TY - CONF A1 - Palásti, Dávid Jenö T1 - Utilizing modern fiber lasers for LIBS N2 - The development of laser sources plays a very important role in the quick advancements in the field of LIBS. However, the development of fiber lasers went mostly unnoticed by the wider LIBS community. These laser sources, traditionally used in industrial cutting and welding processes, despite their high-power output (hundreds of watts) and are very robust nature, were neglected, because they used to work only in continuous mode. Modern fiber lasers however, offer pulsed output with a couple of mJ-s pulse energy, which can be adequate for certain tasks [1,2]. Furthermore, the pulse duration and the pulse repetition rate can be varied in a reasonably wide range, while their price is a fraction of the ones traditionally used in research. In the recent years, our groups made experiences with modern fiber lasers to evaluate the feasibility of their usage in LIBS. The initial experiments proved that they are not just suitable for standard analytical tasks such as quantitative or qualitative analysis, but their unique set of features makes them capable for fundamental research, like no other laser sources currently on the market. The relatively low energy and elongated profile of the pulses are very efficient in ablation and in the generation of low temperature plasmas [3], which means the ionic lines are less numerous, while the emission is mostly free from the background emission typical for the early stages of the plasma lifetime. It can make spectrometer gating and signal integration much simpler and robust. A thorough set of investigations of single pulse, double pulse and even continuous irradiation experiments was performed. The effects of various parameters, such as energy, duration and shape of the pulse as well as inter pulse delay were investigated on the generated signal focusing mainly the signal intensity, the self-absorption and the width of the peaks as well as the plasma properties. T2 - EMSLIBS 2026 CY - Senlis, France DA - 26.01.2026 KW - LIBS KW - Fiber laser PY - 2026 AN - OPUS4-65561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Zöllner, Moritz T1 - Thermal decomposition of dolomite: Raman spectroscopy as a thermometric tool for the analysis of carbonates in mortar binders. N2 - The reconstruction of the thermal history of minerals is an on-going challenge in the study of anthropogenic materials, e.g., ceramics and mortar binders. For millennia carbonate rocks have been used as the starting material, though the exact manufacturing procedures are often unknown. Preparatory parameters such as firing temperature, heating and cooling rates, soaking time, and kiln atmosphere greatly influence the chemical and structural properties of the resulting products. Analysis of replicas produced under well-defined laboratory conditions help identify indicators for such process parameters and therefore provide valuable insights into historical production workflows. Raman micro-spectroscopy is a valuable method here because of its high sensitivity for crystal-chemical alterations coupled with a high spatial resolution. Previous studies on pyrogenic anhydrite were able to distinguish between gypsum materials that were heated at different temperatures between 400 – 900 °C [1, 2]. The results of thermal experiments with natural dolomite powder between 500 – 900 °C are presented, evaluating the thermal decomposition of dolomite and the consequent formation of calcium carbonate. Raman measurements were performed at room temperature on calcinated samples, as well as subsequently hydrated and re-carbonated samples. A peak-fitting routine using python scripts was employed to extract the peak positions and the full width at half maximum (FWHM) values of the ν1-, ν4- and L-bands of the carbonates. The results reveal the formation of Mg-calcite from dolomite at 700 – 750 °C and the formation of Mg-free calcite after calcination above 750 °C and subsequent hydration and re-carbonation. The findings from the thermal experiments are compared with Raman-microscopy mappings on medieval and reenacted mortars containing dolomite. Mg-calcite with comparable peak position and FWHM values have been successfully identified, proving Raman spectroscopy to be a suitable tool for elucidating the manufacturing procedures of anthropogenic materials. T2 - European Mineralogical Conference 2024 CY - Dublin, Ireland DA - 18.08.2024 KW - Raman spectroscopy KW - Dolomite KW - Mineral thermometry PY - 2024 AN - OPUS4-61975 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Zöllner, Moritz T1 - Thermal decomposition of dolomite: Raman spectroscopy as a thermometric tool for the analysis of carbonates in mortar binders. N2 - High-spectral resolution Raman spectroscopy is a powerful tool for the chemical and structural analysis in material sciences. Beyond its usage for the qualitative identification of minerals, Raman spectroscopy has been applied for the quantitative characterisation of chemical phases. The precise measurement of Raman peak position and band width values allows for an empirical differentiation of chemically similar phases and thus provides valuable insights to the structural