode of the original wood pattern in silica and carbon-containing material was explained. Some indications about the composition of the primordial petrifying solution, the rate of the petrifaction process and the recent coloration of the sample could be concluded from the compositional patterns of silica. The boundary between totally and partially petrified zones could be well observed. Received October 2000. Revision March 6, 2001.     

Determination of Nitrogen in Duplex Stainless Steels by EPMA

 We describe the quantitative determination of low nitrogen contents (< 1 %wt) in highly-alloyed, duplex stainless steels by EPMA using a calibration curve. Five monophasic stainless steels with various nitrogen concentrations were used for the calibration curve, namely, three highly alloyed steels prepared in the laboratory, with nitrogen contents 0.066, 0.565 and 1.016 %wt and two industrial alloys with nitrogen concentrations 0.174 %wt and 0.023 %wt. For these samples, the plot of nitrogen X-ray intensities versus nitrogen contents exhibited an acceptable linear relationship. Average nitrogen contents of the analysed duplex alloys were found to vary in the range < 0.045–0.07 %wt in ferrite and 0.52–0.77 %wt in austenite. These results suggest that the nitrogen solubility limit in ferrite has been reached; on the other hand, nitrogen solubility in austenite increases due to the high manganese and low nickel contents.     

Monte Carlo Simulation of Electron Transport and X-Ray Generation. II. Radiative Processes and Examples in Electron Probe Microanalysis

Theoretical models for Monte Carlo simulation of radiative processes, i.e. bremsstrahlung and characteristic x-ray emission, are presented. Possible strategies for simulating electron transport are briefly described. For mechanisms involving energy loss and angular deflections, difficulties for strict implementation of accurate numerical differential cross sections still remain due to the strong correlations between these variables. Practical solutions for the case of inelastic collisions and bremsstrahlung emission are described. Comparisons of simulation results with experimental data for several problems of interest in electron probe microanalysis are presented.     

Detector Calibration and Measurement of Fundamental Parameters for X-Ray Spectrometry

Energy-dispersive X-ray spectrometry offers the opportunity for a fast and reliable determination of the composition of a specimen. For fundamental parameter based quantification, detailed knowledge of the X-ray generation cross sections and of the detection system’s efficiency is required. The detection efficiency is determined comparing the measured and calculated spectrum of undispersed synchrotron radiation (SR) from the electron storage ring BESSY II in the spectral range from 0.1 keV to 100 keV. Alternatively, monochromatized SR in the spectral range from 0.1 keV to 60 keV is used to determine the detection efficiency with a typical relative uncertainty of 1% to 2% by direct comparison with a reference detector. Employing well-calibrated detectors and monochromatized SR of well-known radiant power and high spectral purity, fluorescence yields have been investigated and resonant Raman scattering was studied as an example of a basic effect creating spectral background.     

Analytical Potential of EDS at low Voltages

 This paper addresses some of the principles underpinning chemical microanalysis of bulk specimens in the scanning electron microscope using low beam voltages ( ≤5 kV) and energy dispersive x-ray spectrometry. The advantages of this relatively new method lie primarily in the strong dependence of the sample penetration range on the electron beam energy (∼10x from 5 kV to 20 kV). This directly yields superior spatial resolution and sensitivity for the analysis of sub-micron particles, surface films and at interfaces. The correspondingly shorter x-ray escape range reduces the importance of the complex matrix absorption and fluorescence terms; the parameters for which may not always be known accurately. A useful x-ray signal can only be generated with a beam energy which is at least 1.3x the excitation energy for the relevant characteristic x-rays. Low voltage fluorescent yields are relatively low and depend strongly on overvoltage (U < 3) and low voltage x-ray signals are relatively weak. These considerations lead to the development of a radical new instrument which produces 9000 counts per second from an Aluminium target with a < 2 nm probe containing 0.2 nA of current at 5 kV, fast submicron resolution x-ray maps ( < 0.1 μm is possible), and close to 1 nm electron image resolution at 1 kV. The greatly improved (15x) EDS sensitivity and superior electron and x-ray imaging are being used to extend, to explore and to exploit more fully the superior performance envelope of the SEM with EDS at low voltages.     

Chromate-Free Zinc Conversion Coatings Characterised by Grazing Incidence X-Ray Diffractometry

 Alternative processes for chromate conversion coatings on zinc represent a research challenge for environmental reasons. A potential concept yielding a promising corrosion behaviour without the need for toxic chemical additives is the application of alternating currents (AC) together with the addition of inorganic nitrogen compounds in an electrochemical bath. A first grazing incidence X-ray diffractometry (GIXD) study of the composition and crystallinity of this novel conversion coating system is presented. GIXD has been employed because this technique has proved to be successful in the analysis of electrochemically formed conversion coatings down to 10 nm thickness. Various ion additives like and in NaOH solution were applied in the AC treatment. The nitrite anion, , yielded the best result. It increased the generation rate and crystallinity of the passive layers. The ratio of the crystalline ZnO to Zn(OH)₂ content could be influenced by the AC amplitude and the AC cycling time. GIXD decisively contributed to the improved understanding of this chromate-free zinc conversion process.     

Chemical Interactions by Low-Energy Electron-Induced X-Ray Emission Spectroscopy, LEXES

 The possibilities presented by low-energy electron-induced X-ray emission spectroscopy to study chemical interactions in solids are discussed. Examples of change observed for the emissions between core levels as a function of the chemical environment of the emitting atoms are given. By comparing the partial densities of the valence states associated to each type of atoms in the compound, it is shown that the strength of the metal-ligand interactions can be obtained. Information on the charge densities around each type of atoms can be deduced. Application to the study of the interactions at the atomic scale to solid–solid interfaces is presented.     

EDX-Spectra Simulation in Electron Probe Microanalysis. Optimization of Excitation Conditions and Detection Limits

Standardless determination of absolutely calculated concentrations (P/B based) has been successfully applied for over a decade. The PUzaf-method [1, 2] works without normalization to 100 per cent and without any information in addition to the spectrum, apart from excitation conditions (E ₀, geometry) and detector parameters. The simulation of EPMA spectra is simply the inverse procedure of this real standardless spectra evaluation. The absolute calculation of P/B-ratios based on a fundamental parameter method and a reliable computation of bremsstrahlung over the entire distribution of energies are the basis for the simulation. The accuracy of the data base is crucial for the quality of a simulation [4]. The addition of detector effects and count-statistics are necessary to compute the artificial spectra close to a real EDX data acquisition.     

Analytical X-Ray Microscopy on Psaronius sp. – A Contribution to Permineralization Process Studies

 290 Million years old petrifactions from the Lower Permian Rotliegend of Chemnitz were examined by analytical X-ray microscopy to determine their chemical composition. Mappings show the inhomogeneous distribution of the involved elements, which may reflect the former plant anatomy, as well as some contemporaneous processes of permineralization (with silica and fluorite) and agate-formation. Most prominent advantages of the analytical X-ray microscopy are the low preparation expense of the museum samples, the analysis scanning range and the X-ray spot diameter suitable with the dimension of the fossil plants.