TY - JOUR A1 - Gonzales-Gago, C. A1 - Smid, P. A1 - Hofmann, T. A1 - Venzago, C. A1 - Hoffmann, V. A1 - Gruner, W. A1 - Pfeifer, Jens A1 - Richter, Silke A1 - Kipphardt, Heinrich T1 - Investigations of matrix independent calibration approaches in fast flow glow discharge mass spectrometry JF - JAAS N2 - 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). KW - Fast flow GD KW - GDMS KW - Calibration KW - Matrix independent calibration PY - 2019 DO - https://doi.org/10.1039/c9ja00023b SN - 1364-5544 SN - 0267-9477 VL - 34 IS - 6 SP - 1109 EP - 1125 PB - Royal Society of Chemistry CY - London AN - OPUS4-47842 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hoffmann, V. A1 - Dorka, R. A1 - Wilken, L. A1 - Hodoroaba, Vasile-Dan A1 - Wetzig, K. T1 - Present possibilities of thin-layer analysis by GDOES JF - Surface and interface analysis N2 - The analysis of thin layers of thickness 100 nm has become a new field of application for glow discharge optical emission spectroscopy (GDOES). In this paper an overview is given of the experiences and possibilities gained by the authors in later years at their research, development and application of GDOES. During GDOES analysis of a multilayer system the depth resolution was determined using the inverse maximal slope method. Under optimized discharge conditions a depth resolution of 25 nm at 100 nm depth was achieved. The gas flow in a Grimm-type source for glow discharge mass spectrometry (GDMS) was simulated and a correlation between calculated pressure and crater shape was found. Cleanness of the sample and source turned out to be essential for a fast stabilization time and reduction of the influence of light elements and molecules. Thereby, a 10 nm layer at the top surface of a sample could be quantified. Apart from the influence of density, the reflectivity of the sample surface is discussed. It is shown that a high sample reflectivity can cause up to 100% more light to be measured by the spectrometer. KW - GDOES KW - GDMS KW - Thin-layer analysis PY - 2003 DO - https://doi.org/10.1002/sia.1575 SN - 0142-2421 SN - 1096-9918 VL - 35 IS - 7 SP - 575 EP - 582 PB - Wiley CY - Chichester AN - OPUS4-2624 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, P. A1 - Panne, Ulrich A1 - Traub, Heike A1 - Pfeifer, Jens A1 - Vogl, Jochen T1 - Quantification of sulphur in copper and copper alloys by GDMS and LA-ICP-MS, demonstrating metrological traceability to the international system of units JF - Journal of Analytical Atomic Spectrometry N2 - The quantification of the sulphur mass fraction in pure copper and copper alloys by GDMS and LA-ICP-MS revealed a lack of traceability mainly due to a lack of suitable certified reference materials for calibrating the instruments. Within this study GDMS and LA-ICP-MS were applied as routine analytical tools to quantify sulphur in copper samples by applying reference materials as calibrators, which were characterized for their sulphur mass fraction by IDMS beforehand. Different external calibration strategies were applied including a matrix cross type calibration. Both techniques with all calibration strategies were validated by using certified reference materials (others than those used for calibration) and good agreement with the reference values was achieved except for the matrix cross type calibration, for which the agreement was slightly worse. All measurement results were accompanied by an uncertainty statement. For GDMS, the relative expanded (k = 2) measurement uncertainty ranged from 3% to 7%, while for LA-ICP-MS it ranged from 11% to 33% when applying matrix-matched calibration in the sulphur mass fraction range between 25 mg kg-1 and 1300 mg kg-1. For cross-type calibration the relative expanded (k = 2) measurement uncertainty need to be increased to at least 12% for GDMS and to at least 54% for LA-ICP-MS to yield metrological compatibility with the reference values. The so obtained measurement results are traceable to the international system of units (SI) via IDMS reference values, which is clearly illustrated by the unbroken chain of calibrations in the metrological traceability scheme. KW - Sulfur KW - Copper KW - GDMS KW - LA-ICP-MS KW - Uncertainty KW - Traceability KW - SI PY - 2021 DO - https://doi.org/10.1039/d1ja00137j SN - 0267-9477 VL - 36 IS - 11 SP - 2404 EP - 2414 PB - Royal Society of Chemistry AN - OPUS4-53412 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pisonero, J. A1 - Fandino, J. A1 - Nordlien, J. H A1 - Richter, Silke A1 - Pfeifer, Jens A1 - Quarles, C. D. A1 - Gonzalez, J. A1 - Jakubowski, Norbert A1 - Bordel, N. T1 - Improving the analytical performance of pulsed-GD-SFMS for multi-elemental depth profile analysis of heat-treated Zn coatings on extruded aluminium JF - Journal of Analytical Atomic Spectrometry N2 - The formation of diffusion layers on Zn layers deposited on Al substrates is mainly used to prevent corrosion effects. Evaluation of the influence exerted by different coating methodologies and heat treatments on the formation of these diffusion layers is of great interest for the aluminium industry. Particularly, multi-elemental in-depth distributions of major, minor and trace elements in Zn-coatings is highly demanded before and after heat treatments. A fast characterization of these materials require a direct solid analytical technique able to provide high sensitivity and high depth resolution. For this purpose, an improved analytical method based on the use of pulsed glow discharge sector field mass spectrometry (pulsed-GD-SFMS) is investigated. Glow discharge operating parameters (e.g. pulse duration, pulse frequency), glow discharge source design (e.g. flow tube lengths), and SFMS mass spectra acquisition conditions (e.g. integration time) are evaluated to achieve low sputtering rates, high mass spectra acquisition rates and improved depth resolution. At the optimize conditions Zn coatings deposited by arc-spray and electrodeposition are analysed before and after heat treatments to evaluate the diffusion of different key elements. Moreover, results are validated using femtosecond laser ablation (fs-LA)-ICP-MS, which provides additional information about the heterogeneous distribution of some elements in the Zn coatings. KW - GDMS KW - Pulsed-GD-SFMS KW - Depht profiling KW - Zn KW - Aluminium PY - 2019 DO - https://doi.org/10.1039/c9ja00189a VL - 34 IS - 11 SP - 2252 EP - 2260 PB - Royal Society of Chemistry CY - London AN - OPUS4-49451 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -