TY - JOUR A1 - Gusarova, Tamara A1 - Methven, B. A1 - Kipphardt, Heinrich A1 - Sturgeon, R. A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Calibration of double focusing glow discharge mass spectrometry instruments with pin-shaped synthetic standards N2 - Calibration of two commercially available glow discharge double focusing mass spectrometers, the VG 9000 and Element GD, is described using synthetic pin standards pressed from solution doped copper and zinc matrices. A special pressing die was developed for this purpose and optimal results were obtained with the highest possible pressures, i.e., 95 kN·cm- 2. This calibration approach permits the determination of trace element mass fractions down to µg·kg- 1 with small uncertainties and additionally provides traceability of the GD-MS results in the most direct manner to the SI (International System of Units). Results were validated by concurrent measurements of a number of compact copper and zinc certified reference materials. The impact of the sample pin cross-section (circular or square) was investigated with the use of a new pin-sample holder system for the Element GD. The pin-sample holder was designed by the manufacturer for pin-samples having circular cross-section; however, samples with square pin cross-section were also shown to provide acceptable results. Relative Sensitivity Factors for some 50 analytes in copper (VG 9000, Element GD) and zinc matrices (VG 9000) are presented. The field of applicability of GD-MS may be considerably extended via analysis of pin geometry samples based on their ease of preparation, especially with respect to the accuracy and traceability of the results and the enhanced number of analytes which can be reliably calibrated using such samples. KW - Glow discharge KW - Pin sample KW - Calibration PY - 2011 U6 - https://doi.org/10.1016/j.sab.2011.12.001 SN - 0584-8547 SN - 0038-6987 VL - 66 IS - 11-12 SP - 847 EP - 854 PB - Elsevier CY - Amsterdam AN - OPUS4-25346 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Zayed, Mahamed Mokhtar A1 - Hodoroaba, Vasile-Dan A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Improvement of signal sensitivity using hollow cathode effect in glow discharge optical emission spectroscopy T2 - 13. GDS-Anwendertreffen CY - Hanau, Germany DA - 2006-09-04 PY - 2006 AN - OPUS4-13483 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Lange, Britta A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Analysis of high purity zinc by glow discharge mass spectrometry for use in thermometry T2 - 13th International Conference on ultra high-purity base metals CY - Berlin, Germany DA - 2006-09-11 PY - 2006 AN - OPUS4-13485 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Lange, Britta A1 - Kipphardt, Heinrich A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Analysis of high purity zinc by glow discharge mass spectrometry for use in thermometry T2 - Euromet Workshop -732 / LNE - INM CY - Paris, France DA - 2006-11-23 PY - 2006 AN - OPUS4-13497 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Lange, Britta A1 - Kipphardt, Heinrich A1 - Venzago, C. A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - New way to overcome the drawbacks of RSF- and Standard-RSF quantification concepts for VG 9000 and Element GD T2 - Joint GLADNET - EW-GDS - German GDS Users' Group meeting CY - Brussels, Belgium DA - 2007-09-14 PY - 2007 AN - OPUS4-14799 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Lange, Britta A1 - Kipphardt, Heinrich A1 - Venzago, C. A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - GD-MS: calibration for VG9000 and Element GD - Do RSF- and StRSF-concepts always work? T2 - EuroAnalysis XIV CY - Antwerp, Belgium DA - 2007-09-09 PY - 2007 AN - OPUS4-14800 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Lange, Britta A1 - Kipphardt, Heinrich A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Comparison of different quantification procedures in glow discharge mass spectrometry applied to high-purity metals T2 - 2007 European Winter Conference on Plasma Spectrochemistry CY - Taormina, Italy DA - 2007-02-18 PY - 2007 AN - OPUS4-13680 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Hodoroaba, Vasile-Dan A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Improvement of signal sensitivity using hollow cathode effect in glow discharge optical emission spectroscopy T2 - Interessengemeinschaft Atomspektroskopie IGAS 2006 CY - Berlin, Germany DA - 2006-11-08 PY - 2006 AN - OPUS4-13776 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Hodoroaba, Vasile-Dan A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Enhancement of signal sensitivity in glow discharge optical emission spectroscopy by use of the hollow cathode effect for the analysis of pure metals T2 - 2007 European Winter Conference on Plasma Spectrochemistry CY - Taormina, Italy DA - 2007-02-18 PY - 2007 AN - OPUS4-14639 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Hodoroaba, Vasile-Dan A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Enhancement of signal sensitivity in optical emission spectroscopy by coupling a grimm type glow discharge with hollow cathode T2 - ANAKON 2007 CY - Jena, Germany DA - 2007-03-27 PY - 2007 AN - OPUS4-14640 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Lange, Britta A1 - Kipphardt, Heinrich A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Glimmentladungsmassenspektrometrie im Einsatz für die Thermometrie T2 - CANAS '07, Colloquium Analytische Atomspektroskopie CY - Konstanz, Germany DA - 2007-03-18 PY - 2007 AN - OPUS4-14631 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Hodoroaba, Vasile-Dan A1 - Kipphardt, Heinrich A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Hohlkathode in Kombination mit einer Grimmschen Glimmentladung zur Spurenanalyse von Reinstmetallen T2 - 14. Deutsche GDS-Anwendertreffen CY - Berlin, Germany DA - 2008-04-17 PY - 2008 AN - OPUS4-17539 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rudtsch, S. A1 - Fahr, M. A1 - Fischer, J. A1 - Gusarova, Tamara A1 - Kipphardt, Heinrich A1 - Matschat, Ralf T1 - High-Purity Fixed Points of the ITS-90 with Traceable Analysis of Impurity Contents N2 - The International Temperature Scale of 1990 (ITS-90) is based on thermodynamic equilibrium states of ideally pure substances. The largest contribution to the uncertainty budgets of most metallic fixed points is the influence of impurities on the fixed-point temperature. Therefore, a traceable chemical analysis of the remaining impurities with small uncertainty is the basis of further progress. Further requirements are better knowledge of the phase diagrams at very low impurity contents, impurity segregation, and the quantification and correction of thermal effects during a fixed-point realization. In this article, current and future activities at PTB and BAM in order to develop improved metallic fixed-point cells of the ITS-90 are reviewed. KW - Chemical analysis KW - Fixed points KW - Impurities KW - ITS-90 KW - Phase diagrams KW - Thermal effects PY - 2008 U6 - https://doi.org/10.1007/s10765-007-0358-9 SN - 0195-928X SN - 1572-9567 VL - 29 IS - 1 SP - 139 EP - 150 PB - Springer CY - Dordrecht AN - OPUS4-17455 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gusarova, Tamara A1 - Lange, Britta A1 - Methven, B. A1 - Hoffmann, T. A1 - Kipphardt, Heinrich A1 - Matschat, Ralf A1 - Venzago, C. A1 - Sturgeon, R. A1 - Panne, Ulrich T1 - Calibration of DC GD-MS with synthetic standards T2 - ANAKON 2009 CY - Berlin, Germany DA - 2009-03-17 PY - 2009 AN - OPUS4-18989 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gusarova, Tamara A1 - Hodoroaba, Vasile-Dan A1 - Matschat, Ralf A1 - Kipphardt, Heinrich A1 - Panne, Ulrich T1 - Exploitation of the hollow cathode effect for sensitivity enhancement of Grimm-type DC glow discharge optical emission spectroscopy N2 - The hollow cathode (HC) effect was investigated in non-cooled 15 mm deep drilled flat metallic analytical samples that were easy to prepare. The deep cavity used ("complete HC" in contrast to "recessed HC" with 2-3 mm deep cavity) intensified the HC effect notably and therefore distinctly improved the detection power of the common GD-OES with planar cathodes. A signal enhancement of up to a factor of 150, not reported earlier, in comparison with flat conventional samples was achieved. A better separation of the analytical lines from spectral interferences was observed when the HC assembly was applied. Additionally, an effect of strongly enhanced intensities of atomic lines and somewhat decreased intensities of ionic lines was detected in the case of HC in comparison to usual planar cathodes. The investigations were carried out with samples of copper, steel and zinc matrices using both the same and individually optimised glow discharge (GD) electrical parameters. KW - Hollow cathode KW - Grimm type glow discharge KW - Emission spectroscopy KW - GD-OES KW - Sensitivity PY - 2009 U6 - https://doi.org/10.1039/b814977a SN - 0267-9477 SN - 1364-5544 VL - 24 SP - 680 EP - 684 PB - Royal Society of Chemistry CY - London AN - OPUS4-19600 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rudtsch, S. A1 - Gusarova, Tamara A1 - Aulich, A. A1 - Fahr, M. A1 - Fischer, J. A1 - Kipphardt, Heinrich A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Procedure for the impurity-related correction at the indium fixed-point N2 - Determining the influence of impurities on the fixed-point emperatures of the ITS-90 requires the completion of several tasks. In this paper, the Progress made at Physikalisch-Technische Bundesanstalt (PTB) and BAMFederal Institute for Materials Research and Testing is presented and remaining questions are discussed. The projected characterization procedure at PTB, which is based on the established SIE method (sum of the individual estimates), using a new indium fixed-point cell is described as an example. This procedure includes an SI-traceable chemical Analysis of the material in the fixed-point cell with sufficiently low uncertainties, the individual experimental determination of the influence of the quantified impurities on the fixed-point temperature, and the establishment of direct links to the phase-transition temperatures of the national standard and of an assumed material of ideal purity. A characteristic difference to the common practice is the chemical analysis of the fixed-point metal being done after determining the cell’s freezing temperature. This allows for the detection and consideration of contamination and purification effects due to the filling process, or due to the contact with the carbon crucible and other parts of the fixed-point cell. A chemical analysis of an indium fixed-point was carried out by BAM with relative measurement uncertainties below 30 % which have not been previously achieved. The results provide evidence for the precipitation of some impurities, which is apparently inconsistent with the corresponding binary phase diagrams, but was explained in a recent publication. Implications for the use of the SIE method shall be described briefly at the end. KW - Chemical analysis KW - Fixed-points KW - Impurities KW - ITS-90 PY - 2011 U6 - https://doi.org/10.1007/s10765-011-0915-0 SN - 0195-928X SN - 1572-9567 VL - 32 IS - 1-2 SP - 293 EP - 302 PB - Springer CY - Dordrecht AN - OPUS4-23373 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - THES A1 - Gusarova, Tamara T1 - Wege zur genauen Charakterisierung hochreiner Materialien mit der Glimmentladungs-Massenspektrometrie (GD-MS) N2 - Die vorliegende Arbeit befasst sich mit der Analyse hochreiner Metalle mittels GD-MS (Glimmentladungs-Massenspektrometrie). Der Schwerpunkt war dabei die Verbesserung der genauen Bestimmung von Elementspuren, insbesondere im μg kg-1-Bereich, für den Kalibrierproben bekannter Zusammensetzung praktisch nicht existieren. Zur Überwindung des Problems wurden flüssigdotiere Pulverpresslinge als synthetische Kalibrierproben für die Matrices Zn, In, Cu, Fe sowie Co und das System Co/C hergestellt. Durch umfassende Untersuchungen der Praparationsschritte und eine eingehende Charakterisierung der Presslinge konnte deren Herstellungsprozess optimiert und deren Verhalten in der Glimmentladung besser verstanden werden. Das erarbeitete Quantifizierungskonzept wurde durch die Messung zertifizierter Matrixreferenzmaterialien mit Gehalten im mg kg-1-Bereich validiert, und seine Eignung auf hohem metrologischen Niveau bei der sehr erfolgreichen Teilnahme an einem weltweiten Ringversuch der internationalen Metrologieinstitute nachgewiesen. Gegenüber den bislang mangels tragfähiger Alternative verwendeten kalibrierprobenfreien Quantifizierungskonzepten ist der Einsatz der Presslinge bezüglich Richtigkeit, Unsicherheit und Rückführung auf das internationale Einheitensystem deutlich überlegen. Die GD-MS mit ihren Vorteilen als schnelle direkte Feststoffmethode erreicht so erstmalig die Analysenqualität der etablierten losungsbasierten Analysenmethoden, und erhöht damit ihren Anwendungsbereich deutlich, so dass sie schließlich auch für die Analyse von realen Proben für wichtige metrologische Fragestellungen angewendet werden konnte, wie für die Analyse von Zn-Fixpunktzellen, die für die Definition der internationalen Temperaturskala ITS 90 benötigt werden, oder für Primarnormale der chemischen Analytik. Darüber hinaus wurde grundlegend die Übertragbarkeit der klassischen kalibrierprobenfreien Quantifizierungskonzepte auf das neu auf dem Markt befindliche hochauflösenden GD-MS Gerat (Element GD) untersucht. Dabei wurden insbesondere die Einschränkungen herausgearbeitet, die für das völlig anders konstruierte Vorgängermodell VG 9000 nicht gelten. Ergänzende Untersuchungen zum Hohlkathodeneffekt führten zwar nicht bei der GD-MS, wohl aber bei der GD OES (Glimmentladung mit optischer Emissionsspektrometrie), zu einer enormen Steigerung des Nachweisvermögens für Elementspuren. N2 - The main aim of this work consists in the investigation, development and application of improved possibilities of accurate analysis of high purity materials using the solid sample technique of Glow Discharge Mass Spectrometry (GD-MS), as well as in the sensitivity enhancement of GD Optical Emission Spectrometry (GD-OES) by implicating the hollowcathode effect. The emphasis of the PhD thesis consists in the accurate quantification for GD-MS. As appropriate certified reference materials (CRMs) for calibration are lacking in most cases an accurate quantification especially for trace elements mass fractions at μg kg-1 Level can often not be achieved. To overcome this problem and to expand the possibilities of modern GD-MS hereby, synthetic standards were applied for calibration of both high