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Schlagworte
Organisationseinheit der BAM
In contrast to classical low temperature polymer electrolyte fuel cells (LT-PEFCs), the membrane conductivity in high temperature polymer electrolyte fuel cells (HT-PEFCs) (operating temperature ~ 160 °C) is based on proton transport within phosphorus-oxygen acids at different levels of hydration, orthophosphoric acid (H3PO4) being the simplest example. We present for the first time in-situ synchrotron X-ray radiography measurements applied to a HT-PEFC to gain insight into the local composition of the membrane electrode assembly (MEA) under dynamic operating conditions. Transmission changes during the radiographic measurements exhibit a clear influence of the formation of product water on the membrane composition.
Neu entwickelte Gasturbinen werden im Prüffeld mit wechselnden Belastungen beaufschlagt. Dazu wird die Gasturbine mit einer Wasserreibbremse gekoppelt, mit der eine definierte Last erzeugt werden kann.
Ursprünglich war die Wasserreibbremse für eine bestimmte Leistung, die den früheren Leistungen der Gasturbine entsprach, ausgelegt worden. Die erste Prüfung fand im Jahr 1975 statt. Da neuere Gasturbinen wesentlich höhere Leistungen erbringen und die vorhandene Wasserreibbremse weiterhin eingesetzt werden sollte, musste eine Nachqualifizierung vorgenommen werden. Das Ziel war die Absicherung auf eine mögliche Sprödbruchgefahr.
Zunächst wurde eine Studie zur Prüfbarkeit erstellt. An speziellen Testkörpern wurden im Ultraschallabor der BAM Vorversuche zur Machbarkeit, zur Empfindlichkeitsein-stellung und zur Vorbereitung der Prüfung durchgeführt. Dazu wurden spezielle Gruppenstrahlerprüfköpfe gefertigt und ein an die komplizierte Geometrie der Bremsscheiben angepasster Manipulator gebaut. Ferner wurde, um die Prüfzeiten zu reduzieren, die Software zur Datenerfassung und zur Auswertung angepasst.
Im Werk Berlin der Siemens AG wurde in Zusammenarbeit mit der Siemens AG Erlangen eine Ultraschallprüfung mit der Gruppenstahlertechnik der Wasserreibbremse durchgeführt. Überprüft wurde das gesamte Volumen auf axial, radial und tangential beanspruchte Fehler in den Bereichen der Welle und der Bremsscheibe.Die Überprüfung ergab keine relevanten Fehler, so dass die Wasserreibbremse weiterhin eingesetzt werden kann.
Fe-ZSM-5 Catalysts for the Selective Reduction of NO by Isobutane - The Problem of the Active Sites
(2002)
Relations between the structure of FeZSM-5 catalysts prepared by interaction of FeCl3 with HZSM-5 and their catalytic behavior in the SCR of NO by isobutane were investigated by combining results of catalytic studies (1000 ppm NO, 1000 ppm isobutane, and 2% O2 in He, 30,000 h-1) and of physicochemical characterization (XRD, EXAFS, Mössbauer spectroscopy, TPR, IR, XPS). By variation of the preparation conditions (method of FeCl3 introductionchemical vapor deposition or solid-state ion exchange, washing intensity, calcination regime) and of the matrix (HZSM-5 with normal and high defect density), FeZSM-5 materials with strongly varying properties (aggregation degree of the Fe phase, acidity) were obtained. Significant discrepancies between conclusions derived from EXAFS, TPR, and Mössbauer spectroscopy were ascribed to a preference of Mössbauer spectroscopy for the detection of aggregated phases and a high defectivity of Fe oxide clusters formed upon calcination. The critical step for the preparation of a highly disperse Fe phase is extensive washing after Fe introduction. The catalytic behavior of overexchanged FeZSM-5 materials prepared by interaction of FeCl3 with HZSM-5 of normal defect density was not influenced by aggregation of a significant part of the Fe phase. The comparison of their catalytic properties with those of a Fe2O3/HZSM-5 mechanical mixture and of catalysts prepared by aqueous ion exchange or by CVD of FeCl3 into HZSM-5 of high defect density implies that the particular activity of overexchanged FeZSM-5 arises from minority sites. In these, the Fe ions are probably isolated. Other Fe sites of low nuclearity appear to add to the activity. The poor SCR performance (at a given ability for isobutane activation) of FeZSM-5 prepared with a defective ZSM-5 matrix may indicate that the Fe sites which provi de the particular activity of overexchanged FeZSM-5 require the cooperation of acidic sites.
The first hard X-ray beamline at BESSY II will be installed by BAM and PTB at a superconducting 7 T wavelength shifter. The main optical elements of the beamline are a Double-Multilayer-Monochromator and a Double-Crystal-Monochromator. The two devices can be used separately or in-line. Main applications of monochromatic radiation with photon energies up to 50 keV are X-ray fluorescence analysis, micro-computed tomography, X-ray topography, detector calibration and reflectometry. Calculable undispersed radiation up to 200 keV will be available for radiometric applications.
The impact of very high cycle fatigue (VHCF) load conditions on the microstructure of specimens consisting of nodular cast iron is analyzed by means of micro-computed tomography (µCT) utilizing both monochromatic synchrotron radiation and polychromatic X-ray tube radiation. Using 3D µCT, the microstructure in the region of the smallest cross-sections of shouldered round specimens is imaged in different stages of the VHCF loading. By digital image correlation (DIC) of these tomograms strain fields are analyzed three-dimensionally. Strain levels in the range of a few percent were detected. It is proven that a localization of strain allows to predict the site of the crack which precedes and induces the macroscopic failure of the specimens.
A complete metrological traceability system for measurement results of chemical analysis was set up. Core components are pure substances (national standards) characterised at the highest metrological level, primary solutions prepared from these pure substances and secondary solutions deduced from the primary solutions and intended for sale. The relative uncertainty of the element mass fraction of the primary substances and solutions is < 0.01 and < 0.05%, respectively. For the certification of transfer solutions and for stability testing, a precision measurement method for element contents has been developed by means of optical emission spectrometry (ICP OES) by which uncertainties between 0.1 and 0.05% can be achieved. The dissemination to field laboratories is effected with the aid of a calibration laboratory of the German Calibration Service (DKD) which certifies the element content of the secondary solutions with an uncertainty <= 0.3%. Calibration with these solutions enables the user to establish traceability of his measurement results to the International System of Units (SI). Currently, the system comprises Cu, Fe, Bi, Ga, Si, Na, K, Sn, W, and Pb.
Die Größenbewertung von Anzeigen und die Bestimmung der Nachweisgrenze spielen bei der Ultraschallprüfung eine zentrale Rolle: Sie stellen sicher, dass kritische Ungänzen erfasst und bruchmechanisch behandelt werden können.
Bei SAFT wurde bisher die Größe von Ungänzen dadurch bestimmt, dass die räumliche Anzeigenausdehnung im Rekonstruktionsergebnis ausgewertet wird, d.h. die Anzahl von Voxel über die sich eine Anzeige erstreckt. Auf diese Weise lassen sich jedoch nur Defektanzeigen bewerten, die größer oder gleich der Wellenlänge sind. Bei kleinen Defekten versagt diese Methode, d.h. es ist keine Größenbewertung möglich. Außerdem bietet diese Methode keine Aussage über die Nachweisgrenze des Verfahrens.
Ein Hauptvorteil von SAFT gegenüber der konventionellen Ultraschallprüfung ist aber gerade die Verbesserung der Nachweisgrenze, denn SAFT steigert das Signal-Rausch-Verhältnis (SNR) gegenüber dem Gefügerauschen und reduziert statistisches Rauschen. Um diesen Hauptvorteil nutzen (und quantifizieren) zu können, wird für SAFT eine Methode zur Nachweisgrenzenbestimmung und zur Größenbewertung der Anzeigen kleiner Ungänzen benötigt.
Neben ihrer räumlichen Ausdehnung lassen sich Anzeigen im SAFT-Ergebnis auch durch ihre Amplitude charakterisieren, wenn die Prüfkopfeigenschaften und die geometrischen Verhältnisse beim Scan berücksichtigt werden. Genauer gesagt durch die Amplitudensumme, in die - neben der Echoamplitude - auch die winkelabhängige Streucharakteristik eingeht.
Im Folgenden wird dargelegt, dass sich die Amplitudensumme zur Nachweisgrenzenbestimmung und zur Größenbewertung kleiner Ungänzen eignet.
Es wird der Zusammenhang zwischen der Amplitudensumme und der Größe von Ungänzen dargestellt, und es wird gezeigt, dass auch die Anzeigenposition und die Form des Prüfobjektes eine Rolle spielen können. Auf dieser Basis wird eine Methode zur Größenbestimmung kleiner Anzeigen im SAFT-Ergebnis entwickelt.
Damit lässt sich das SAFT-Ergebnis als Ersatzfehlergröße darstellen, so wie das bei konventioneller Ultraschallprüfung z.B. mit Hilfe von AVG-Diagrammen erfolgt.
Durch die Vervollständigung um die Größenbewertung ist SAFT nicht mehr nur ein bildgebendes Verfahren, sondern es kann vielmehr als vollwertiges Messverfahren dienen.
The performance of glow discharge mass spectrometry (GD-MS) is investigated for the accurate quantification of metallic impurities and oxygen in solid samples using the fast flow source GD-MS instrument ELEMENT GD.
Different quantification approaches based on relative and absolute sensitivity factors are evaluated for the determination of metallic impurities using three sample matrixes (Al, Cu and Zn). The effect of the discharge conditions (voltage, current, discharge gas pressure/flow) on the sensitivity is investigated and the parameters are optimized to favour matrix independent calibrations. Improved standard relative sensitivity factors (StdRSFs) are calculated under optimal conditions based on multi-matrix calibrations. The sputtering rate corrected calibration is also presented as a multi-matrix calibration approach.
The capabilities of GD-MS for oxygen determination are also investigated using a set of new conductive samples containing oxygen with mass fractions in the percent range in three different matrices (Al, Mg and Cu) produced by a sintering process. Poor limits of detection (in the order of g/kg) were obtained as consequence of the reduced sensitivity of oxygen in GD-MS and high oxygen background signal intensity as well as its variations. The absolute sensitivity procedure is shown as a matrix-independent approach, which provides quantitative values consistent with those obtained by carrier gas hot extraction (CGHE).
This Report describes the certification of the reference material antimony implanted in Si/SiO2 intended to be used for calibration of surface and near surface analytical methods. It describes the preparation, homogeneity measurements and the analytical work performed for the certification of both Areal density of antimony Atoms (retained dose) and the isotope amount Ratio as well as giving considerations on the stability of the material.
An automatic sample changer chamber for total reflection X-ray fluorescence (TXRF) and X-ray absorption near-edge structure (XANES) analysis in TXRF geometry was successfully set up at the BAMline at BESSY II. TXRF and TXRF-XANES are valuable tools for elemental determination and speciation, especially where sample amounts are limited (<1 mg) and concentrations are low (ng ml⁻¹ to μg ml⁻¹). TXRF requires a well defined geometry regarding the reflecting surface of a sample carrier and the synchrotron beam. The newly installed chamber allows for reliable sample positioning, remote sample changing and evacuation of the fluorescence beam path. The chamber was successfully used showing accurate determination of elemental amounts in the certified reference material NISTwater 1640. Low limits of detection of less than 100 fg absolute (10 pg ml⁻¹) for Ni were found. TXRF-XANES on different Re species was applied. An unknown species of Re was found to be Re in the +7 oxidation state.
This key comparison aims to assess the core capabilities of the participants in gas analysis. Such competences include, among others, the capabilities to prepare Primary Standard gas Mixtures (PSMs), perform the necessary purity analysis on the materials used in the gas mixture preparation, the verification of the composition of newly prepared PSMs against existing ones, and the capability of calibrating the composition of a gas mixture. According to the Strategy for Key Comparisons of the Gas Analysis Working Group, this key comparison is classified as an RMO track A key comparison.
The artefacts were binary mixtures of propane in nitrogen at a nominal amount-of-substance fraction level of 1000 μmol/mol. The values and uncertainties from the gravimetric gas mixture preparation were used as key comparison reference values (KCRVs). Each transfer standard had its own KCRV. The results are generally good. All results are within ± 1 % of the KCRV.
Core–shell nanoparticles (CSNPs) have become indispensable in various industrial applications. However, their real internal structure usually deviates from an ideal core–shell structure. To control how the particles perform with regard to their specific applications, characterization techniques are required that can distinguish an ideal from a nonideal morphology. In this work, we investigated poly(tetrafluoroethylene)–poly(methyl methacrylate) (PTFE–PMMA) and poly(tetrafluoroethylene)–polystyrene (PTFE–PS) polymer CSNPs with a constant core diameter (45 nm) but varying shell thicknesses (4–50 nm). As confirmed by transmission scanning electron microscopy (T-SEM), the shell completely covers the core for the PTFE–PMMA nanoparticles, while the encapsulation of the core by the shell material is incomplete for the PTFE–PS nanoparticles. X-ray photoelectron spectroscopy (XPS) was applied to determine the shell thickness of the nanoparticles. The software SESSA v2.0 was used to analyze the intensities of the elastic peaks, and the QUASES software package was employed to evaluate the shape of the inelastic background in the XPS survey spectra. For the first time, nanoparticle shell thicknesses are presented, which are exclusively based on the analysis of the XPS inelastic background. Furthermore, principal component analysis (PCA)-assisted time-of-flight secondary-ion mass spectrometry (ToF-SIMS) of the PTFE–PS nanoparticle sample set revealed a systematic variation among the samples and, thus, confirmed the incomplete encapsulation of the core by the shell material. As opposed to that, no variation is observed in the PCA score plots of the PTFE–PMMA nanoparticle sample set. Consequently, the complete coverage of the core by the shell material is proved by ToF-SIMS with a certainty that cannot be achieved by XPS and T-SEM.
This is a corrigendum to the original article "Determining the thickness and completeness of the shell of polymer core-shell nanoparticles by X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and transmission scanning electron microscopy" that was published in "The journal of physical chemistry C", vol. 123 (2019), no. 49 pp. 29765-29775.
KEY COMPARISON
High purity elements can serve as a realization of the SI unit amount of substance for the specific element. Solutions prepared from high purity metals by applying gravimetric preparation and the concept of molar mass are used as 'calibration' solutions in many fields of analytical chemistry and provide the metrological basis in elemental analysis. Since ideal purity does not exist for real materials, the actual purity of the high purity material must be known with a specified uncertainty. As required uncertainties around 10-4 relative on the purity statement are not accessible in almost all cases by a direct measurement of the element in itself, the indirect approach is followed, where all elements excepting the matrix element itself are measured and their sum is subtracted from the value for ideal purity, which is 1 kg/kg.
It was the aim of this comparison to demonstrate the capability of national metrology institutes and designated institutes to determine the purity of pure elements. In order to limit the effort within this comparison, only six metallic impurities (Ag, Al, Cd, Cr, Ni, Tl) in the low mg/kg range are considered in a zinc matrix. It has to be underlined here that the task was to measure the purity of zinc based on the determination of six analytes. The task is not trace analysis of specific analytes in zinc. This subtle distinction defines different measurands.
The sample, pure Zn, was cut in pieces of cubic geometry for wet chemical analysis or of pin geometry for GDMS analysis and was sent to the participants. The comparison was run under the auspices of the Inorganic analysis Working Group (IAWG) of the CCQM and was piloted by the BAM Federal Institute for Materials Research and Testing, Berlin, Germany. The majority of the participants applied ICP-MS techniques and only two participants used additionally atomic absorption spectrometry. GDMS was used only by one participant.
The observed spreads for the measurement results reported by the participants were significantly lower than those of the preceding study CCQM-P107 and were well below the target uncertainty of 30% relative. As a consequence, comparability within the participating laboratories is demonstrated to be established. The individual measurement results, mean values and medians derived were in all cases very consistent with the reference values obtained by IDMS and so the accuracy of the measurement results for the participating laboratories is as well demonstrated to be established. Especially with the results of CCQM-P62 and CCQM-P107 in mind, the outcome of CCQM-K72 can be considered as a big step forward in the community.
CCQM is aware of the difference between a characterization based on only six analytes and a complete characterization. Therefore, the pilot study CCQM-P149 has been initiated and already started, which focuses on the fit-for-purpose approaches for the purity determination of metals (here: zinc) to be used as primary standards in elemental analysis. Another follow-up in the form of a pilot study on non-metal impurities is mandatory, because non-metal impurities such as oxygen, nitrogen and sulfur often make up the largest contributions.
Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/.
The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).