properties of a material. In the field of archaeometry, the crystal structure of minerals can be used to elucidate the preparatory parameters of historical samples, such as the firing temperature. Comparison of historical materials with replicas produced under well-defined laboratory conditions help identify indicators for such process parameters. Previous Raman studies on pyrogenic anhydrite were able to distinguish between gypsum materials that were heated at different temperatures between 400–900 °C [1–3]. The results of thermal experiments with natural dolomite powder between 500–900 °C are presented, evaluating the thermal decomposition of dolomite and the consequent formation of calcium carbonate. Raman measurements were performed with excitation at 532 nm and 1800 mm-1 grating at room temperature on calcinated samples, as well as subsequently hydrated and re-carbonated samples. These high-resolution conditions are necessary to resolve the individual spectral contributions of different calcium/magnesium carbonate species. However, this sensitivity does not come without potential pitfalls. While the usage of micro-Raman spectroscopy with high spectral resolution shows great promise for evaluating minor shifts in peak positions and band widths, several technical aspects must be considered. For example, great care must be taken to exclude the thermal impact of the highly focused Raman laser on the sample. Similarly, exact standard operating procedures have to be followed to circumvent mechanical hysteresis in the alignment of the spectrographs’ grating. The influence of these two effects is presented and effective countermeasures are introduced to avoid resulting systematic errors. Statistical reliability and chemical imaging both rely on the individual analysis of thousands of Raman spectra. Thus, besides the spectral acquisition, also highly automated data analysis must be applied. Therefore, a peak-fitting routine using python scripts was employed to extract the peak positions and the full width at half maximum (FWHM) values of the ν1-, ν4- and L-bands of the carbonates. The results reveal the formation of Mg-calcite from dolomite at 700–750 °C and the formation of Mg-free calcite after calcination above 750 °C and subsequent hydration and re-carbonation (Fig. 1a). The findings from the thermal experiments are compared with Raman-microscopy mappings on medieval and reenacted mortars containing dolomite. Mg-calcite with comparable peak position and FWHM values have been successfully identified (Fig. 1b), proving Raman spectroscopy to be a suitable tool for elucidating the manufacturing procedures of anthropogenic materials. T2 - 16th GeoRAMAN Conference CY - Rhodes, Greece DA - 24.09.2024 KW - Raman spectroscopy KW - Dolomite KW - Mineral thermometry PY - 2024 AN - OPUS4-61977 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Zöllner, Moritz T1 - Thermal decomposition of dolomite: Raman spectroscopy as a thermometric tool for the analysis of carbonates in mortar binders N2 - The reconstruction of the thermal history of minerals is an on-going challenge in the study of anthropogenic materials, e.g., ceramics and mortar binders. For millennia carbonate rocks have been used as the starting material, though the exact manufacturing procedures are often unknown. Preparatory parameters such as firing temperature, heating and cooling rates, soaking time, and kiln atmosphere greatly influence the chemical and structural properties of the resulting products. Analysis of replicas produced under well-defined laboratory conditions help identify indicators for such process parameters and therefore provide valuable insights into historical production workflows. Raman micro-spectroscopy is a valuable method here because of its high sensitivity for crystal-chemical alterations coupled with a high spatial resolution. Previous studies on pyrogenic anhydrite were able to distinguish between gypsum materials that were heated at different temperatures between 400–900 °C [1-3]. The results of thermal experiments with natural dolomite powder between 500–900 °C are presented, evaluating the thermal decomposition of dolomite and the consequent formation of calcium carbonate. Raman measurements were performed at room temperature on calcinated samples, as well as subsequently hydrated and re-carbonated samples. Raman band positions and the full width at half maximum (FWHM) values of the ν1-, ν4- and L-bands of the carbonates are extracted and reveal the formation of Mg-calcite from dolomite at 700–750 °C and the formation of Mg-free calcite after calcination above 750 °C and subsequent hydration and re-carbonation. The findings from the thermal experiments are compared with Raman-microscopy mappings on medieval and reenacted mortars containing dolomite. Mg-calcite with comparable peak position and FWHM values have been successfully identified, proving Raman spectroscopy to be a suitable tool for elucidating the manufacturing procedures of anthropogenic materials. T2 - SciX 2024 CY - Raleigh, NC, USA DA - 20.10.2024 KW - Raman spectroscopy KW - Dolomite KW - Mineral thermometry PY - 2024 AN - OPUS4-61978 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 - Zöllner, Moritz T1 - Raman spectroscopy as a thermometric tool for the analysis of mortar binders N2 - The reconstruction of the thermal history of anthropogenic materials is crucial for understanding historical manufacturing techniques. Preparatory parameters such as firing temperature, heating and cooling rates, soaking time, and kiln atmosphere significantly affect the chemical and structural properties of the final product. Comparing historical materials with replicas produced under well-defined laboratory conditions helps identify indicators for these parameters. This comparative approach is greatly enhanced by spectroscopic analyses. Raman spectroscopy has proven to be a powerful tool in this field due to its high sensitivity to crystal-chemical alterations and high spatial resolution. The results of thermal experiments with gypsum and carbonate raw materials at burning temperatures up to 1000 °C are presented. Precise measurements of Raman peak positions and Raman band widths enable the differentiation of chemically similar phases. Changes in the Raman band parameters are evident even after the subsequent hydration-hardening process of the fired samples, allowing the spectral discrimination of samples treated at different temperatures steps. These findings from the thermal experiments are further applied to Raman micro-spectroscopic mappings of medieval and reenacted mortars. The extracted Raman band parameters show comparable values between the experimental and real-life samples, proving Raman spectroscopy as a suitable tool for estimating the burning temperature and thus elucidating the manufacturing procedures of anthropogenic materials. T2 - Jahrestagung Archäometrie und Denkmalpflege 2025 CY - Dresden, Germany DA - 18.03.2025 KW - Raman spectroscopy KW - Mineral thermometry PY - 2025 AN - OPUS4-62778 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schmid, Thomas T1 - Raman microspectroscopy elucidates Early Medieval art technology: high-fired gypsum mortar and Egyptian blue from the church St. Peter above Gratsch (South Tyrol, Northern Italy) N2 - Raman microspectroscopy enables imaging of the distributions of mineral phases as well as physical properties of materials, such as crystal orientations and crystallinities, with down to sub-micrometre resolution. In a combination with other spectroscopic and microscopic techniques, this approach was applied to the analysis and elucidation of ancient production technologies of stucco fragments made of high-fired gypsum mortar and Egyptian blue pigment discovered on a monochrome wall painting fragment originating from the Early Medieval (5th/6th century AD) construction phase of the church St. Peter above Gratsch in South Tyrol (Northern Italy). T2 - Analytica Conference 2022 CY - Munich, Germany DA - 21.06.2022 KW - Raman microspectroscopy KW - Gypsum KW - Pigments PY - 2022 AN - OPUS4-55896 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Plasma Fundamentals and Diagnostics N2 - This course will provide an introduction to plasma diagnostic techniques. The major focus of the course will be on the discussions of the practical procedures as well as the underlying physical principles for the measurements of plasma fundamental characteristics (e.g., temperatures and electron number density). Particular emphasis will be placed on laser induced plasma–atomic emission spectrometry, but other analytical plasmas will also be used as examples when appropriate. Selected examples on how one can manipulate the operating conditions of the plasma source, based on the results of plasma diagnostic measurements, to improve its performance used for spectrochemical analysis will also be covered. Topics to be covered include thermal equilibrium, line profiles, temperatures, electron densities, excitation processes, temporal and spatial resolution. T2 - 2022 Winter Conference on Plasma Spectrochemistry CY - Tucson, Arizona, USA DA - 17.01.2022 KW - Thermal equilibrium KW - Excitation processes KW - Electron number density KW - Temperatures KW - Spatial information KW - Emission line profiles PY - 2022 AN - OPUS4-54288 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Plasma Fundamentals and Diagnostics N2 - This course will provide an introduction to plasma diagnostic techniques. The major focus of the course will be on the discussions of the practical procedures as well as the underlying physical principles for the measurements of plasma fundamental characteristics (e.g., temperatures, thermodynamic properties, and electron number density). Particular emphasis will be placed on inductively coupled plasma–atomic emission spectrometry, but other analytical plasmas will also be used as examples when appropriate. Selected examples on how one can manipulate the operating conditions of the plasma source, based on the results of plasma diagnostic measurements, to improve its performance used for spectrochemical analysis will also be covered. Topics to be covered include thermal equilibrium, line profiles, temperatures, electron densities, excitation processes, micro reactions, pump and probe diagnostics, tomography, temporal and spatial resolution. Basis of plasma computer modeling will be presented. T2 - 2024 Winter Conference on Plasma Spectrochemistry CY - Tucson, Arizona, USA DA - 15.01.2024 KW - Plasma KW - Plasma fundamentals KW - Plasma diagnostics PY - 2024 AN - OPUS4-59430 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Optical Detection of Defects during Laser Metal Deposition N2 - Laser metal deposition is a rapidly evolving method for additive manufacturing that combines high performance and simplified production routine. Quality of production depends on an instrumental design and operational parameters, which require constant control during the process. In this work, feasibility of using optical spectroscopy as a control method is studied via modeling and experimentally. A simplified thermal model is developed based on the time-dependent diffusion-conduction heat equation and geometrical light collection into detection optics. Intense light emitted by a laser-heated spot moving across a sample surface is collected and processed to yield the temperature and other temperature-related parameters. In the presence of surface defects, the temperature field is distorted in a specific manner that depends on shape and size of the defect. Optical signals produced by such the distorted temperature fields are simulated and verified experimentally using a 3D metal printer and a sample with artificially carved defects. Three quantities are tested as possible metrics for monitoring the process: temperature, integral intensity, and correlation coefficient. The shapes of the simulated signals qualitatively agree with the experimental signals; this allows for a cautious inference that optical spectroscopy can detect surface defects and, possibly, predict their characters, e.g., inner or protruding. T2 - Colloquium Spectroscopicum Internationale XLII (CSI XLII) CY - Gijon, Spain DA - 30 May 2022 KW - Additive manufacturing KW - Laser metal deposition KW - Optical sensor KW - Optical emission spectroscopy KW - Process control PY - 2022 AN - OPUS4-55063 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Multifaceted laser induced plasma: spectroscopy and beyond N2 - In this presentation, I will give a brief overview of my personal experience with laser induced plasma (LIP). I will start from my and colleagues’ early works, where we used LIP as an atomic reservoir for laser induced fluorescence (LIP). We applied LIP-LIF for a sensitive detection of trace elements in various materials and demonstrated that under certain conditions the technique can even be used for isotope analysis. Next, I will discuss the application of LIP spectroscopy, i.e., LIBS, to material identification that nowadays constitutes one of the best applications of this technique. In those early days, we used correlation analysis for spectra processing; it is now replaced by more powerful chemometric methods. Further, I will stop on our efforts in modeling LIP that we first intended for the improved quality of spectroscopic analysis and later extended to non-spectroscopic fields such as chemical vapor deposition and surface structuring. We developed a version of calibration-free LIBS, in which we iterated model-generated spectra until a close match was achieved between experimental and synthetic spectra to determine concentrations. Next, I will briefly overview our recent developments in plasma modeling that include plasma chemistry. This was important in view of widening application of LIBS as a molecular technique. I will also address several plasma diagnostics, e.g., Radon transform tomography that we developed to get more insight about LIP that was helpful for both analytic spectroscopy and modeling. Finally, I will mention several exotic applications of LIP such as LIP-based lasers and chemical reactors to illustrate a real multifaceted character of laser induced plasma and usefulness of its study for many science fields. T2 - SciX 2022, The Federation of Analytical Chemistry and Spectroscopy Societies (FACSS) CY - Cincinnati, OH, USA DA - 02.10.2022 KW - Emission spectroscopy KW - Laser ablation KW - Laser induced plasma deposition KW - Surface coating KW - Hydrodynamic model KW - Plasma chemistry PY - 2022 AN - OPUS4-55968 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Molecule formation in reactive LIBS plasmas: model and experiment N2 - Formation and detection of molecules in laser induced plasmas (LIP) is a hot topic. In analytical plasmas like LIBS, the detection of molecules is important for identification of geological and other materials, analysis of isotopes and difficult elements (Cl, F, etc.) via molecular emission. In chemical plasmas, like PECVD (plasma enhanced chemical vapor deposition) or PLD (pulsed laser deposition), molecules formed in the plasma determine a composition and a thickness of deposits. Similarly, molecules play an important role in microstructuring and oxidizing metal surfaces by laser ablation. It is unfortunate that different communities, which utilize plasma methods and seek for solutions of similar problems, do not strongly overlap, and do not fully use knowledge accumulated by each other. In this presentation, mechanisms of formation of molecules will be analyzed on the example of LIPs used for chemical vapor deposition and