resolution GD-MS instruments “VG 9000” and “Element GD”. The standards were prepared by doping of matrix powder with trace element standard solutions followed by drying and pressing the doped powder to compact pellets. With the quantification approach worked out and described here accurate analysis results with small uncertainties can be achieved for most elements of periodic table in almost every matrix composition. Furthermore direct traceability of the analytical results to the International System of Units (SI) is provided ensuring their higher metrological quality. Numerous additional systematic investigations concerning the preparation of the synthetic standards and their properties were carried out. The results of calibration of GD-MS instruments with synthetic standards for Co (Co-C), Cu, In, Fe and Zn matrices were checked by measuring CRMs. These results were also contrasted with those of other quantification approaches, as usually used in GD-MS routine. The results achieved with synthetic standards had the highest accuracy. The successful participation in the round robin test CCQM-P107 between international metrological institutes for analysis of high purity zinc demonstrated the high quality of the results based on the calibration procedure with synthetic standards. The quality of the results was comparable to those of established liquid sample methods. Additionally in the frame of this work high purity materials to be used for important metrological purposes of thermometry (fixpoint materials) and of analytical chemistry (primary standard materials) were comprehensively analyzed using the proposed quantification strategy. T3 - BAM Dissertationsreihe - 55 KW - Glimmentladung KW - Reinstmetalle KW - Rückführung KW - Massenspektrometrie KW - synthetische Standards PY - 2010 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-1035 SN - 978-3-9813346-1-6 SN - 1613-4249 VL - 55 SP - 1 EP - 225 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-103 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kipphardt, Heinrich A1 - Matschat, Ralf A1 - Vogl, Jochen A1 - Gusarova, Tamara A1 - Czerwensky, Michael A1 - Heinrich, Hans-Joachim A1 - Hioki, A. A1 - Konopelko, L.A. A1 - Methven, B. A1 - Miura, T. A1 - Petersen, O. A1 - Riebe, Gundel A1 - Sturgeon, R. A1 - Turk, G.C. A1 - Yu, L. L. T1 - Purity determination as needed for the realisation of primary standards for elemental determination: status of international comparability N2 - Within the National Metrology Institutes (NMIs) and designated laboratories, an interlaboratory comparison, CCQM-P107, was conducted to verify the degree of international comparability concerning the results of purity analysis. The mass fractions of Ag, Bi, Cd, Cr, Ni, Tl at the lower mg/kg-level in a high purity zinc material were determined, but the real measurand in metrological sense was the sum of the six mass fractions. Homogeneity was investigated by glow discharge mass spectrometry, reference values were obtained using isotope dilution mass spectrometry. Six NMIs participated, contributing eight independent data sets. The agreement amongst the results of the participants, their median and the agreement with the reference values were usually excellent and in almost all cases below the target uncertainty of 30% relative. In this manner, the accuracy of results and the comparability between the participants was demonstrated to be established. KW - Interlaboratory comparison KW - Purity analysis KW - High purity metals KW - CCQM-P107 KW - Zinc PY - 2010 U6 - https://doi.org/10.1007/s00769-009-0557-0 SN - 0949-1775 SN - 1432-0517 VL - 15 IS - 1 SP - 29 EP - 37 PB - Springer CY - Berlin AN - OPUS4-20767 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gusarova, Tamara A1 - Hofmann, T. A1 - Kipphardt, Heinrich A1 - Venzago, C. A1 - Matschat, Ralf A1 - Panne, Ulrich T1 - Comparison of different calibration strategies for the analysis of zinc and other pure metals by using the GD-MS instruments VG 9000 and element GD N2 - Synthetic pressed metal powder standards doped with standard solutions were used for the calibration of both commercially available high resolution GD-MS instruments Element GD and VG 9000 for zinc matrix. Different quantification procedures (IBR, Standard RSF, matrix matched RSF from the calibration with CRMs and use of doped synthetic standards) are compared using zinc matrix as an example, whereas the calibration with doped pellets turned out to be the best quantification technique for high-purity materials. The applicability of the Standard RSF concept is scrutinised. In this context, RSF values for several Matrices (Co, Cu, Fe, In and Zn) are reported additionally. PY - 2010 U6 - https://doi.org/10.1039/b921649a SN - 0267-9477 SN - 1364-5544 VL - 25 SP - 314 EP - 321 PB - Royal Society of Chemistry CY - London AN - OPUS4-22376 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -