TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Data-Driven Spectrochemical Methods for Elemental and Isotopic Analysis N2 - High-resolution optical spectrometers generate spectra containing tens of thousands of data points per sample. Picometre-scale isotope shifts, matrix-induced line broadening, and strong inter-feature correlations render classical peak fitting unreliable. Current analytical challenges, therefore, require rigorous algorithms able to expose latent structure, quantify uncertainty, and remain chemically interpretable. The research program presented in this lecture integrates state-of-the-art spectrochemical instrumentation with mathematically disciplined data models. Principal Component Analysis and Partial Least Squares provide chemically meaningful latent variables, while gradient-boosted decision trees or deep neural networks (ANNDL) capture residual non-linearity without sacrificing traceability. All models are trained on isotope-enriched or synthetically generated spectra and distributed with full validation workflows. T2 - Chemisches Institutskolloquium, Humboldt-Universität zu Berlin CY - Berlin, Germany DA - 21.05.2025 KW - Spectrochemistry KW - Isotopes KW - Machine learning KW - Battery KW - Data fusion PY - 2025 AN - OPUS4-63488 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Lithium isotope fractionation as a diagnostic tool for aging lithium-ion batteries N2 - Lithium-ion batteries (LIBs) are central to modern energy storage technologies, powering applications from portable electronics to electric vehicles and grid storage systems. Their popularity comes from their high energy density, efficiency, and extended cycle life. However, over time, various aging mechanisms lead to capacity loss, increased internal resistance, and, ultimately, battery failure. Understanding and predicting these aging processes is crucial for enhancing the reliability and longevity of LIBs. This necessity makes the development of advanced diagnostic tools essential. This study uses plasma-based spectrometry techniques to explore lithium isotope fractionation (LIF) as a predictive tool for monitoring LIB aging and degradation. Mass spectrometric techniques —including MC-ICP-MS, LA-ICP-MS, and MICAP-MS— were employed to analyze lithium isotopic composition in both new and aged lithium cobalt oxide (LCO) cells, including lab-made coin cells and commercial batteries. An isotopic fractionation was identified during electrochemical cycling: 6Li migrates towards the anode, while 7Li accumulates in the cathode. These isotopic patterns correlate with structural degradation, including solid electrolyte interphase (SEI) growth and crack formation, as confirmed by FIB-SEM, XANES, and EXAFS analyses. This correlation demonstrates that LIF aligns with key aging mechanisms in model coin cells and commercial batteries, such as capacity fade and impedance growth. LIF provides a powerful diagnostic tool for battery health monitoring and aging prediction by linking isotopic fractionation to structural degradation. This approach offers significant potential to extend battery lifespan and improve the reliability of energy storage systems. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Isotope KW - Lithium KW - Battery aging KW - Degradation KW - Fractionation KW - Battery PY - 2025 AN - OPUS4-63487 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Zengchao A1 - Akkus, Asli A1 - Weisheit, W. A1 - Giray, Thorsten A1 - Penk, Sibylle A1 - Buttler, Sabine A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique T1 - Multielement analysis in soils using nitrogen microwave inductively coupled atmospheric pressure plasma mass spectrometry N2 - In this study, we employed nitrogen microwave inductively coupled atmospheric-pressure plasma (MICAP) combined with quadrupole mass spectrometry (MS) and a liquid sample introduction system to analyze heavy metals in soils. The vanadium, cobalt, nickel, zinc, copper, chromium, arsenic, lead, and cadmium contents in seven reference and three environmental soil samples determined using MICAP-MS were within the uncertainty of the reference values, indicating that MICAP-MS is promising for soil analysis similar to the conventional inductively coupled plasma mass spectrometry (ICP-MS) technique. In addition, the limits of detection (LODs) and sensitivity of both techniques using N2 and Ar plasma were of the same order of magnitude. Furthermore, the performance of MICAP-MS under different N2 purity was investigated, and we found that the plasma formation and ionization efficiency were not influenced by the impurities in the gas. A prominent advantage of MICAP-MS is the low operating cost associated with gas consumption. In this work, MICAP-MS used nitrogen, which is cheaper than argon, and consumed 25% less gas than ICP-MS. Using low-purity N2 can further reduce the gas cost, making MICAP-MS more cost effective than ICP-MS. These results suggest that MICAP-MS is a promising alternative to ICP-MS for the analysis of heavy metals in the soil. KW - Soil KW - Microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) KW - Nitrogen plasma KW - Multi-element analysis PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-561048 DO - https://doi.org/10.1039/d2ja00244b SN - 0267-9477 VL - 37 IS - 12 SP - 2556 EP - 2562 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-56104 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kowalewska, Z. A1 - Abad Andrade, Carlos Enrique A1 - Okruss, M. A1 - Recknagel, Sebastian T1 - Feasibility of high-resolution continuum source molecular absorption spectrometry for vanadium determination N2 - This work aimed to evaluate high-resolution continuum source molecular absorption spectrometry (HR-CS MAS), traditionally used to determine non-metals, for the determination of a new element, metal, vanadium. VO was selected as a target molecule because it is relatively stable and was expected to be spontaneously generated in a flame or a graphite furnace (GF). The high-resolution overview spectra of the molecule were obtained in a wide range of 480–630 nm, and absorption due to the X4Σ−–C4Σ− electronic transition was registered. A unique instrumental setup, comprising a prototype Modular Simultaneous Echelle Spectrograph (MOSES) and a commercial HR-CS MAS apparatus, was applied in the research. Finally, the spectral area centered at 550.6230 nm was selected for analysis. A method was developed to determine V in solutions of catalysts of heavy petroleum oil hydroprocessing using a commercial HR-CS spectrometer in a flame version. Although sensitivity was relatively poor (characteristic concentration 380 mg L−1), an extremely low noise enabled reaching a satisfactory detection limit (20 mg L−1 in solution, i.e. 0.1% m:m in the catalyst). For the first time vanadium was determined using ordinary air-acetylene flame. The obtained results were consistent with the results of atomic absorption spectrometry with N2O-C2H2 flame. Unfortunately, only a small population of VO molecules could have been generated in GF measurements. Furthermore, the observed VO molecules appeared only at unfavorably high temperatures. The work shows the potential of HR-CS MAS as a scientific tool for investigating the mechanism of processes occurring in the GF. This work can inspire other research of new analytes for HR-CS MAS. KW - Vanadium KW - HR-CS-MAS KW - VO KW - High-resolution continuum source molecular absorption spectrometry KW - AAS PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-569899 DO - https://doi.org/10.1039/D2JA00281G SN - 0267-9477 VL - 38 IS - 2 SP - 472 EP - 483 PB - Royal Society of Chemistry AN - OPUS4-56989 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Zengchao A1 - Winckelmann, Alexander A1 - Vogl, Jochen A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique T1 - Determination of calcium, iron, and selenium in human serum by isotope dilution analysis using nitrogen microwave inductively coupled atmospheric pressure plasma mass spectrometry (MICAP-MS) N2 - In this study, we demonstrate the applicability of nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) for Ca, Fe, and Se quantification in human serum using isotope dilution (ID) analysis. The matrix tolerance of MICAP-MS in Na matrix was investigated, uncovering that high Na levels can suppress the signal intensity. This suppression is likely due to the plasma loading and the space charge effect. Moreover, 40Ca and 44Ca isotopic fractionation was noted at elevated Na concentration. Nine certified serum samples were analyzed using both external calibration and ID analysis. Overestimation of Cr, Zn, As, and Se was found in the results of external calibration, which might be resulted from C-induced polyatomic interference and signal enhancement, respectively. Further investigations performed with methanol showed a similar enhancement effect for Zn, As, and Se, potentially supporting this assumption. The mass concentrations determined with ID analysis show metrological compatibility with the reference values, indicating that MICAP-MS combined with ID analysis can be a promising method for precise Ca, Fe, and Se determination. Moreover, this combination reduces the influences of matrix effects, broadening the applicability of MICAP-MS for samples with complex matrix. KW - Selenium KW - Nitrogen microwave inductively coupled atmospheric pressure mass spectrometry KW - Isotope dilution KW - Human serum KW - Calcium KW - Iron PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598664 DO - https://doi.org/10.1007/s00216-024-05274-0 SN - 1618-2642 SP - 3117 EP - 3125 PB - Springer CY - Berlin AN - OPUS4-59866 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Recknagel, Sebastian A1 - Vogel, Kristin T1 - Berechnung und Nutzung von Unsicherheiten zertifizierter Werte von Referenzmaterialien N2 - Referenzmaterialien sind entscheidend für die Qualitätssicherung von Laboratorien. Diese nutzen Referenzmaterialien unter anderem zur Validierung von Messverfahren und zur Kalibrierung von Geräten. Dabei ist zu beachten, dass zertifizierte Merkmalswerte stets eine gewisse Unsicherheit aufweisen. Die Ermittlung dieser Unsicherheitsbeiträge ist Gegenstand des Artikels. Des Weiteren wird ein Vorgehen beschrieben, wie die Unsicherheit von Messverfahren mit Hilfe eines Referenzmaterials bestimmt werden kann. KW - Referenzmaterial KW - Messunsicherheit KW - Qualitätskontrolle PY - 2024 DO - https://doi.org/10.1515/teme-2024-0025 SN - 0171-8096 SP - 1 EP - 7 PB - De Gruyter AN - OPUS4-60564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - You, Zengchao T1 - Multi-element analysis in different matrices using nitrogen microwave inductively coupled atmospheric pressure plasma mass spectrometry (MICAP-MS) N2 - Inductively coupled plasma mass spectrometry (ICP-MS) emerged as a powerful technique for trace analysis of soil due to its multi-element capability, high sensitivity and low sample consumption. However, despite its success and widespread use, ICP-MS has several persistent drawbacks, such as high argon gas consumption, argon-based polyatomic interferences and the need for complicated RF-power generators. Unlike argon-based ICP, the nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) uses nitrogen as plasma gas, which eliminates high operating costs associated with argon-gas consumption as well as the argon-based interferences1. In this work, the applicability of MICAP-MS for elemental analysis in different matrices is investigated. For this purpose, reference soil samples and steel samples are digested with aqua regia and used for analysis. Concentrations of selected elements are determined using MICAP-MS and validated with ICP-MS und certified values. Sensitivities, limits of detection and gas consumption for both methods are compared and discussed in detail. Performance of MICAP-MS under different nitrogen plasma gas concentrations is investigated and compared. Moreover, the performance of MICAP-MS in alloy matrices is investigated and discussed. T2 - EWCPS 2023 CY - Ljubljana, Slovenia DA - 29.01.2023 KW - Microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) KW - Multi-element analysis KW - Soil KW - Steel KW - Nitrogen plasma PY - 2023 AN - OPUS4-56994 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Laser spectroscopy methods for calcium isotope analysis N2 - Calcium isotope analysis can be an important tool for paleoclimate studies of the carbon cycle, as well in carbon capture technology, but its utility is limited by challenges using conventional mass spectrometry. We propose a new fast, precise, and high-throughput technology based on multiple complementary high-resolution spectroscopies analyzed by machine-learning. T2 - Seminars Chemical Physics Caltech CY - Pasadena, CA, USA DA - 13.04.2022 KW - Calcium KW - Atomic spectroscopy KW - CaF KW - Calcium monofluoride KW - Carbon cycle KW - Doppler effect KW - Sub-doppler spectroscopy KW - Laser spectroscopy PY - 2022 AN - OPUS4-56499 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - On developments of continuum source atomic and molecular absorption spectrometry N2 - Der Bunsen-Kirchhoff-Preis 2022 wurde am 23.06.2022 anlässlich der analytica conference in München an Dr. Carlos Abad verliehen - in Anerkennung seiner exzellenten Entwicklungen im Bereich der continuum source atomic absorption spectrometry (CS-AAS). Dr. Carlos Abad ist ein herausragender Experte auf dem Gebiet der Atom- und molekularen Absorptionsspektrometrie. insbesondere trug er maßgeblich zur substanziellen Weiterentwicklung von Echelle-Spektrometern für die CS-AAS bei. So gelang es, einen quantitativen Zugang zu Elementen wie Bor, Chlor, Fluor und Schwefel, mittels AAS zu erreichen. Erstmals demonstriert Dr. Carlos Abad am Beispiel eines Zr-Modifier, dass durch die Zeitauflösung der eingesetzten Echelle-Systeme mechanistische Untersuchungen zur Wirkung des Modifiers im Graphitrohrofen möglich sind. Besonders hervorzuheben sind seine Arbeiten zum Einsatz der CS-AAS für die Analyse von Isotopen, die eine Genauigkeit aufweist, welche an die der Multikollektor-induktiv gekoppelten Plasma-Massenspektrometrie (MC-ICP-MS) heranreicht. Damit ergeben sich völlig neue Einsatzmöglichkeiten für technologisch hochrelevante Applikationen, wie z.B. die Untersuchung der Alterung von Lithium-Batterien oder die Lithium-Analyse in Blutserum. T2 - Analytica Conference: Bunsen-Kirchhoff-Preis 2022 der Deutsche Arbeitskreis für Analytische Spektroskopie (DAAS) CY - Munich, Germany DA - 23.06.2022 KW - Isotopes KW - Fluorine KW - Halogens KW - Non-metals KW - HR-CS-MAS KW - HR-CS-AAS KW - Bunsen-Kirchhoff-Preis KW - Continuum source atomic absorption spectrometry KW - Zr-Modifier KW - Graphite furnace KW - Lithium PY - 2022 AN - OPUS4-56500 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Optical spectrometry for isotope analysis N2 - Isotope analysis is a tool for material research. For example, it may provide information about the provenance of a sample or changes in dynamic systems. Here is presented optical spectroscopy as an analytical alternative to mass spectrometry for isotope quantification based on the isotopic shift of atoms and diatomic molecules. T2 - Isotopic Tools for the Investigation of Materials WS 21/22 CY - Leoben, Austria DA - 01.10.2021 KW - Isotopes KW - HR-CS-AAS KW - Lithium KW - Atomic absorption spectrometry KW - Diatomic molecules PY - 2022 AN - OPUS4-56495 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Avci, Fatma T1 - Characterization of black mass by X-Ray fluorescence spectroscopy N2 - X-ray fluorescence analysis (XRF) is a method of elemental analysis that is used either as wavelength dispersive XRF (WDXRF) or energy dispersive XRF (EDXRF). Using EDXRF, it is possible to analyze samples within a few minutes without time-consuming sample preparation. This makes the method potentially suitable for analyzing larger sample quantities under industrial conditions. However, the XRF method is matrix-dependent. Depending on the cathode material of the recycled batteries, there are significant differences in the composition of the resulting black mass. This means that specific calibration models must be developed for different types of black mass. The aim of our work is to use the EDXRF method to reliably analyze black mass of different origins with regard to the elements that are particularly interesting for recycling: nickel (Ni), manganese (Mn), cobalt (Co), aluminum (Al), iron (Fe), zinc (Zn), silicon (Si), copper (Cu), and phosphorus (P). Based on the different mass fractions of the elements mentioned, black masses from used lithium-ion batteries can be divided into three groups according to the cathode chemistry: lithium nickel manganese cobalt oxide (NMC), lithium cobalt oxide (LCO), and mixed chemistries (MC), the latter of which may contain lithium iron phosphate (LFP). The division into groups is necessary to determine the matrices and thus select the appropriate calibration model for the analysis of the EDXRF data in order to achieve the most accurate determination of the elemental content possible. Reference analyses are performed using WDXRF. The score plots obtained by PLS-DA of the specific elemental composition of the black masses examined to date by both WDXRF and EDXRF reveal a correct separation of the BM matrix types LCO, NMC, and MC. Our preliminary results with test samples yielded 100 % correct predictions with both data sets. However, only two matrix types, NMC and LCO, have been tested with the EDXRF data so far. Data for MC is pending as work progresses. T2 - Doctoral seminar 2025 - Working Group Chemometrics and Quality Assurance (GDCh) CY - Hamburg, Germany DA - 11.09.2025 KW - Black Mass KW - XRF Spectroscopy KW - Chemometric Modeling KW - PLS-DA PY - 2025 AN - OPUS4-64095 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Paul, Andrea T1 - Classification of mineral wool by spectroscopic methods N2 - Mineral wools from demolition projects are currently disposed of in landfills. To reintroduce them into the material cycle, it is essential (i) to distinguish between glass wool (GW) and rock wool (RW), (ii) to detect foreign substances, and (iii) to assess the period of production (before/after 2000) to identify “old”, potentially carcinogenic wool. Both X-ray and NIR spectroscopic methods are being developed for this purpose and handheld (portable) devices are being tested for field application. To this end, more than 160 mineral wool samples were collected and examined. Since no reference information on the “material” or “age” was available for many samples, we characterized the elemental composition of the mineral wool using wavelength dispersive X-ray fluorescence spectroscopy (WDXRF). For this purpose, pellets and melt tablets were evaluated using a spectrometer-integrated semi-quantitative approach (Omnian). The resulting mass fractions of SiO2, Al2O3, CaO, MgO, K2O, Na2O, Fe2O3, and TiO2 could be used to distinguish between GW and RW and, in the case of RW, also whether it was “old” or “new” wool according to VDI guideline 3492. In some cases, however, ambiguous results were obtained in the material classification. Therefore, a principal component analysis (PCA) was performed enabling the identification of possible outliers and subgroups. Since the classification of “old” and “new” rock wool based on VDI 3492 yielded many unclear results, with the help of partial least squares discriminant analysis (PLS-DA), the classification was significantly improved [1]. WDXRF spectroscopy delivers accurate results, however, the spectrometers are not mobile and require time demanding sample preparation (pellets, melt tablets). Therefore, it was examined whether useful results could be achieved with portable energy dispersive (EDXRF) spectrometers. For this purpose, a portable EDXRF spectrometer (pXRF) was calibrated based on the WDXRF results. In general, oxides of the lighter elements (MgO and Na2O) could not be analyzed with EDXRF. Although prediction of oxide contents in melt tablets was successful by this approach, no reliable results could be obtained when predicting the oxide content of natural mineral wools. Attempts to perform calibration based on natural wools also failed. However, PCA of EDXRF spectra in the “Light” range was able to distinguish between GW and RW, even with “real-world” samples from so-called Bigbags [2], in which mineral wool in Germany is collected in recycling centers. In addition to XRF, a previous study has already demonstrated that at least the distinction between GW and RW can be performed using near-infrared spectroscopy (NIR) [3]. For this reason, measurements were also carried out with a handheld NIR device (pNIR) in parallel with the pXRF investigations. Using PLS-DA, it was possible to classify RW and GW using the handheld device with a sensitivity and specificity of 95% for 38 test samples, including wool from big bags. pNIR also remains sensitive when it comes to determining non-metallic “foreign materials.” For example, materials such as brick, plaster, concrete, and organic fibers could be detected by SIMCA as “non-mineral” wool with a specificity of 92% for 19 tested interferents [2]. Questions regarding the detection of metallic impurities based on EDXRF measurements are the subject of ongoing investigations. T2 - Doctoral Seminar of the Working Group Chemometrics & Quality Assurance CY - Hamburg, Germany DA - 10.09.2025 KW - Mineral wool KW - X-ray fluorescence KW - Data analyis PY - 2025 AN - OPUS4-64077 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blanchard, V. A1 - Traub, Heike T1 - Central project for biochemical analysis of proteoglycans and glycosaminoglycans and for element-specific microscopy N2 - Nearly all disease processes are associated with variations of components of the extracellular matrix (ECM) that are typically observed during the development of inflammation. This concerns for example proteoglycans and their associated glycosaminoglycans (GAG), which have been shown to bind to cationic metal imaging probes due to their strong complexing activity. The complexing activity largely depends on the degree of GAG sulfation and/or carboxylation as well as on the GAG isomericity. In this central project, we investigate GAG structures from inflammatory disorders (namely cardiovascular diseases, inflammatory intestinal diseases and neuroinflammation) provided by researchers of the Collaborative Research Center at the molecular disaccharidic level using chromatographic and mass spectrometric methods. In parallel, the spatial localization and quantification of metal-based imaging probes are evaluated by LA-ICP-MS imaging. T2 - 1st International Symposium In vivo Visualization of Extracellular Matrix Pathology CY - Online Meeting DA - 27.05.2021 KW - Laser ablation KW - ICP-MS KW - MALDI PY - 2021 AN - OPUS4-52716 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - How does solid microanalysis profit from innovations in EUV research N2 - Research into new sources for EUV lithography is driving advancements in experimental methods tailored for this short wavelength range. This progress enables the exploration of spectroscopic techniques aimed at monitoring electronic transitions within this energy spectrum. Laser-induced breakdown spectroscopy (LIBS) serves as a rapid tool for elemental analysis, primarily established in the UV-vis range. However, LIBS encounters challenges such as limited repeatability precision and elevated background noise resulting from continuum radiation. In parallel, laser-induced extreme UV spectroscopy (LIXS) delves into the initial stages of plasma evolution, characterized by the emergence of soft X-ray and extreme UV radiation. The method benefits from a fast timeframe and constrained plasma confinement, leading to better precision. Nevertheless, LIXS encounters convoluted spectra arising from unresolved transition arrays (UTA), particularly pronounced for heavier elements. This complexity renders conventional univariate data analysis impractical, demanding the adoption of a multivariate data analysis approach. Multiple cathode samples, each coated with varying stoichiometries of lithium nickel manganese cobalt oxide (NMC), were prepared and used for calibration purposes. Through the application of Partial Least Squares (PLS) regression, a robust correlation with an R2 value exceeding 0.97 was achieved. The LIXS technique underwent a comparative evaluation against UV-vis LIBS. Furthermore, a comparison between univariate and multivariate analysis approaches was conducted, incorporating validation through y-randomization to mitigate overfitting risks. The viability of this approach was confirmed through the testing of an NMC reference material. The results showed metrological compatibility with reference values, underscoring the potential capability of the proposed methodology. T2 - 322. PTB Seminar 2023 - VUV and EUV Metrology CY - Berlin, Germany DA - 14.11.2023 KW - Laser induced XUV spectroscopy KW - Lithium-ion batteries KW - Solid microanalysis PY - 2023 UR - https://www.euv2023.ptb.de/ AN - OPUS4-58834 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Recknagel, Sebastian A1 - Vogel, Kristin T1 - Berechnung und Nutzung von Unsicherheiten zertifizierter Werte von Referenzmaterialien N2 - Referenzmaterialien sind unter anderem ein wichtiges Werkzeug zur Qualitätskontrolle von Messungen bestimmter Merkmalswerte. Dabei ist zu berücksichtigen, dass zertifizierte Merkmalswerte immer eine gewisse Unsicherheit haben. Die Ermittlung dieser Unsicherheitsbeiträge ist Gegenstand des Vortrags. Referenzmaterialien sind gleichzeitig ein wertvolles Werkzeug zur Ermittlung der Unsicherheit von Messverfahren und -Analysen unbekannter Proben. Die Vorgehensweise bei der Ermittlung der Messunsicherheit mit Hilfe eines Referenzmaterials wird beschrieben. T2 - 11. VDI-Fachtagung Messunsicherheit und Prüfprozesse CY - Erfurt, Germany DA - 14.11.2023 KW - Referenzmaterial KW - Messunsicherheit KW - ISO Guide 35 PY - 2023 AN - OPUS4-58946 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Study of lithium-ion battery aging using laser-induced XUV spectroscopy (LIXS) N2 - Laser-induced XUV spectroscopy (LIXS) is an emerging technique for elemental mapping. In comparison to conventional laser-induced breakdown spectroscopy in UV-vis (LIBS), it has a higher precision and wider dynamic range, and it is well suited for the quantification light elements like lithium and fluorine. Further it can spot oxidation states. The XUV spectra are produced at a very early stage of the plasma formation. Therefore, effects from plasma evolution on the reproducibility can be neglected. It has been shown, that high-precision elemental quantification in precursor materials for lithium-ion batteries (LIBs) can be performed using LIXS. Based on these results, LIXS mapping was used to investigate aging processes in LIBs. Different cathode materials with varying compositions of fluorine containing polymer binders were compared at different stages of aging. Due to effects comparable to X-ray photoelectron spectroscopy but in reverse, monitoring of changes in the oxidation state is envisioned, which makes information about the chemical environment of the observed elements accessible. The combination of elemental distribution and structural information leads to a better understanding of aging processes in LIBs, and the development of more sustainable and safe batteries. T2 - Conference on Applied Surface and Solid Material Analysis - AOFKA 2023 CY - Zurich, Switzerland DA - 11.09.2023 KW - Lithium Ion Batteries KW - Laser-induced XUV spectroscopy KW - Multivariate data analysis PY - 2023 AN - OPUS4-58587 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Multivariate data analysis for laser-induced XUV spectroscopy (LIXS) N2 - The application of multivariate data analysis is essential in extracting the full potential of laser-induced XUV spectroscopy (LIXS) for high-precision elemental mapping. LIXS offers significant advantages over traditional laser-induced breakdown spectroscopy in UV-vis (LIBS), including higher precision and a wider dynamic range,[1,2] while making it possible to determine light elements like lithium and fluorine. However, it is challenged by the presence of unresolved transition arrays (UTAs) for heavier elements. These UTAs add considerable complexity to the spectral data, often concealing crucial information. In this study, we employ well-established multivariate data analysis techniques and intensive data preprocessing to unravel this contained information. The refined analysis reveals a high level of detail, enabling the precise identification of inhomogeneities within material samples. Our approach has particular relevance for studying aging processes in lithium-ion batteries (LIBs), specifically in relation to varying cathode materials and fluorine-containing polymer binder content. By combining elemental distribution with structural information, this improved method can offer a more comprehensive understanding of sample inhomogeneities and aging processes in LIBs, contributing to the development of more reliable and sustainable battery technologies. T2 - Berliner Chemie in Praxis Symposium - BCPS 2023 CY - Berlin, Germany DA - 06.10.2023 KW - Lithium Ion Batteries KW - Laser-induced XUV spectroscopy KW - Multivariate data analysis PY - 2023 AN - OPUS4-58588 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - You, Zengchao T1 - Determination of calcium, iron, and selenium in human serum by isotope dilution analysis using MICAP-MS N2 - Trace elemental analysis in human serum is integral in both clinical and research settings. Analyzing the level of some specific elements like Se and Zn helps indicate the nutritional and health status. Furthermore, elucidating the roles of trace elements in various physiological and pathological conditions can shed light on disease mechanisms and potential treatments. Inductively coupled plasma mass spectrometry (ICP-MS) stands out as a preeminent method for trace elemental analysis, given its exceptional sensitivity and minimal sample requirements. However, ICP-MS has challenges, such as argon-related interferences that hinder the accurate quantification of elements like Ca, Fe, and Se. The naturally most abundant isotopes of Ca (40Ca), Fe (56Fe), and Se (80Se) are subject to isobaric interference from 40Ar+, 40Ar16O+, and 40Ar2+, thereby complicating their direct measurement and preventing isotope dilution analysis. In response to these challenges, nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) emerges as a viable alternative to ICP-MS, eliminating argon consumption and associated interferences. This study employed MICAP-MS to quantify Ca, Fe, and Se in 11 certified reference human serums using matrix-matched calibration and isotope dilution with the isotopes 40Ca, 56Fe, and 80Se. The results obtained with both methods were validated against certified values, and the suitability of MICAP-MS for isotope dilution was evaluated. Additionally, the performance of MICAP-MS in the Na matrix was investigated and discussed alongside the impact of organic species. T2 - Winter Conference on Plasma Spectrochemistry 2024 CY - Tucson, AZ, USA DA - 15.01.2024 KW - MICAP-MS KW - Isotope-dilution KW - Human serum PY - 2024 AN - OPUS4-60210 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Taking Chances – Cheese, Chocolate and Laser Spectroscopy N2 - Science Café Adlershof is having its next edition in 2024 on February 20th '24! We will have one speaker next week: Alexander Winckelmann is a PhD student at Bundesanstalt für Materialforschung und -Prüfung and will give a talk about his stay abroad in Switzerland - there will be free chocolates! There will be enough time to ask questions or simply chat with the guests and participants. T2 - Science Café Adlershof CY - Berlin, Germany DA - 20.02.2024 KW - Laser-induced XUV Spectroscopy KW - Multivariate Data Analysis KW - Science Communication PY - 2024 AN - OPUS4-60197 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Recknagel, Sebastian T1 - Certified reference material for the determination of hydrolytic resistance of borosilicate glass N2 - The preparation, analysis and certification of a new certified glass reference material (CRM) for the determination of hydrolytic resistance of borosilicate glass with the glass grains test is described. The CRM BAM-S053 is available in the form of glass rods (length: 185 mm, diameter: 9 mm, weight: 27·5 g). Certified properties are the acid consumption determined according to the procedures described in ISO 720, USP<660>, Ph.Eur. 3.2.1, data obtained following the procedure of ISO 719 was scattering too widely. The certified values are based on the results of 15 laboratories which participated in the certification interlaboratory comparison. The CRM is intended for the quality control when applying ISO 720, USP<660>, Ph.Eur. 3.2.1 and with limitations ISO 719. KW - CRM KW - Hydrolytic resistance KW - Borosilicate glass PY - 2021 DO - https://doi.org/10.13036/17533562.62.1.001 VL - 62 IS - 1 SP - 25 EP - 27 AN - OPUS4-52195 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Optical spectrometry for isotope analysis N2 - Isotope analysis plays a critical role in various disciplines, including environmental science, archaeology, and forensic investigations. Traditional methods such as mass spectrometry provide precise isotopic data but often require complex, costly setups and extensive sample preparation. As an alternative, optical spectrometry has emerged as a versatile and less invasive technique. This presentation explores the advancements and applications of optical spectrometry methods in isotope analysis, emphasizing their benefits and challenges. T2 - University of Calgary PHYS 561 - Stable And Radioactive Isotope - Winter 2024 CY - Online meeting DA - 07.03.2024 KW - Isotopes KW - HR-CS-MAS KW - Chemometrics KW - Laser Ablation Molecular Absorption spectrometry KW - LAMIS PY - 2024 AN - OPUS4-59948 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Isotope analysis through the integration of chemometrics into optical spectroscopy N2 - Lithium (Li), Boron (B), Nitrogen (N), Magnesium (Mg), and Calcium (Ca) are pivotal elements across various spheres such as the hydrosphere, biosphere, and lithosphere, significantly impacting (bio-) geochemical and physiological processes. These elements exhibit stable isotopes with substantial roles in geological, environmental, and biological studies. The traditional method for measuring isotope amount ratios has been through mass spectrometry, which, despite its accuracy, comes with high operational costs, the need for skilled operators, and time-consuming sample preparation processes. Combining optical spectroscopy with chemometrics introduces an innovative, cost-effective approach by the hand of high-resolution continuum source atomic and molecular absorption spectrometry (HR-CS-AAS and HR-CS-MAS) for the analysis of isotope ratios in Li, B, N, Mg, and Ca. By analyzing the atomic or molecular absorption spectrum of the in-situ generated cloud of atoms of diatomic molecules (e.g., Li, BH, NO, MgF, CaF) during the electronic transition from the fundamental state, this method allows for the rapid determination of isotope ratios directly from sample solutions without the need for complex sample preparation. For each element, the respective atomic or molecule's absorption spectrum was deconvoluted into its isotopic components using partial least squares regression or machine learning algorithms. Robust calibration models were developed, calibrated with enriched isotope, and validated against certified reference materials. Spectral data underwent preprocessing to optimize the modeling to determine the optimal number of latent variables. The findings showcase that this optical spectrometric method yields results that agree with those obtained via inductively coupled plasma mass spectrometry (ICP-MS), offering a promising, cost-effective, and rapid alternative for isotope analysis with precisions as low as ± 0.2‰. This approach is a significant advancement in analytical chemistry, providing a new way to study isotope variations in biological, environmental, and geological samples. T2 - Analytica Conference CY - Munich, Germany DA - 09.04.2024 KW - Isotopes KW - HR-CS-MAS KW - Chemometrics KW - Lithium KW - Boron KW - Magnesium KW - Nitrogen PY - 2024 AN - OPUS4-59946 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Recknagel, Sebastian A1 - Vogel, Kristin T1 - Berechnung und Nutzung von Unsicherheiten zertifizierter Werte von Referenzmaterialien N2 - Referenzmaterialien sind unter anderem ein wichtiges Werkzeug zur Qualitätskontrolle von Messungen bestimmter Merkmalswerte. Dabei ist zu berücksichtigen, dass zertifizierte Merkmalswerte immer eine gewisse Unsicherheit haben. Die Ermittlung dieser Unsicherheitsbeiträge ist Gegenstand des Vortrags. Referenzmaterialien sind gleichzeitig ein wertvolles Werkzeug zur Ermittlung der Unsicherheit von Messverfahren und -Analysen unbekannter Proben. Die Vorgehensweise bei der Ermittlung der Messunsicherheit mit Hilfe eines Referenzmaterials wird beschrieben. T2 - Jahrestagung des GDMB-Chemiker-Ausschusses CY - Kassel, Germany DA - 07.11.2023 KW - Referenzmaterial KW - Messunsicherheit KW - ISO Guide 35 PY - 2023 AN - OPUS4-58929 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hommel, C. A1 - Hassler, J. A1 - Matschat, Ralf A1 - Vogt, T. A1 - Detcheva, A. K. A1 - Recknagel, Sebastian T1 - A fast and robust direct solid sampling method for the determination of 27 trace, main and minor elements in soda-lime glass based on ETV-ICP OES and using a gaseous halogenating modifier N2 - A method, based on electrothermal vaporization (ETV) coupled to inductively coupled plasma optical emission spectrometry (ICP OES), has been optimized for direct solid sampling analysis of soda-lime glass - the most common type of industrially manufactured glass. This method allows fast and reliable quantification of the main elements - Al, Ca, K, Mg, Na, and Si - and trace elements - As, Ba, Cd, Ce, Co, Cr, Cu, Fe, Mn, Mo, Ni, (P), Pb, Sb, (Se), Sn, Sr, Ti, V, Zn, and Zr. In the presented ETV-ICP OES method, calibration is performed predominantly with matrix-free synthetic samples. This metrological advantage is normally not achieved with direct solid sampling methods and is one of the goals of the present study. In a certification interlaboratory comparison for the soda-lime glass CRM BAM-S005c, 2 out of 16 laboratories employed the ETV-ICP OES method. An improved analytical performance was obtained compared with the results of laboratories that used conventional liquid ICP OES. For both methods, the average relative deviations between the laboratory results and certified values as well as the average values of relative standard deviation were with a few exceptions <10%, in most cases even <5%, which indicated high trueness and precision. KW - ICP-OES KW - ETV KW - Soda-lime glass KW - Reference material PY - 2021 DO - https://doi.org/10.1039/d1ja00081k SN - 0267-9477 SN - 1364-5544 VL - 36 IS - 8 SP - 1683 EP - 1693 PB - Royal Society of Chemistry CY - London AN - OPUS4-53181 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fernandez-Menendez, L. J. A1 - Mendez-Lopez, C. A1 - Abad Andrade, Carlos Enrique A1 - Fandino, J. A1 - Gonzalez-Gago, C. A1 - Pisonero, J. A1 - Bordel, N. T1 - A critical evaluation of the chlorine quantification method based on molecular emission detection in LIBS N2 - The entire process involving the determination of Cl by molecular emission detection in Laser-Induced Breakdown Spectroscopy (LIBS) is thoroughly studied in this paper. This critical evaluation considers how spectra are normalized, how interferences from other molecular species signals are removed, and how signal integration is applied. Moreover, a data treatment protocol is proposed to achieve reliable and accurate Cl determination from the CaCl molecular spectral signal, not requiring the use of more complex numerical approaches. Calcium chloride dihydrate (CaCl2⋅2H2O) and high purity anhydrite samples (CaSO4) are used to optimize the acquisition conditions and data treatment of CaCl emission signal. Using the developed protocol, calibration curves for Cl, covering the concentration range from 0 μg/g to 60,000 μg/g of Cl, are successfully achieved. Finally, the suitability of the proposed methodology for Cl determination is successfully applied in industrial gypsum waste samples, where the results obtained by LIBS are validated using high-resolution molecular absorption spectroscopy (HR-CS-MAS) and potentiometric titration. KW - Laser induced breakdown Spectrocopy (LIBS) KW - Molecular spectra KW - Chlorine determination KW - CaCl emission bands KW - Industrial gypsum PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-544292 DO - https://doi.org/10.1016/j.sab.2022.106390 SN - 0584-8547 VL - 190 SP - 1 EP - 9 PB - Elsevier B.V. CY - Amsterdam, Netherlands AN - OPUS4-54429 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - You, Zengchao T1 - Multi element analysis in soil using nitrogen microwave inductively coupled plasma mass spectrometry (MICAP MS) N2 - Due to the fast growth of industry and the use of metal-containing compounds such as sewage sludge in agricultural fields, soil pollution associated with heavy metals presents a terrifying threat to the environment. Throughout the world, there are already 5 million sites of soil contaminated by heavy metals1. Some heavy metals pollutants can influence food chain safety and food quality, which in turn affects human health. According to the German Federal Soil Protection and Contaminated Site Ordinance (BBodSchV) 13 heavy metals such as arsenic (As), lead (Pb) and cadmium (Cd) are classified as heavily toxic to human health2. Therefore, elemental analysis and precise quantification of the heavy metals in soil are of great importance. Inductively coupled plasma mass spectrometry (ICP-MS) emerged as a powerful technique for trace analysis of soil due to its multi-element capability, high sensitivity and low sample consumption. However, despite its success and widespread use, ICP-MS has several persistent drawbacks, such as high argon gas consumption, argon-based polyatomic interferences and the need for complicated RF-power generators. Unlike argon-based ICP, the nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) uses nitrogen as plasma gas, which eliminates high operating costs associated with argon-gas consumption as well as the argon-based interferences3. For the first time, the applicability of MICAP-MS for elemental analysis of environmental soils is investigated in this work. For this purpose, 7 reference- and 3 random soil samples containing vanadium (V), cobalt (Co), zink (Zn), copper (Cu), chrome (Cr), mercury (Hg), As, Pb and Cd are digested with aqua regia and used for analysis. Concentrations of selected elements are determined using MICAP-MS and validated using ICP-MS. Sensitivities, limits of detection and gas consumption for both methods are compared and discussed in detail. Moreover, the performance of MICAP-MS under different nitrogen plasma gas concentrations is investigated and compared. T2 - BAM Adlershofer Kolloquium CY - Online meeting DA - 21.06.2022 KW - Microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) KW - Multi-element analysis KW - Soil KW - Nitrogen plasma PY - 2022 AN - OPUS4-55182 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - You, Zengchao T1 - Multi element analysis in soil using nitrogen microwave inductively coupled plasma mass spectrometry (MICAP MS) N2 - Due to the fast growth of industry and the use of metal-containing compounds such as sewage sludge in agricultural fields, soil pollution associated with heavy metals presents a terrifying threat to the environment. Throughout the world, there are already 5 million sites of soil contaminated by heavy metals1. Some heavy metals pollutants can influence food chain safety and food quality, which in turn affects human health. According to the German Federal Soil Protection and Contaminated Site Ordinance (BBodSchV) 13 heavy metals such as arsenic (As), lead (Pb) and cadmium (Cd) are classified as heavily toxic to human health2. Therefore, elemental analysis and precise quantification of the heavy metals in soil are of great importance. Inductively coupled plasma mass spectrometry (ICP-MS) emerged as a powerful technique for trace analysis of soil due to its multi-element capability, high sensitivity and low sample consumption. However, despite its success and widespread use, ICP-MS has several persistent drawbacks, such as high argon gas consumption, argon-based polyatomic interferences and the need for complicated RF-power generators. Unlike argon-based ICP, the nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) uses nitrogen as plasma gas, which eliminates high operating costs associated with argon-gas consumption as well as the argon-based interferences3. For the first time, the applicability of MICAP-MS for elemental analysis of environmental soils is investigated in this work. For this purpose, 7 reference- and 3 random soil samples containing vanadium (V), cobalt (Co), zink (Zn), copper (Cu), chrome (Cr), mercury (Hg), As, Pb and Cd are digested with aqua regia and used for analysis. Concentrations of selected elements are determined using MICAP-MS and validated using ICP-MS. Sensitivities, limits of detection and gas consumption for both methods are compared and discussed in detail. Moreover, the performance of MICAP-MS under different nitrogen plasma gas concentrations is investigated and compared T2 - Spectroscopium Colloquium CY - Gijon, Spain DA - 30.05.2022 KW - Microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) KW - Multi-element analysis KW - Soil KW - Nitrogen plasma PY - 2022 AN - OPUS4-55181 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Abad Andrade, Carlos Enrique A1 - Mimus, S. A1 - Recknagel, Sebastian A1 - Jakubowski, N. A1 - Panne, Ulrich A1 - Becker-Ross, H. A1 - Huang, M.-D. T1 - Determination of organic chlorine in water via AlCl derivatization and detection by high-resolution continuum source graphite furnace molecular absorption spectrometry N2 - High-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GF-MAS) was employed for determining adsorbable organic chlorine (AOCl) in water. Organic chlorine was indirectly quantified by monitoring the molecular absorption of the transient aluminum monochloride molecule (AlCl) around a wavelength of 261.42 nm in a graphite furnace. An aluminum solution was used as the molecularforming modifier. A zirconium coated graphite furnace, as well as Sr and Ag solutions were applied as modifiers for a maximal enhancement of the absorption signal. The pyrolysis and vaporization temperatures were 600 °C and 2300 °C, respectively. Non-spectral interferences were observed with F, Br, and I at concentrations higher than 6 mg L-1, 50 mg L-1, and 100 mg L-1, respectively. Calibration curves with NaCl, 4-chlorophenol, and trichlorophenol present the same slope and dynamic range, which indicates the chlorine atom specificity of the method. This method was evaluated and validated using synthetic water samples, following the current standard DIN EN ISO 9562:2004 for the determination of the sum parameter adsorbable organic halides (AOX) for water quality. These samples contain 4-chlorophenol as the chlorinated organic standard in an inorganic chloride matrix. Prior to analysis, organic chlorine was extracted from the inorganic matrix via solid-phase extraction with a recovery rate >95%. There were no statistically significant differences observed between measured and known values and for a t-test a confidence level of 95% was achieved. The limits of detection and characteristic mass were found to be 48 and 22 pg, respectively. The calibration curve was linear in the range 0.1–2.5 ng with a correlation coefficient R2 = 0.9986. KW - Chlorides KW - Chlorine KW - Graphite furnace KW - Spectrometry KW - Diatomic molecule KW - Water KW - AlCl PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-534426 DO - https://doi.org/10.1039/D1AY00430A SN - 1759-9660 VL - 13 IS - 33 SP - 3724 EP - 3730 PB - The Royal Society of Chemistry CY - London, UK AN - OPUS4-53442 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bashiri, Termeh A1 - Yu, Phelan A1 - Hutzler, Nicholas R. A1 - Steimle, Timothy C. A1 - Abad Andrade, Carlos Enrique A1 - Okumura, Mitchio T1 - A Molecular Beam Spectroscopic Study of the A2Π − X2Σ + Band of CaF Isotopologues N2 - This study presents an experimental determination of spectroscopic parameters for the less-abundant isotopologues 42CaF and 44CaF, alongside 40CaF, by high resolution laser-induced fluorescence spectroscopy in a skimmed free jet expansion. We recorded spectra near the natural linewidth limit and derived spectroscopic constants for both 𝑋2𝛴+ and 𝐴2𝛱 states, including the fine and 19F magnetic hyperfine parameters. We also estimated the r(44Ca/40Ca) isotope amount ratio, demonstrating the potential use of optical spectroscopy for isotope analysis. KW - High-resolution spectroscopy KW - Molecular beam spectrometer KW - Isotope ratios KW - Isotopologues KW - Calcium KW - CaF KW - Calcium fluoride PY - 2025 DO - https://doi.org/10.1016/j.jms.2025.112023 SN - 1096-083X VL - 410 SP - 1 EP - 6 PB - Elsevier Inc. AN - OPUS4-63506 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Versatility of nitrogen microwave-induced plasma mass spectrometry in elemental and isotopic analysis N2 - The introduction of Nitrogen-based Microwave Inductively Coupled Atmospheric-Pressure Plasma Mass Spectrometry (MICAP-MS) addresses the necessity for a plasma source that matches the capabilities of traditional argon-based Inductively Coupled Plasma Mass Spectrometry (ICP-MS) while exploiting the availability and cost-effectiveness of nitrogen gas. MICAP-MS uses nitrogen plasma, offering significant advantages such as reduced operational costs and eliminating specific isobaric interferences common in argon plasma systems [1]. This presentation explores the principles of MICAP-MS, highlighting its similarities to conventional ICP-MS in terms of analytical performance while emphasizing unique benefits like eliminating interferences from argon-based polyatomic species. MICAP-MS exhibits robust performance using nitrogen gas of varying purities—including ultra-high purity and industrial-grade nitrogen—without compromising analytical results [2]. We have applied MICAP-MS for multielement analysis in soil samples, serving as a proof of concept for environmental monitoring applications. The technique achieved figures of merit comparable to traditional ICP-MS, even when analyzing real-world samples with complex matrices [2]. MICAP-MS demonstrated high tolerance to high-concentration matrices, maintaining accuracy and precision without extensive sample preparation or matrix separation [3]. In clinical diagnostics, MICAP-MS was employed for the precise and traceable quantification of calcium, iron, and selenium in human serum using isotope dilution analysis [4]. These elements often face interferences in argon-based ICP-MS due to argon-associated isobaric interferences (40Ca+, 56Fe+, and 80Se+); however, MICAP-MS effectively overcomes these challenges, providing traceable and accurate determinations. The stability of the microwave plasma in MICAP-MS facilitates precise isotopic analysis. This capability investigated age-induced lithium isotope fractionation in lithium-ion batteries, offering critical insights into battery aging mechanisms and performance degradation [5]. MICAP-MS is a versatile analytical tool that combines the operational benefits of nitrogen plasma with the strengths of traditional ICP-MS. Its ability to handle complex matrices, reduce interferences, and perform precise elemental and isotopic analyses across various applications makes it a valuable instrument. T2 - European Winter Conference on Plasma Spectrochemistry CY - Berlin, Germany DA - 02.03.2025 KW - MICAP-MS KW - Nitrogen plasma KW - Isotope dilution analysis KW - Matrix tolerance KW - Argon interference elimination KW - Trace analysis PY - 2025 AN - OPUS4-63485 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Winckelmann, Alexander A1 - Roik, Janina A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique A1 - You, Zengchao T1 - Investigation of matrix effects in nitrogen microwave inductively coupled atmospheric-pressure plasma mass spectrometry (MICAP-MS) for trace element analysis in steels N2 - We investigated the performance of nitrogen microwave inductively coupled atmospheric-pressure plasma mass spectrometry (MICAP-MS) under matrix effects and its applicability to trace element analysis in steels. Influences of different gas flows and ion optics on the matrix tolerance are studied, indicating that nebulizer gas flow has the most significant impact. Optimization of ion optics improves matrix tolerance for light elements due to the reduction of the inelastic collisional scattering effect. With optimized operating conditions, MICAP-MS achieves an internal standard intensity recovery of over 90% at an Fe concentration of 500 mg L−1. Even at an Fe concentration of 1 g L−1, the recovery remains above 80%. Three certified reference materials – non-alloy, low-alloy and high-alloy steel – were analyzed using MICAP-MS. The determined mass concentrations of the trace and minor components show metrological compatibility to the reference values. No significant differences are observed between the results obtained with aqueous and matrix-matched calibration, demonstrating the strong matrix tolerance of MICAP-MS, and its promising applicability to steel analysis. KW - MICAP-MS KW - Trace Analysis KW - Steel PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576323 DO - https://doi.org/10.1039/d3ja00088e SN - 0267-9477 VL - 38 IS - 6 SP - 1253 EP - 1260 PB - Royal Society of Chemistry AN - OPUS4-57632 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Recknagel, Sebastian T1 - Certified reference material for the determination of hydrolytic resistance of borosilicate glass N2 - The preparation of certified reference material for the determination of hydrolytic resistance of borosilicate glass is described. Certified properties are the acid consumption according to the relevant standard procedures described in ISO 720, USP<660> and Ph.Eur. 3.2.1. T2 - 26. International Congress on Glass CY - Berlin, Germany DA - 03.07.2022 KW - Borosilicate glass KW - CRM KW - Hydrolytic resistance PY - 2022 AN - OPUS4-55521 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - High-resolution optical spectrometry for lithium isotope ratio analysis N2 - An alternative method for lithium isotope amount ratio analysis is proposed by combining atomic absorption spectrometry with spectra data analysis by machine leaning. It is based on the well-known isotope shift of around 15 pm for the electronic transition at wavelength 670.7845 nm which can be measured by a high-resolution continuum source atomic absorption spectrometer (HR-CS-AAS). For isotope amount ratio analysis, a scalable three boosting machine learning algorithm (XGBoost) was employed and calibrated with a set of samples with a 6Li isotope amount fraction ranging from 99% to 6%. The absolute Li isotope amount fractions of these calibration samples were previously measured by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) and used as ab-initio data for the machine learning algorithm. Validation of the machine leaning model was performed with two standard reference materials (LSVEC and IRMM-016). The procedure was employed for the isotope amount ratio determination of a set of stock chemicals (Li2CO3, LiNO3, LiCl, LiOH, and LiF) as well as a BAM candidate LiMNC cathode reference material. Achieved uncertainties are one order of magnitude higher than those obtained by MC-ICP-MS. This precision and accuracy is nonetheless sufficient to resolve natural occurring variations in Lithium isotope ratios. Also, the LiMNC material was analyzed by HR-CS-AAS with and without matrix purification. The results are comparable within statistical error. T2 - Groupseminar - GFZ Potsdam CY - Online Meeting DA - 27.10.2020 KW - Lithium batteries KW - HR-CS-AAS KW - Machine learning KW - Isotope analysis PY - 2020 AN - OPUS4-51572 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Why do I have to charge my phone twice a day? N2 - Aging Mechanisms of Lithium Batteries: How can we make batteries more durable and more sustainable in the future? Lithium batteries are particularly susceptible to ageing processes. During each charging and discharging process in an electric battery, lithium ions are deposited in the electrodes of the cell like in the pores of a sponge. Over time, however, fractures and cracks occur in the filigree structures. The result: more and more lithium ions no longer fit into the hollow spaces of the „sponge“, instead they accumulate in heaps around the electrodes and hinder the movement of other ions. The performance of the battery decreases. We present our new project, in which we are developing a fast and cost-effective method with which companies that produce lithium batteries can already assess the ageing behaviour of their batteries in the laboratory. T2 - Berlin Science Week 2022 CY - Online meeting DA - 10.11.2022 KW - Lithium Ion Batteries KW - Aging Mechanisms PY - 2022 UR - https://berlinscienceweek.com/de/event/why-do-i-have-to-charge-my-phone-twice-a-day/ UR - https://www.youtube.com/watch?v=bF7bQTY49rQ AN - OPUS4-56245 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mohr, Gunther A1 - Sommer, Konstantin A1 - Knobloch, Tim A1 - Altenburg, Simon A1 - Recknagel, Sebastian A1 - Bettge, Dirk A1 - Hilgenberg, Kai T1 - Process Induced Preheating in Laser Powder Bed Fusion Monitored by Thermography and Its Influence on the Microstructure of 316L Stainless Steel Parts N2 - Undetected and undesired microstructural variations in components produced by laser powder bed fusion are a major challenge, especially for safety-critical components. In this study, an in-depth analysis of the microstructural features of 316L specimens produced by laser powder bed fusion at different levels of volumetric energy density and different levels of inter layer time is reported. The study has been conducted on specimens with an application relevant build height (>100 mm). Furthermore, the evolution of the intrinsic preheating temperature during the build-up of specimens was monitored using a thermographic in-situ monitoring set-up. By applying recently determined emissivity values of 316L powder layers, real temperatures could be quantified. Heat accumulation led to preheating temperatures of up to about 600 °C. Significant differences in the preheating temperatures were discussed with respect to the individual process parameter combinations, including the build height. A strong effect of the inter layer time on the heat accumulation was observed. A shorter inter layer time resulted in an increase of the preheating temperature by more than a factor of 2 in the upper part of the specimens compared to longer inter layer times. This, in turn, resulted in heterogeneity of the microstructure and differences in material properties within individual specimens. The resulting differences in the microstructure were analyzed using electron back scatter diffraction and scanning electron microscopy. Results from chemical analysis as well as electron back scatter diffraction measurements indicated stable conditions in terms of chemical alloy composition and austenite phase content for the used set of parameter combinations. However, an increase of the average grain size by more than a factor of 2.5 could be revealed within individual specimens. Additionally, differences in feature size of the solidification cellular substructure were examined and a trend of increasing cell sizes was observed. This trend was attributed to differences in solidification rate and thermal gradients induced by differences in scanning velocity and preheating temperature. A change of the thermal history due to intrinsic preheating could be identified as the main cause of this heterogeneity. It was induced by critical combinations of the energy input and differences in heat transfer conditions by variations of the inter layer time. The microstructural variations were directly correlated to differences in hardness. KW - Additive manufacturing KW - Laser powder bed fusion KW - In-situ process monitoring KW - Thermography KW - Heat accumulation KW - Inter layer time KW - Cellular substructure PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529240 DO - https://doi.org/10.3390/met11071063 VL - 11 IS - 7 SP - 1063 PB - MDPI CY - Basel, Schweiz AN - OPUS4-52924 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Battistella, Beatrice T1 - Microwave-Induced Nitrogen-Plasma Mass Spectrometric Analysis of Cathodic Materials for Lithium-Ion Batteries N2 - Lithium-ion batteries (LIBs) are multi-component devices ubiquitously used for powering small consumer devices as well as in the electric mobility sector and for energy storage. From the first successful test in 1986, LIBs performances have improved substantially, doubling their specific energy from 120 to 270 Wh kg−1 in about 30 years, while mass production contributed to a decline of about 98% of their price. The demand is set to grow steadily and is expected to lead to further improvements in performance and falls in prices. [1] In view of the current clean energy transition, the extensive use of this technology is accompanied by an increase of end-of-life LIBs, containing critical minerals for the production of new batteries. The recycling of exhausted batteries is a topic destined to draw increasing attention, and for this purpose, LIBs composition determination is a crucial premise. While the first commercialized LIB contained about 60% cobalt by mass, the current trend is to lower the Co content by the use of lithium nickel manganese cobalt (NMC) oxide as cathodic material (ca. 6% Co), increasing the cell-specific energy and reducing the raw material price. [2] Besides the change in the layered transition metal oxide composition, elemental substitution, surface treatment and concentration gradient structures, used to increase battery performances, further contribute to increase the cathodic material complexity. [3] In this work, the composition of several commercial NMC oxides was investigated by Microwave-Induced Nitrogen-Plasma Mass Spectrometry, suitable for the trace analysis on these materials due to its high matrix tolerance in presence of high concentration of transition metals and the easy-to-ionize lithium. [4] Additionally, the effects of different gas flows and ion optics on the matrix tolerance were studied. The method was validated by analyzing BAM-S014 (NMC oxide) as reference material and allowed the generation of a library for such metal oxides. Determination of their exact elemental composition helps users to predict the properties of the cathodic material (e. g. presence of particles coating, additives, or doping elements), and at the same time allows the design of safe recycling procedures, which must consider the presence of health and environment hazardous elements such as uranium, cadmium, or other heavy metals. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Nitrogen-Plasma Mass Spectrometry KW - Lithium-Ion Battery KW - Recycling PY - 2025 AN - OPUS4-62817 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Advantages of N2-MICAP-MS for Trace Metal Analysis in Steel N2 - The climate and energy crisis are extreme challenges. One possible solution could be hydrogen technology. Safety is a big concern. Steel used for pipelines and storage is under permanent stress from low temperatures and high pressures. The content of different alloyed metals determines the performance of the steel. Nitrogen microwave inductively coupled atmosphere pressure plasma mass spectrometry (N2-MICAP-MS) is a promising method for trace metal analysis in steel. Nitrogen is cheap and can be generated on site. It has fewer interferences than argon. Additionally, MICAP-MS is very matrix tolerant, proving the matrix-matched calibration expendable. Safety in technology and chemistry is the mission of BAM. Providing reference methods and materials can create trust in future technologies like hydrogen. T2 - SALSA Make and Measure 2022 CY - Berlin, Germany DA - 15.09.2022 KW - Trace analysis KW - Steel KW - Microwave plasma KW - Mass spectrometry KW - Safety PY - 2022 AN - OPUS4-55792 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Advanced spectroscopic methods for fluorine microanalysis in lithium-ion batteries N2 - To address the challenges of the climate crisis, multiple solutions for sustainable energy sources and storage systems are needed. One such solution is lithium-ion batteries (LIBs). Currently, 5 to 30 % of LIBs are discarded immediately after manufacturing. The homogeneous distribution of all materials used in the coating of cathodes and anodes is critical for the quality of LIBs. Furthermore, during formation i.e., the first steps of the charge/discharge cycling, the solid-electrolyte interphase forms on the anode particles, which has a huge impact on the performance. The same happens to some extent on the cathode, forming the cathode-electrolyte interphase. Fluorinated polymers and electrolytes are used in the manufacturing of LIBs. The electrolyte in particular is prone to degradation during formation and aging of the batteries. The interface of the cathode material with the aluminum current collector is also a critical point where degraded fluorine components cause pitting corrosion and at the same time promote passivation of the metal foil. Monitoring the spatial distribution of fluorine on these surfaces and interfaces is essential for sustainable LIB production. T2 - SALSA Kick-Off Meeting CY - Berlin, Germany DA - 11.04.2024 KW - Lithium Ion Batteries KW - solid microanalysis KW - depth-profiling KW - fluorine PY - 2024 AN - OPUS4-60199 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Jakubowski, N. A1 - Borrmann, S. A1 - Recknagel, Sebastian A1 - Roik, Janina A1 - Rickert, F. T1 - Comparison of peristaltic pumps used for sample introduction in Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) N2 - In this investigation, two conventional peristaltic pumps are compared with a new pump based on the “easy click” principle using a simultaneous ICP-AES instrument with standard operating conditions. It is found that the figures of merit achieved are quite comparable for all three pumps. Relative standard deviations (RSDs) range between 0.2% and 1.8%, and limits of detection as low as 0.1 μg/L have been achieved , demonstrating that the easy click principle of the new pump does not compromise the analytical figures of merit. KW - ICP-AES KW - Peristaltic pumps KW - ICP-MS PY - 2020 IS - 35 / S4 SP - 6 AN - OPUS4-52020 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Recknagel, Sebastian T1 - Analytische Chemie Gusseisen, Gummi, Bodenproben N2 - Die BAM stellt seit über 100 Jahren Referenzmaterialien (RM) her. Seit damals haben sich die Anforderungen an RM stark verändert. Der Artikel gibt einen Einblick in Anforderungen und die Herstellungsweise von Referenzmaterialien. KW - Referenzmaterialien KW - ISO-Guide 35 KW - Boden PY - 2021 SP - 51 EP - 53 AN - OPUS4-53695 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Recknagel, Sebastian T1 - Certified reference materials for the determination of cadmium (Cd) in cocoa N2 - BAM has produced three cocoa CRMs certified for cadmium (ERM-BD513 – 515) as tools for checking analytical methods for Cd-determination. KW - Certified reference material KW - Cocoa KW - Cadmium PY - 2021 SP - 4 EP - 4 AN - OPUS4-53694 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Tanz der Moleküle: Herkunftsbestimmung mittels optischer Spektroskopie N2 - Wie lässt sich die Herkunft von Rohstoffen, Lebensmitteln oder Umweltschadstoffen einfacher, schneller und kostengünstiger als mit bisherigen Methoden bestimmen? Die Dissertation zeigt auf, dass man das grundlegende physikalische Prinzip einer Isotopverschiebung mit in Adlershof entwickelten Optik-Instrumenten für die Herkunftsbestimmung nutzen kann. Die entwickelte Methode ermöglicht es in Zukunft den Ursprung von Rohstoffen, Lebensmitteln oder Umweltschadstoffen kostengünstiger und wesentlich schneller bestimmen, als dies mit bisherigen Methoden möglich ist. Kann man das grundlegende physikalische Prinzip einer Isotopieverschiebung mit einem Optik-Instrument für die Herkunftsbestimmung nutzen? Carlos Abad hat eine wegweisende Methode entwickelt, die es in Zukunft ermöglicht den Ursprung von Rohstoffen, Lebensmitteln oder Umweltschadstoffen kostengünstiger und wesentlich schneller bestimmen, als dies mit bisherigen Techniken möglich ist. T2 - Dissertationspreis Adlershof 2019 CY - Berlin, Germany DA - 12.02.2020 KW - Herkunftsbestimmung KW - Isotopenanalyse KW - Isotope KW - Optischer Spektroskopie KW - Coltan PY - 2020 AN - OPUS4-51993 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Isotopic analysis by high-resolution optical spectroscopy N2 - Isotope analysis can be used to determine the age and provenance of geological samples or to study dynamic systems like Li-ion batteries. Modern techniques in optical spectrometry allow us a fast and slow-cost isotope analysis. These techniques include high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS) and laser ablation molecular isotopic spectrometry. This seminar will discuss our recent work on precise and accurate isotope analysis of boron, magnesium, and lithium with geology, climate, and energy research applications. T2 - Recent Trends in Chemical Science and Technology, Christian College Chengannur, India CY - Online meeting DA - 29.09.2020 KW - Isotopes KW - Optical spectrometry KW - Machine learning PY - 2020 AN - OPUS4-51997 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Isotope analysis by high-resolution optical spectroscopy: a tool for planetary science N2 - Isotope analysis can be used to determine the age and provenance of geological samples. Modern techniques in optical spectrometry allow us a stand-off isotope analysis. This seminar will discuss how planetary science with the next Moon and Mars missions drive optical spectrometry into precise and accurate isotope analysis and how BAM will contribute. T2 - Adlershofer Kolloquium CY - Online meeting DA - 19.05.2020 KW - Provenance KW - Dating KW - Isotopes KW - Optical spectroscopy KW - Isotopic shift KW - Planetary science PY - 2020 AN - OPUS4-51995 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Advances and Applications of Molecular Absorption Spectrometry: from Non-Metals to Isotope Analysis N2 - Wie kann Nicht-Messbares messbar gemacht werden? Die Antwort der Dissertation auf diese zentrale Frage der analytischen Chemie lautet: die Anwendung der hochauflösenden optischen Spektroskopie der diatomischen Moleküle. In der Arbeit wird in einem ersten Schritt in Grafitöfen, die wie Chemiereaktoren funktionieren, und durch die Anwendung verschiedener analytischer Methoden die diatomische Molekülbildung nachvollzogen. In einem zweiten Schritt werden die aufgedeckten Mechanismen auf die Bestimmung von Nichtmetallen und die Analyse von Isotopen angewendet. Die Isotopenanalytik ist das zukunftsweisendes Herzstück der Dissertation und von alltäglicher und politischer Relevanz: Mittels dieser Technik lässt sich die Herkunft von Lebensmitteln aber auch Chemiewaffen kostengünstiger und wesentlich schneller bestimmen als mit bisherigen Methoden der Massenspektrometrie. Möglich ist die Bestimmung, da alles um uns herum aus Atomen verschiedener Elemente besteht und die meisten Elemente mehrere Isotope haben. Isotope unterscheiden sich hinsichtlich ihres Gewichts, da sie über eine unterschiedliche Anzahl an Neutronen verfügen. Die Informationen über das Verhältnis von schweren und leichten Isotopen lässt sich nutzen, um zu bestimmen wo etwas entstanden ist. Jeder Ort auf unserem Planeten hat seinen persönlichen Element- und Isotopenanteil (Isotopenfingerabdruck). Das in der Arbeit angewandte Instrument misst das Verhältnis indirekt und nutzt hierzu die Interaktion zwischen Licht und Materie. Für das schwerere Isotop wird mehr Licht/Energie benötigt, um es in Bewegung zu bringen, als für das leichtere. Diese kleinen Unterschiede an Energie, die wir dafür aufwenden müssen, werden gemessen und ermöglichen die Herkunftsbestimmung. Damit leistet die Arbeit nicht nur einen wichtigen Beitrag zur Grundlagenforschung in der analytischen Chemie, sondern kann mit den aufgezeigten Ergebnissen auch Anwendung in den Bereichen Verbraucherschutz, Umweltforschung und Waffenkontrolle finden. N2 - The present work covers two main aspects of high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS), an analytical technique for elemental trace analysis. First, a comprehensive mechanistic study of molecule formation in graphite furnaces is presented, which is a key step into the recovery of analytical signals. For this, the molecule formation of CaF was studied, which is used for the indirect analytical determination of fluorine in HR-CS-GFMAS. A zirconium coating catalyzes the CaF formation, and its structure was investigated. The kinetics of this reaction was established by monitoring its molecular spectrum at different atomisation temperatures. An Arrhenius plot showed a pseudo-first order reaction with respect to fluorine (n = 1). An intermediate state was isolated, and its structure was elucidated by spectroscopic methods: scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XANES and EXAFS), and Raman microspectroscopy. Here a mechanism is proposed, where ZrO2 works as a heterogeneous catalyst: after a pyrolytic step, an intermediate state of ZrO(OCaF) is activated, and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. Second, analytical methods were developed by using HR-CS-MAS as detector for non-metals and isotope analysis. Therefore, the determination of organic absorbable chlorine in water, the quantification of fluorine in consume care products with declared perfluorinated ingredients, and the determination of sulfur content in crude oils were investigated. Finally, the high resolution of the instrumentation allows to measure isotopic shifts with high precision in some observed molecular spectra. Consequently, the molecular spectra of enriched isotopes of boron and magnesium were investigated, establishing so the potential of HR-CS-MAS for the accurate and precise determination of isotopic amount ratios. T2 - Applied Photonics Award 2020 CY - Jena, Germany DA - 22.09.2020 KW - Herkunftsbestimmung KW - Isotopenanalyse KW - Isotope KW - Optischer Spektroskopie PY - 2020 AN - OPUS4-51996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Riedel, Jens T1 - Recent Trends in Inexpensive Lithium Isotopic Analysis N2 - Lithium exists in two stable isotopes, 6Li and 7Li. The ratio of these in every ore varies depending on the geological history of the sample, thus providing a tool for fingerprinting the distinct origin of Li containing samples. Determination of the exact isotope ratio for e.g. designation of provenance today relies on expensive and bulky instrumentation such as multi `collector inductively coupled plasma mass spectrometry` (MC-ICP-MS). These instruments, however, are known to bear pitfalls in the characterization of particular elements including Lithium. BAM recently developed two alternative analytical devices for this task, solely relying on inexpensive optical spectroscopy in combination with state-of-the-art multivariate data analysis such as Machine learning algorithms. Both techniques have been comprehensively studied using certified reference materials and comparing the results to MC-ICP-MS results and could be shown to result in comparable figures of merit, paving the way for a more general accessibility to provenance determination instrumentation. The results also pave the way towards even further simplification of the laboratory infrastructure demands and to further include additional elements into the isotopic fingerprinting methodology. T2 - Lithium-Days CY - Halle, Germany DA - 06.12.2021 KW - Lithium KW - Isotopes KW - Optical Spectroscopy PY - 2021 AN - OPUS4-53966 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Recknagel, Sebastian T1 - ISO-Guide 35 in der Praxis eines RM-Herstellers N2 - Der ISO-Guide 35 beschreibt die notwendigen Schritte zur Herstellung von zertifizierten Referenzmaterialien. Anhand praktischer Beispiele wird die Umsetzung des Guide 35 in der BAM dokumentiert. T2 - DAkkS-Begutachterschulung Modul E zur Akkreditierung von Eignungsprüfungsanbietern und Referenzmaterialherstellern CY - Online meeting DA - 04.02.2021 KW - ISO-Guide 35 KW - Referenzmaterial-Herstellung KW - ZRM PY - 2021 AN - OPUS4-52099 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hoffmann, V. A1 - Uhlemann, M. A1 - Richter, Silke A1 - Pfeifer, jens T1 - Calibration capacity of hot-pressed hydrogen standards for glow discharge optical emission and mass spectrometry N2 - Mixed copper and titanium hydride powder was hot-pressed and characterized by Carrier Gas Hot Extraction, XRay Diffraction, Thermal Gravimetric Analysis coupled with Mass Spectrometry, and Scanning Electron Microscopy. The hot-pressed and five conventional samples were applied for calibration of hydrogen in Glow Discharge Optical Emission and Mass Spectrometry. Up to the introduction of 15 ng/s hydrogen the Emission yield model is useful in Glow Discharge Optical Emission Spectrometry. A correlation between saturation and even reversal of the emission yield of the spectral lines H121, H486 and H656 and low sputtering rates was found. Hydrogen effects exist for the spectral lines of Cu(II) 219 and Ti(I) 399. In Glow Discharge Mass Spectrometry, a linear dependency of the 1H ion current on the sputtered mass per time exists over the total range of hydrogen content investigated. Hydrogen effects also exist for the sensitivity of 48Ti and 63Cu. The sputtering rate of two-phase materials depends linearly on the sputtered mass per time of one phase, which allows the sputtering rate of two-phase materials with known composition to be predicted. KW - Hot-pressing KW - GD-OES KW - GD-MS KW - Calibration KW - Hydrogen KW - Titanium hydride KW - Sputtering KW - Two-phase system PY - 2021 DO - https://doi.org/10.1016/j.sab.2020.106039 VL - 176 SP - 106039 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-52074 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Soba, L. A1 - Tuma, Dirk T1 - Messung der Schallgeschwindigkeit in Neopentan bei Temperaturen von (263 bis 373) K und Drücken bis 20 MPa N2 - Alkan-Isomere haben signifikanten Einfluss als Spurenstoffe auf thermodynamische Eigenschaften von Erdgasgemischen. In Erdgas sind bis zu 0.35 mol-% Neopentan enthalten. Gemischmodelle basieren auf Reinstoffzustandsgleichungen der beteiligten Komponenten. Die hier untersuchte Schallgeschwindigkeit ist von besonderer Bedeutung für die Entwicklung hochgenauer Gleichungen. T2 - Thermodynamik-Kolloquium 2025 CY - Hamburg, Germany DA - 22.09.2025 KW - Neopentan KW - Schallgeschwindigkeit KW - Zustandsgleichung PY - 2025 AN - OPUS4-64226 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Winckelmann, Alexander A1 - Morcillo Garcia-Morato, Dalia A1 - Richter, Silke A1 - Recknagel, Sebastian A1 - Riedel, Jens A1 - Vogl, Jochen A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - Determination of lithium in human serum by isotope dilution atomic absorption spectrometry N2 - The therapeutic dose of lithium (Li) compounds, which are widely used for the treatment of psychiatric and hematologic disorders, is close to its toxic level; therefore, drug monitoring protocols are mandatory. Herein, we propose a fast, simple, and low-cost analytical procedure for the traceable determination of Li concentration in human serum, based on the monitoring of the Li isotope dilution through the partially resolved isotope shift in its electronic transition around 670.80 nm using a commercially available high-resolution continuum source graphite furnace atomic absorption spectrometer. With this technique, serum samples only require acidic digestion before analysis. The procedure requires three measurements—an enriched 6Li spike, a mixture of a certified standard solution and spike, and a mixture of the sample and spike with a nominal 7Li/6Li ratio of 0.82. Lanthanum has been used as an internal spectral standard for wavelength correction. The spectra are described as the linear superposition of the contributions of the respective isotopes, each consisting of a spin-orbit doublet, which can be expressed as Gaussian components with constant spectral position and width and different relative intensity, reflecting the isotope ratio in the sample. Both the spectral constants and the correlation between isotope ratio and relative band intensity have been experimentally obtained using commercially available materials enriched with Li isotopes. The Li characteristic mass (mc) obtained corresponds to 0.6 pg. The procedure has been validated using five human serum certified reference materials. The results are metrologically comparable and compatible to the certified values. The measurement uncertainties are comparable to those obtained by the more complex and expensive technique, isotope dilution mass spectrometry. KW - Lithium KW - Human serum KW - Isotope dilution KW - Atomic absorption spectrometry KW - High-resolution continuum source graphite furnace atomic absorption spectrometry PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532446 DO - https://doi.org/10.1007/s00216-021-03636-6 VL - 414 IS - 1 SP - 251 EP - 256 PB - Springer CY - Berlin AN - OPUS4-53244 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Applications of atomic absorption spectrometry for lithium isotope analysis N2 - An alternative method for lithium isotope analysis by using high-resolution atomic absorption spectrometry (HR-CS-AAS) is proposed herein. This method is based on monitoring the isotope shift of approximately 15 pm for the electronic transition 22P←22S at around the wavelength of 670.8 nm, which can be measured by state-of-the-art HR-CS-AAS. Isotope analysis can be used for (i) the traceable determination of Li concentration and (ii) isotope amount ratio analysis based on a combination of HR-CS-AAS and spectral data analysis by machine learning (ML). In the first case, the Li spectra are described as the linear superposition of the contributions of the respective isotopes, each consisting of a spin-orbit doublet, which can be expressed as Gaussian components with constant spectral position and width and different relative intensity, reflecting the isotope ratio in the sample. Precision was further improved by using lanthanum as internal spectral standard. The procedure has been validated using human serum-certified reference materials. The results are metrologically comparable and compatible with the certified values. In the second case, for isotope amount ratio analysis, a scalable tree boosting ML algorithm (XGBoost) was employed and calibrated using a set of samples with 6Li isotope amount fractions ranging from 0.06 to 0.99 mol mol−1. The training ML model was validated with certified reference materials. The procedure was applied to the isotope amount ratio determination of a set of stock chemicals and a BAM candidate reference material NMC111 (LiNi1/3Mn1/3Co1/3O2), a Li-battery cathode material. These determinations were compared with those obtained by MC-ICP-MS and found to be metrologically comparable and compatible. The residual bias was −1.8‰, and the precision obtained ranged from 1.9‰ to 6.2‰. This precision was sufficient to resolve naturally occurring variations. The NMC111 cathode candidate reference material was analyzed using high-resolution continuum source atomic absorption spectrometry with and without matrix purification to assess its suitability for technical applications. The results obtained were metrologically compatible with each other. T2 - Colloquium Spectroscopicum Internationale XLII (CSI XLII) CY - Gijón, Spain DA - 30.05.2022 KW - Lithium KW - HR-CS-AAS KW - Chemometrics KW - Atomic spectrometry PY - 2022 AN - OPUS4-56498 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Recknagel, Sebastian A1 - Bresch, Harald A1 - Kipphardt, Heinrich A1 - Resch-Genger, Ute A1 - Koch, Matthias A1 - Rosner, M. T1 - Trends in selected fields of reference material production N2 - For more than 110 years, BAM has been producing reference materials for a wide range of application fields. With the development of new analytical methods and new applications as well as continuously emerging more stringent requirements of laboratory accreditation with regard to quality control and metrological traceability, the demand and requirements for reference materials are increasing. This trend article gives an overview of general developments in the field of reference materials as well as developments in selected fields of application in which BAM is active. This includes inorganic and metal analysis, gas analysis, food and consumer products, and geological samples. In addition to these more traditional fields of application, developments in the areas of optical spectroscopy, particulary fluorescence methods, and nanomaterials are considered. T2 - 150 years BAM: Science with impact CY - Berlin, Germany DA - 01.01.2021 KW - Reference material KW - ISO REMCO KW - Gas analysis KW - Food KW - Nanomaterials KW - Fluorescence PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-548407 DO - https://doi.org/10.1007/s00216-022-03996-7 SN - 1618-2642 SN - 1618-2650 VL - 414 IS - Topical collection: Analytical methods and applications in the materials and life sciences SP - 4281 EP - 4289 PB - Springer CY - Berlin AN - OPUS4-54840 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -