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This contribution provides an overview of the BAMline synchrotron radiation beamline, which specializes in hard X-ray spectroscopy techniques for materials research. The BAMline offers X-ray absorption spectroscopy (XAS), x-ray fluorescence spectroscopy (XRF), and tomography to study materials' electronic structure, chemical composition, and structure. Key capabilities include standard and dispersive XAS for electronic structure, micro-XRF for elemental mapping, coded aperture imaging, and depth-resolved grazing exit XAS. The BAMline enables in situ characterization during materials synthesis and functions for energy, catalysis, corrosion, biology, and cultural heritage applications.
Ongoing developments like the implementation of machine learning techniques for experiment optimization and data analysis will be discussed. For instance, Bayesian optimization is being used to improve beamline alignment and scanning. An outlook to the future, where the BAMline will continue pioneering dynamic and multi-scale characterization, aided by advanced data science methods, to provide unique insights into materials research, will be given.
Fourteen hollow and one cast anthropomorphic and zoomorphic figurines produced in Incan times for ritual offerings from the Ethnologisches Museum in Berlin were selected to investigate the technologies and alloys used for their fabrication with portable optical microscopy and non-destructive XRF elemental analysis. This group of gold and silver figurines includes typical specimens of the Inca production, such as the four silver figurines from the Island Coati in Lake Titicaca and the two gold figurines from Pachacamac, as well as specimens that are seldom present in collections, which makes them atypical. In addition to the tall figurines with atypical hair or standing pose, one bicolour figurine half silver, half gold) and another with coloured inlays were included in this study for comparison. The large majority of the silver specimens are made from very high quality alloys and the gold figurines are made from alloys containing low copper contents and silver ranging from 30wt% to 52wt%.
We report on the trace analysis of copper and iron impurities in multicrystalline silicon wafers with the microbeam X-ray fluorescence (µ-XRF) technique. The efficiency of solar cells, which are based on multicrystalline silicon wafers, is strongly influenced by minor contamination with metals such as copper and iron. Application of compound refractive lenses (CRLs) in µ-XRF allows versatile two-dimensional mapping of relevant contaminations and localization of their sites of deposition. In this context, the measured bulk average limit of detection (LOD) was one picogram of iron and copper per gram of silicon. We suggest that µ-XRF is a valuable tool for non-destructive spatial (3D) quantification of metal impurities in a wide range of materials and devices whose functioning could be critically affected by impurities.
Partial least squares (PLS) regression-based methods have been proven to be a good alternative for quantification in X-ray fluorescence spectroscopy. These methods are fast and easy to use though giving satisfactory results under certain conditions. One of these conditions is the necessity of having a great number of spectra to build the model (training set). The choice of the constituent concentration range in the training set has a big influence on the accuracy of the model. Better accuracy is obtained if the model is built in relatively narrow regions containing (or close to) the real concentration value.
In the present work, Monte Carlo (MC) simulated spectra are used to form the training set. The advantage to use MC generated training spectra is the unlimited availability of perfect standards.
This paper aims to improve the accuracy of the method by introducing a multiple step procedure in order to build the PLS model using narrow concentration range close to (or containing) the real concentration values in the samples to be measured.
This approach consists of an initial guess of the constituents' concentrations and a preliminary PLS model before building the final model. The prediction of ten MC simulated alloy standard samples containing Ti, Mn, Fe, Co, Cu, Zn, Sr, Zr, and Mo using this method allowed to have average relative prediction errors less than 5% for elements with narrow concentration ranges.
High Speed, High Resolution imaging spectrometers based on pnCCDs for XRF and XRD applications
(2016)
For many years pnCCDs have been well known as X-ray detectors for spectroscopic imaging in many fields of science: X-Ray Fluorescence analysis (XRF), X-ray Diffraction (XRD) with light sources in large accelerator facilities as well as with laboratory light sources or with X-rays from celestial sources in X-ray astronomy. A brief introduction in GEXRF (Grazing Emission XRF) measurements with a laboratory laser produced plasma source will be given, PIXE (Particle Induced X-ray Emission) measurements and D2XRF (Double Dispersive X-Ray Fluorescence) and Slicing experiments with pnCCDs coupled to polycapillary optics performed at the BESSY synchrotron will be shown. Energy-dispersive Laue diffraction with ultra-hard X-rays for the analysis of defects in metals will conclude the overview of spectroscopic X-ray imaging measurements in the field of structure and dynamics of matter.
Studies by Synchrotron Radiation-X-Ray Fluorescence (SR-XRF) for the search of the presence of trace elements like Sb, Sn, Te and Pb in archaeological metallic objects found on the territory of Romania-old coins and Bronze Age jewelry, aimed to determine the provenance of the gold used in their manufacture. The results are compared with the detailed elemental composition of alluvial or primary gold samples, obtained by the same technique. This work attempted to establish the origin of the gold used for the mint of two different types of koson coins. We found that the kosons with monogram are made of refined gold, while the one used for the kosons without monogram is mainly alluvial. The gold used in the manufacture of the Calarasi Vulchitrun-type disk and the Tauteu hair ring is also of alluvial origin.
To gain insight into the possible origin of the gold used in the production of tesserae containing gold leaf less than 0.5 μm thick placed between two layers of glass, we propose a non-destructive synchrotron radiation (SR) XRF protocol based on sequential analysis under optimised analytical conditions. Using this protocol, trace element analysis is achieved with detection limits of 1–6 mg/kg. As Pt and Au have adjacent fluorescence energies, we tested the most challenging situation, when Pt is present in very low concentrations in gold. Data obtained by double-dispersive XRF (D2XRF) and μXRF for fourth–ninth-century mosaics decorating nine Eastern and Western religious buildings show that the Eastern and Western tesserae are made from different alloys.
However, these alloys are identical to those used to make gold leaf for gilding, because plastic deformation requires the use of gold alloys with high ductility and malleability. Although trace element composition of gold used in the concerned period is only available for coins, by comparing the amounts of Pt contained in the tesserae and in the coins we show that Roman tesserae are made from Roman gold, as described in the documentary sources. We observe for the Byzantine period the use of a Byzantine gold and of gold supposedly from different stages of recycling, and we suggest the use of Umayyad and Abbasid gold for the production of Islamic tesserae.
Getting more efficient – The use of Bayesian optimization and Gaussian processes at the BAMline
(2022)
For more than 20 years, BAM is operating the BAMline at the synchrotron BESSY II in Berlin Adlershof. During this time, the complexity of the setup and the amount of data generated have multiplied. To increase the effectiveness and in preparation for BESSY III, algorithms from the field of machine learning are increasingly used.
In this paper, several examples in the areas of beamline alignment and measurement time optimization based on Bayesian optimization (BO) with Gaussian processes (GP) are presented. BO is a method for finding the global optimum of a function using a probabilistic model represented by a GP. The advantage of this method is that it can handle high-dimensional problems, does not depend on the initial estimate, and also provides uncertainty estimates.
After a short introduction to BO and GP, the first example is the automatic alignment of our double multilayer monochromator (DMM). To achieve optimal performance, up to three linear and two angular motor positions have to be optimized. To achieve this with a grid scan, at least 100^5 measurement points would be required. Assuming that all positions can be aligned independently, 100*5 points are still necessary. We show that with BO and GP less than 100 points are sufficient to achieve equal or better results.
The second example is the optimization of measurement time in XRF scanning. Here we will show the advantage of the BO GP approach over point-by-point scanning. As can be seen in Fig. 1, the number of points required and thus the measurement time can be reduced by a factor of 50, while the loss in image quality is acceptable. The advantages and limitations of this approach will be discussed.
Getting more efficient – The use of Bayesian optimization and Gaussian processes at the BAMline
(2022)
For more than 20 years, BAM is operating the BAMline at the synchrotron BESSY II in Berlin Adlershof. During this time, the complexity of the setup and the amount of data generated have multiplied. To increase the effectiveness and in preparation for BESSY III, algorithms from the field of machine learning are increasingly used.
After a short introduction to BO and GP, the first example is the automatic alignment of our double multilayer monochromator (DMM).
The second example is the optimization of measurement time in XRF scanning.
Within an interdisciplinary project, preliminary results of which were published in 2007, a group of 65 silver coins (denarii) of Trajan, evenly distributed over the entire span of his reign (2nd to 6th consulate), as well as 3 coins from the reign of his predecessor, the emperor Nerva (AD 9698), had been acquired on the coin market. These pieces could be cross-sectioned in order to carry out analyses. Measurements were performed with µ-XRF and µ-SRXRF to check the fineness of the denarius alloy as well as to investigate if the coins of the different consulates showed distinct traits concerning the main impurities which could suggest a change of ore sources. Furthermore, it was examined whether the influx of precious metals into the Roman treasury after Trajan's Dacian campaigns (AD 101/102 and 105/106) could have had any repercussions on the composition of the denarius alloy; comparative data was provided by the analysis of nine imitations of Roman Republican denarii presumably struck in Dacia. Documentation of the cross-sections was performed with SEM/EDX in order to clarify details concerning the specific microstructure of the coins. An enrichment of Ag of approx. 100 to 200 µm in the near surface regions of most of the coins could be observed, which is due to corrosion effects. Previous metallographic analyses done by several scholars had been inadequate to clarify the central numismatic and economic questions. With the presented analyses, it was possible to correct the results of the earlier research and to provide, for the first time, a secure basis of data for the investigation of the development of the silver alloy used for denarii in Trajan's reign.
Gold is one of the seven metals already known in antiquity and was used from time immemorial as a medium of exchange and for the production of jewelry because of its luster and rarity. In addition, it is easy to work and largely resistant to chemical influences. Investigations of gold using synchrotron radiation excited X-ray fluorescence analysis are non-destructive and provide information about the chemical elements present in the sample under investigation. The investigations presented here at BAMline focus on questions such as the origin, manufacturing process, and association of gold findings. The different questions are explained by a number of examples ranging from the Viking treasure from Hiddensee to the Nebra Sky Disk and finds from Egypt. The find from Bernstorf is discussed in detail. A Bayesian treatment of the authenticity is shown.
Spatially resolved X-ray fluorescence analysis using synchrotron radiation (SR-XRF) at the wavelength shifter beamline, BAMline, at BESSY was used to investigate Renaissance silverpoint drawings as it is extremely sensitive, non-destructive and can be carried out in air using an excitation spot in the hundred micrometer range.
This paper deals with first results of the study of silverpoint drawings of Albrecht Dürer (14711528) belonging to the sketchbook that Albrecht Dürer used during a travel to the Netherlands in 1520/21. These results are compared to a PIXE study performed on drawings from the same sketchbook.
The minor element composition of the silverpoint used for the drawings in the sketchbook was (10.6 ± 3.5) wt.% of Cu and traces of Zn. Mercury was found in the marks but does not belong to the initial composition of the silverpoint as it is attributed to an alteration phenomenon. One drawing of the sketchbook represents an exception. It consists of silver marks containing an additional minor element, Zn, in the marks and was, therefore, created with another silverpoint, probably at a different time than the other drawings.
Gold mosaics, made from gold and glass, are one of the best expressions of Late Antique Byzantine and Early Islamic art. The gold alloys, whose composition seems to indicate that gold coins were re-used to fabricate the tesserae, can be used to provide information on the mosaics chronology. Monetary Byzantine gold is in fact characterized by the presence of Pt, which contents in the gold alloy change over time, but Pt must be measured in 0.2-0.4 µm thickness gold leaves that were beaten to be sandwiched between two glass layers.
To analyze this samples the D²XRF set-up at the BAMline at the BESSY synchrotron in Berlin was used. The combination of a crystal for wavelength dispersion and an energy resolving single photon counting pnCCD allows the realization of this very simple wavelength dispersive detection system. With this system an MDL of 1 μg/g for the determination of Pt in Au under optimal conditions can be reached.
Gold leaf tesserae from nine archaeological sites, covering the period that goes from the 5th c. to the 8th c., were analyzed. The presence of Pt in the majority of the samples confirmed the re-use of coins. The Pt contents separate the samples in three groups, one of which having the same chemical characteristics as the Byzantine gold could be compared to dated coins for chronology. The higher Pt contents for one of other groups suggest
The newly developed EXAFS set-up comprises both time- and spatially-resolved EXAFS information simultaneously in a single-shot. This facile, stable and scanningless set-up was tested at the BAMline @ BESSY-II (Berlin, Germany). The primary broadband beam is generated by a filter/X-ray-mirror combination (bandpass). The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by an area sensitive detector based on a CCD camera, in a theta - 2 theta geometry.
The first in situ measurements were successfully carried out and hereby presented. The case-study involved a well known reaction, in which structural changes are induced over time, and continuously measured. We were able to track structural changes within a 1s time resolution.
Trace elements of ancient gold such as Pt, give fundamental information on the circulation of the metal in the past. In the case of objects from the cultural heritage, the determination of trace elements requires non-destructive point analysis in general. These conditions and the need of good detection limits restrain the number of applicable analytical techniques.
After the development of a PIXE set-up with a selective Cu or Zn filter of 75 µm and of a PIXE-XRF set-up using a primary target of As, we tested the possibilities of spatially resolved Sy-XRF to determine Pt in gold alloys. With a Zn filter, PIXE showed a detection limit of 1000 ppm in gold while PIXE-XRF lowers this detection limit down to 80 ppm. This last value being constrained by the resonant Raman effect produced on gold. In order to improve the detection limit of Pt keeping the non-destructiveness and access to point analysis, we developed an analytical protocol for XRF with synchrotron radiation at BESSY II, using the BAMline set-up. The L-lines of Pt were excited by a beam of energy above and below 11.564 keV and measured using a Si(Li) detector with a 50 µm Cu filter. A µ-beam of 100250 µm2 was used according to the size of the sample. The determination of the Pt content in the samples was carried out by Monte-Carlo simulation and subtraction of Au and Pt spectra obtained on pure standards. The limit of detection for Pt of 20 ppm was determined by using certified standards. The detection limits of a small set of other characteristic elements of gold were also measured using an incident energy of 33 keV.
In this study, we propose the use of nondestructive, depth-resolved, element-specific characterization using grazing exit X-ray absorption near-edge structure spectroscopy (GE-XANES) to investigate the corrosion process in compositionally complex alloys (CCAs). By combining grazing exit X-ray fluorescence spectroscopy (GE-XRF) geometry and a pnCCD detector, we provide a scanning-free, nondestructive, depth-resolved analysis in a sub-micrometer depth range, which is especially relevant for layered materials, such as corroded CCAs. Our setup allows for spatial and energy-resolved measurements and directly extracts the desired fluorescence line, free from scattering events and other overlapping lines. We demonstrate the potential of our approach on a compositionally complex CrCoNi alloy and a layered reference sample with known composition and specific layer thickness. Our findings indicate that this new GE-XANES approach has exciting opportunities for studying surface catalysis and corrosion processes in real-world materials.
EXAFS analysis of pure elements, binary and ternary equiatomic refractory alloys within the Nb-Zr-Ti-Hf- Ta system is performed at the Nb and Zr K-edges to analyze the evolution of the chemical local environ- ment and the lattice distortion. A good mixing of the elements is found at the atomic scale. For some compounds, a distribution of distances between the central atom and its neighbors suggests a distortion of the structure. Finally, analysis of the Debye-Waller parameters shows some correlation with the lat- tice distortion parameter δ², and allows to quantify experimentally the static disorder in medium entropy alloys.
Examples of XRF and PIXE imaging with few microns resolution using SLcam® a color X-ray camera
(2015)
We present results of recent development of the color X-ray camera, type SLcam®, allowing detection of X-ray images with few microns resolution. Such spectral resolution is achieved with the use of high-quality polycapillary optics combined with sub-pixel resolution. Imaging of Siemens star resolution test chart reveals that the resolution limit of SLcam® can go down to nearly 5µm. Several real sample examples of measurements carried out at the laboratory, synchrotron, and particle-induced X-ray emission beamlines are shown. This is the first time SLcam® is used as particle-induced X-ray emission detector.
A major source of capacity fade of the common vanadium redox flow battery (VRFB) is the vanadium ion transport through the separator. However, different transport models disagree significantly in the diffusion coefficient for the different V species and the influence of different transport mechanisms. The underlying hypothesis of this work is that reactions inside the membrane are partly responsible for these discrepancies. Accordingly, it was investigated if redox reactions inside the nanoscopic water body of Nafion 117 can occur. X-ray absorption near edge structure spectroscopy (XANES) was used to distinguish between the different V species inside hydrated Nafion 117 and novel PVDF-based membranes. It was validated that the speciation of vanadium can be performed using the pre-edge peak energy and intensity. The experiments were performed as follows: strips of the membrane were exposed from one site to a V3+ solution (green) and from the other site to a VO2+ solution (yellow). The ions could diffuse into the membrane from both sides. A change of color of the membrane strip was observed. The blue color in the middle of the strip indicated that VO2+ was formed where V3+ and VO2+ got in contact. Using XANES this reaction inside Nafion was proven.
Evaluation of total reflection X-ray fluorescence (TXRF) analysis using a color X-ray camera (CXC)
(2013)
Gold ist eines der sieben schon im Altertum bekannten Metalle und wurde wg. seines Glanzes und seiner Seltenheit von alters her als Tauschmittel und zur Herstellung von Schmuck benutzt. Außerdem ist es einfach bearbeitbar und weitestgehend gegen chemische Einflüsse resistent.
Die Untersuchungen von Gold mit synchrotronstrahlungsangeregter Röntgenfluoreszenzanalyse sind zerstörungsfrei und geben Auskunft über die in der untersuchten Probe vorhandenen chemischen Elemente.
Bei den hier vorgestellten Untersuchungen an der BAMline stehen Fragestellungen wie Herkunft, Herstellungsverfahren und Zusammengehörigkeit von Goldfunden im Vordergrund. Die verschiedenen Fragestellungen werden an einer Reihe von Beispielen erläutert die vom Wikingerschatz aus Hiddensee über die Himmelsscheibe von Nebra bis hin zu Funden aus Ägypten langen. Zusätzlich werden die modernen Messmethoden vorgestellt, die am Synchrotron heutzutage zur Verfügung stehen.
Enhancing efficiency at bamline: employing data science and machine learning for x-ray research
(2023)
This talk discusses how data science and machine learning techniques are being applied at the BAM Federal Institute for Materials Research and Testing to enhance efficiency and automation at the BAMLine synchrotron facility. The methods presented include Gaussian processes and Bayesian optimization for beamline adjustment and optimization of X-ray measurements. These statistical techniques allow automated alignment of beamline components and active learning scanning to reduce measurement time.
Additional machine learning methods covered are neural networks for quantification of X-ray fluorescence (XRF) data and decoding coded apertures.
Our aim is to develop a simple and inexpensive method for full field X-ray fluorescence imaging.We combine an energydispersive array detector with a coded aperture to obtain high resolut ion images. To obtain the information from the recorded image a reconstruction step is necessary. The reconstruction methods we have developed, were tested on simulated data and then applied to experimental data. The first tests were carried out at the BAMline @BESSY II. This method enables the simultaneous detection of multiple elements,which is important e.g. in the field of catalysis.
A liver biopsy specimen from a Wilson’s disease (WD) patient was analyzed by means of micro-X-ray fluorescence (mXRF) spectroscopy to determine the elemental distribution. First, bench-top mXRF was utilized for a coarse scan of the sample under laboratory conditions. The resulting distribution maps of copper and iron enabled the determination of a region of interest (ROI) for further analysis. In order to obtain more detailed elemental information, this ROI was analyzed by synchrotron radiation (SR)-based mXRF with a beam size of 4 mm offering a resolution at the cellular level. Distribution maps of additional elements to copper and iron like zinc and manganese were obtained due to a higher sensitivity of SR-mXRF. In addition to this, X-ray absorption near edge structure spectroscopy (XANES) was performed to identify the oxidation states of copper in WD. This speciation analysis indicated a mixture of copper(I) and copper(II) within the WD liver tissue.
Electron probe microanalysis (EPMA) measurement of thin-film thickness in the nanometre range
(2002)
The thickness of thin films of platinum and nickel on fused silica and silicon substrates has been determined by EPMA using the commercial software STRATAGEM for calculation of film thickness. Film thickness ranged in the order 10 nm. An attempt was made to estimate the confidence range of the method by comparison with results from other methods of analysis. The data show that in addition to the uncertainty of the spectral intensity measurement and the complicated fitting routine, systematic deviation caused by the underlying model should be added. The scattering in the results from other methods does not enable specification of a range of uncertainty, but deviations from the real thickness are estimated to be less than 20%.
With the aim of improving limits of detection (LOD) of trace elements in a matrix with adjacent fluorescence energies, a simple double dispersive X-ray fluorescence detection system (D2XRF) was constructed to operate at the beamlines BAMline and the mySpot @ BESSY II. This system is based on the combination of a crystal analyzer with an energy resolving single photon counting pnCCD. Without further collimators, the efficient suppression of the background by the pnCCD and the good energy resolution of the crystal results in improved LOD. In first order reflections, an energy resolution of 13 eV for Cu Kα was reached, and an energy range of 1 keV was covered in one shot.
This new system was applied to the detection of platinum (Pt) in gold leaves with a LOD of 0.9 mg/kg, which is the lowest attained by totally non-destructive methods nowadays. The presence of Pt in gilded objects from Abydos and Byzantine mosaics provides vital information, as it indicates the alluvial origin of the gold for these examples.
X-ray absorption spectroscopy (XAS) provides a unique, atom-specific tool to probe the electronic structure of solids. By surmounting long-held limitations of powder-based XAS using a dynamically averaged powder in a Resonant Acoustic Mixer (RAM), we demonstrate how time-resolved in situ (TRIS) XAS provides unprecedented detail of mechanochemical synthesis. The use of a custom-designed dispersive XAS (DXAS) setup allows us to increase the time resolution over existing fluorescence measurements from ∼15 min to 2 s for a complete absorption spectrum. Hence, we here establish TRIS-XAS as a viable method for studying mechanochemical reactions and sampling reaction kinetics. The generality of our approach is demonstrated through RAM-induced (i) bottom-up Au nanoparticle mechanosynthesis and (ii) the synthesis of a prototypical metal organic framework, ZIF-8. Moreover, we demonstrate that our approach also works with the addition of a stainless steel milling ball, opening the door to using TRIS-DXAS for following conventional ball milling reactions. We expect that our TRIS-DXAS approach will become an essential part of the mechanochemical tool box.
Phoenician ivory objects (8th century B.C., Syria) from the collections of the Badisches Landesmuseum, Karlsruhe, Germany, have been studied with full field X-ray fluorescence microimaging, using synchrotron radiation (SR-FF-microXRF). The innovative Color X-ray Camera (CXC), a full-field detection device (SLcam), was used at the X-ray fluorescence beamline of the ANKA synchrotron facility (ANKA-FLUO, KIT, Karlsruhe, Germany) to noninvasively study trace metal distributions at the surface of the archeological ivory objects. The outstanding strength of the imaging technique with the CXC is the capability to record the full XRF spectrum with a spatial resolution of 48 µm on a zone of a size of 11.9 × 12.3 mm² (264 × 264 pixels). For each analyzed region, 69696 spectra were simultaneously recorded. The principal elements detected are P, Ca, and Sr, coming from the ivory material itself; Cu, characteristic of pigments; Fe and Pb, representing sediments or pigments; Mn, revealing deposited soil minerals; Ti, indicating restoration processes or correlated with Fe sediment traces; and Au, linked to a former gilding. This provides essential information for the assessment of the original appearance of the ivory carvings. The determined elemental maps specific of possible pigments are superimposed on one another to visualize their respective distributions and reconstruct the original polychromy and gilding. Reliable hypotheses for the reconstruction of the original polychromy of the carved ivories are postulated on this basis.
Rund ein Jahr haben DIN und DKE in einem gemeinsamen Projekt mit dem Bundesministerium für Wirtschaft und Energie und zusammen mit ca. 300 Fachleuten aus Wirtschaft, Wissenschaft, öffentlicher Hand und Zivilgesellschaft an der Normungsroadmap Künstliche Intelligenz gearbeitet. Eine hochrangige Steuerungsgruppe unter dem Vorsitz von Prof. Wolfgang Wahlster hat die Erarbeitung koordiniert und begleitet.
Ziel der Roadmap ist die frühzeitige Entwicklung eines Handlungsrahmens für die Normung und Standardisierung, der die internationale Wettbewerbsfähigkeit der deutschen Wirtschaft unterstützt und europäische Wertmaßstäbe auf die internationale Ebene hebt.
The development of earth-abundant catalysts for selective electrochemical CO2 conversion is a central challenge. Cu-Sn bimetallic catalysts can yield selective CO2 reduction toward either CO or formate. This study presents oxide-derived Cu-Sn catalysts tunable for either product and seeks to understand the synergetic effects between Cu and Sn causing these selectivity trends. The materials undergo significant transformations under CO2 reduction conditions, and their dynamic bulk and surface structures are revealed by correlating observations from multiple methods—X-ray absorption spectroscopy for in situ study, and quasi in situ X-ray photoelectron spectroscopy for surface sensitivity. For both types of catalysts, Cu transforms to metallic Cu0 under reaction conditions. However, the Sn speciation and content differ significantly between the catalyst types: the CO-selective catalysts exhibit a surface Sn content of 13 at. % predominantly present as oxidized Sn, while the formate-selective catalysts display an Sn content of ≈70 at. % consisting of both metallic Sn0 and Sn oxide species. Density functional theory simulations suggest that Snδ+ sites weaken CO adsorption, thereby enhancing CO selectivity, while Sn0 sites hinder H adsorption and promote formate production. This study reveals the complex dependence of catalyst structure, composition, and speciation with electrochemical bias in bimetallic Cu catalysts.
The content of chromium in different oxidation states in chromium-treated wood was studied with XANES (X-ray absorption near-edge structure) measurements at the Cr K absorption edge. It could be shown that wood samples treated with Cr(VI) (pine and beech) did still contain a measurable content of Cr(VI) after four weeks conditioning. If such wood samples were heat exposed for 2 h with 135 °C prior conditioning, Cr(VI) was no longer detected by XANES, indicating a complete reduction to chromium (III).
In this study, a multi-proxy approach combining 29Si, 27Al and 1H MAS-NMR, FEG-EPMA, XANES at the Cu K-edge and XRD analytics with hydrochemical tools such as ICP-OES analyses, oxygen-isotope signatures, and thermodynamic modelling was applied to K-silicate-activated metakaolin specimens - with and without CuSO4·5H2O addition - exposed to sulfuric acid at pH = 2 for 35 days. The results revealed a multistage deterioration mechanism governed by (i) acid diffusion, (ii) leaching of K-A-S-H, (iii) microstructural damage related to precipitation of expansive (K,Ca,Al)-sulfate-hydrate phases (iv) complete dissolution of the K-A-S-H framework, (v) and formation of silica gel in the outermost corroded regions. Copper ions were mainly located in layered spertiniite-chrysocolla-like phases in the as-cured materials. The results demonstrate an overall negative effect of Cu addition on chemical material durability, implying that the reported higher durability of Cu-doped AAM in biocorrosion environments can be best explained by bacteriostatic effects.
Das Hiddensee-Projekt
(2009)
Gold ist eines der sieben bereits in der Antike bekannten Metalle und wurde wegen seines Glanzes und seiner Seltenheit seit jeher als Tauschmittel und zur Herstellung von Schmuck verwendet. Außerdem ist es leicht zu bearbeiten und weitgehend resistent gegen chemische Einflüsse.
Die Analyse von Gold mit der durch Synchrotronstrahlung angeregten Röntgenfluoreszenzanalyse ist zerstörungsfrei und liefert Informationen über die in der untersuchten Probe vorhandenen chemischen Elemente.
Im Mittelpunkt der hier vorgestellten Untersuchungen an der BAMline stehen Fragen nach der Herkunft, dem Herstellungsprozess und der Zugehörigkeit von Goldfunden. Die verschiedenen Fragestellungen werden anhand einer Reihe von Beispielen erläutert, die vom Wikingerschatz von Hiddensee über die Himmelsscheibe von Nebra bis hin zu Funden aus Ägypten reichen. Darüber hinaus werden die heute am Synchrotron verfügbaren modernen Messmethoden vorgestellt.
Metakaolin-based alkali activated mortars (AAM) - with and without CuSO4·5H2O and ZnO addition (mass ratio Mn+/solid binder 0.08% to 1.7%) - were casted and exposed within an extensive long-term field campaign over the period of 20 months to a sewer basin, strongly affected by biogenic acid corrosion. (Un-)exposed AAM were tested regarding their physicochemical and microstructural properties, bioreceptivity and overall durability. Metal addition led to a retarding effect during alkali-activation reaction, as well as to an increase in open porosity of up to 3.0% and corresponding lower compressive strength of up to 10.9%. Reduced microbial colonization and diversity were observed on AAM with Cu, while Zn addition led to increased biodiversity. We propose that the observed higher durability of Cu-doped AAM is due to antibacterial effects and associated reduction of biogenic acid production, superseding overall negative effects of metal-dosage on physical material properties. Observed lower durability of Zn-doped AAM was related to combined negative physicochemical and microbial effects.
With the increase in the awareness of the public in the environmental impact of oil shale utilization, it is of interest to reveal the mobility of potentially toxic trace elements in spent oil shale. Therefore, the Cr and As oxidation state in a representative Jordanian oil shale sample from the El-Lajjoun area were investigated upon different lab-scale furnace treatments. The anaerobic pyrolysis was performed in a retort flushed by nitrogen gas at temperatures in between 600 and 800 °C (pyrolytic oil shale, POS). The aerobic combustion was simply performed in porcelain cups heated in a muffle furnace for 4 h at temperatures in between 700 and 1000 °C (burned oil shale, BOS). The high loss-on-ignition in the BOS samples of up to 370 g kg–1 results from both calcium carbonate and organic carbon degradation. The LOI leads to enrichment in the Cr concentrations from 480 mg kg–1 in the original oil shale up to 675 mg kg–1 in the ≥850 °C BOS samples. Arsenic concentrations were not much elevated beyond that in the average shale standard (13 mg kg–1). Synchrotron-based X-ray absorption near-edge structure (XANES) analysis revealed that within the original oil shale the oxidation states of Cr and As were lower than after its aerobic combustion. Cr(VI) increased from 0% in the untreated or pyrolyzed oil shale up to 60% in the BOS ash combusted at 850 °C, while As(V) increased from 64% in the original oil shale up to 100% in the BOS ash at 700 °C. No Cr was released from original oil shale and POS products by the European compliance leaching test CEN/TC 292 EN 12457-1 (1:2 solid/water ratio, 24 h shaking), whereas leachates from BOS samples showed Cr release in the order of one mmol L–1. The leachable Cr content is dominated by chromate as revealed by catalytic adsorptive stripping voltammetry (CAdSV) which could cause harmful contamination of surface and groundwater in the semiarid environment of Jordan.
X-ray imaging methods are used in many fields of research, as they allow a non-destructive Investigation of the elemental content of various samples. As for every imaging method, for X-ray imaging the optics are of crucial importance. However, these optics can be very expensive and laborious to build, as the requirements on surface roughness and precision are extremely high. Angles of reflection and refraction are often in the range of a few mrad, making a compact design hard to achieve. In this work we present a possibility to simplify X-ray imaging. We have adapted the coded aperture method, a high energy radiation imaging method that has its origins in astrophysics, to full field X-ray fluorescence imaging. In coded aperture imaging, an object is projected through a known mask, the coded aperture, onto an area sensitive detector. The resulting image consists of overlapping projections of the object and a reconstruction step is necessary to obtain the information from the recorded image. We recorded fluorescence images of different samples with an energy-dispersive 2D detector (pnCCD) and investigated different reconstruction methods. With a small coded aperture with 12 holes we could significantly increase the count rate compared to measurements with a straight polycapillary optic. We show that the reconstruction of two different samples is possible with a deconvolution approach, an iterative algorithm and a neural network. These results demonstrate that X-ray fluorescence imaging with coded apertures has the potential to deliver good results without scanning and with an improved count rate, so that measurement times can be shortened compared to established methods.