metal microstructuring. Theoretical analysis includes equilibrium chemistry calculations combined with plasma hydrodynamics. First, LIP excited in a gas mixture of BCl3 or BF3 with H2 or CH4 will be analyzed; this chemical system is used for obtaining deposits of refractory solid boron and boron carbide. Second, a breakdown in the SiF4 + SiCl4 gas mixtures will be described; this method allows synthesis of fluorochlorosilanes SiFxCl4-x (x = 1, 2, 3), the good etching agents (Figure). Third, solid ablation of Mo in BF3+H2 and Ti in air will be considered aimed at obtaining deposits of high hardness MoxBy and films of TixOy on textured Ti surfaces, correspondingly. In experiment, reaction gases before and after laser illumination, and solid deposits are analyzed by optical emission spectroscopy (OES), IR and mass spectrometry (MS), SEM, X-ray, and AFM. It will be shown that the hydrodynamic-chemical model adequately predicts the composition of LIPs, zones of molecular formation, dependence on reactant stoichiometry, plasma temperature and pressure. T2 - Euro-Mediterranean Symposium on Laser-Induced Breakdown Spectroscopy CY - Gijon, Spain DA - 29.11.2021 KW - Laser induced plasma KW - Plasma chemistry KW - Molecules formation KW - Plasma enhanced chemical deposition PY - 2021 AN - OPUS4-53850 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling, Diagnostics and Applications of Laser Induced Plasma N2 - Laser-induced plasmas are widely used in many areas of science and technology; examples include spectrochemical analysis, thin film deposition, and material processing. Several topics will be addressed. First, general phenomenology of laser-induced plasmas will be discussed. Then, a chemical model will be presented based on a coupled solution of Navier-Stokes, state, radiative transfer, material transport, and chemical equations. Results of computer simulations for several chemical systems will be shown and compared to experimental observations obtained by optical imaging, spectroscopy, and tomography. The latter diagnostic tools will also be briefly discussed. Finally, a prospective application of laser-induced plasma and plasma modeling will be illustrated on the example of chemical vapor deposition of molybdenum borides and micro processing and coating of titanium dental implants. T2 - University of Saragossa, Department of Chemistry CY - Saragossa, Spain DA - June 30, 2022 KW - Laser ablation KW - Laser induced plasma KW - Plasma modeling KW - Plasma diagnostics KW - Surface coating PY - 2022 AN - OPUS4-55166 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling laser-induced plasma in vacuum and low-pressure co2 atmosphere N2 - The aim of the project is to develop an adequate model of laser induced plasma for conditions expected in space missions, i.e., vacuum, or low-pressure CO2 atmosphere. Numerical modeling will help to find optimal experimental parameters for the laser ablation under artificial lunar or Martian environments and obtain both qualitative, in terms of a composition, and quantitative, in terms of an elemental abundance, information about interrogated samples based on spectral data generated by the model. The best operational conditions will be found at a low cost without conducting tedious and time-consuming optimization experiments. The modeling approaches will be supported by machine learning to accelerate the optimization. T2 - Workshop on DFG project CY - Brno, Czech Republic DA - 10.08.2023 KW - Laser induced plasma KW - CFD computational fluid dynamic KW - Plasma modeling PY - 2023 AN - OPUS4-58595 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling Equilibrium Chemistry in Laser Induced Plasmas and Plasma Chemical Reactors N2 - A brief introduction will be given on modeling chemical reactions in laser induced plasmas using stoichiometric and non-stoichiometric approaches. Several applications will be considered, which can benefit from such modeling. Those include plasma enhanced chemical vapor deposition (PECVD), surface modification and surface coating, and molecular analysis by LIBS. Each application will be illustrated by simulations of relevant chemical systems. For PECVD, chemical systems are BCl3/H2/Ar, BF3/H2/Ar, BCl3/BF3, Mo/BF3/H2; for surface modification/coating it is Ti/air; for molecular LIBS they are CaCO3/Ar, Ca(OH)2/Ar, and CaCl2/Ar. Advantages and shortcomings of equilibrium chemical hydrodynamic models of laser induced plasmas will be discussed. T2 - 1st NIP Conference National Institute of Physics (IKF), the Albanian Academy of Sciences CY - Online meeting DA - 10.02.2022 KW - Laser ablation KW - Laser induced plasma deposition KW - Surface coating KW - Titanium dioxide KW - Emission spectroscopy KW - Hydrodynamic model KW - Plasma chemistry PY - 2022 AN - OPUS4-54328 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling Equilibrium Chemistry in Laser Induced Plasmas and Plasma Chemical Reactors N2 - A brief introduction will be given on modeling chemical reactions in laser induced plasmas using stoichiometric and non-stoichiometric approaches. Several applications will be considered, which can benefit from such modeling. Those include plasma enhanced chemical vapor deposition (PECVD), surface modification and surface coating, and molecular analysis by LIBS. Each application will be illustrated by simulations of relevant chemical systems. For PECVD, chemical systems are BCl3/H2/Ar, BF3/H2/Ar, BCl3/BF3, Mo/BF3/H2; for surface modification/coating it is Ti/air; for molecular LIBS they are CaCO3/Ar, Ca(OH)2/Ar, and CaCl2/Ar. Advantages and shortcomings of equilibrium chemical hydrodynamic models of laser induced plasmas will be discussed. T2 - Moscow University, Department of Chemistry CY - Moscow, Russia DA - 26.10.2021 KW - Laser ablation KW - Laser induced plasma deposition KW - Emission spectroscopy KW - Surface coating KW - Hydrodynamic model KW - Plasma chemistry PY - 2021 AN - OPUS4-53629 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - model of laser induced plasma relevant to structuring and coating of titanium implants N2 - The presentation will give a brief overview of the processes occurring in laser-induced plasma and methods of modeling these processes. In particular, a chemical-hydrodynamic model will be considered, which is related to the modification of the surface of metallic titanium by laser pulses. The details and simplifications of this model, its shortcomings and the possibilities of their elimination will be discussed. This model is related to the structuring of the surface of dental implants with a laser and the deposition of an oxide film on it. T2 - THE 2-nd THEMATIC INTERNATIONAL SCIENTIFIC AUTUMN SCHOOL ON LASER MICRO- & NANOTHECHNOLOGIES: 2021 – BIOMEDICAL TECHNOLOGIES CY - St. Petersburg, Russia DA - 09.11.2021 KW - Laser ablation KW - Laser induced plasma deposition KW - Surface coating KW - Emission spectroscopy KW - Hydrodynamic model KW - Plasma chemistry PY - 2021 AN - OPUS4-53718 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - You, Yi T1 - MicroPhase: An Open-Source Flexible Ultrasonic Phased Array Based on Microcontrollers N2 - The use of resonant acoustic fields has gained significant attention due to their capability for contactless manipulation of objects in the open air and other media, referred to as ultrasonic levitation. To overcome the limitations in air-coupling efficiency, Langevin-type ultrasonic transducers are often employed, as they can operate at relatively high power, ranging from several tens to thousands of watts. However, such platforms typically lack the ability to move acoustically trapped objects efficiently, often requiring additional mechanical structures for even basic motion control, such as translation. In contrast, ultrasonic phased arrays offer clear advantages by leveraging their inherent beam-forming capabilities, which allows for dynamic shaping of acoustic fields in situ. Unfortunately, phased array control systems are not readily accessible, particularly when specific geometric or performance criteria must be met. Most commercially available phased array controllers are designed to operate in the MHz range; those are suitable only for high acoustic impedance media, such as water. Conversely, platforms for open-air applications typically utilize ultrasonic speakers operating at 40 kHz. In both cases, these systems are built on field-programmable gate arrays (FPGAs). However, interfacing FPGAs with computers and developing FPGA firmware (e.g., in VHDL) can be technically demanding, and analog components such as power amplifiers further complicate the system design. These limitations severely restrained the use of flexible ultrasonic levitations in analytical chemistry. Here, we present a novel platform for controlling ultrasonic phased arrays using single modern microcontrollers. This platform leverages the connectivity features of microcontrollers, allowing straightforward interfacing with computers via common programming languages (e.g., Python). The system employs fast direct memory access (DMA) to control up-to 256 ultrasonic transducers with a resolution of 0.5 µs, which is suitable for air-based applications in the 20-50 kHz range. Additionally, the platform can interface with traditional Langevin-type transducers, enabling their conversion into phased arrays. Optical characterization of acoustic field optimization is also discussed. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Acoustic ion manipulation PY - 2025 AN - OPUS4-64112 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Riedel, Jens T1 - LIBs–trends and developments for recycling applications N2 - Recent years have brought up many challenges for an analytical tracing of material flows. While planetary boundaries force end of life material into circular recycling pathways, geopolitical tension creates demands regarding the origin of raw materials. The analytical demands on any instrumentation to tackle the arising challenges of this scenario are straight forward: No sample preparation, precision in the percentage region, and high throughput at comparably low cost. All these demands make LIBS a perfect candidate, why it is time for a re-evaluation of how it exploits the potential possibilities arising from todays’ technology. While being a relatively young technique, the vast majority of conducted LIBS experiments still relies on well established instrumentation, sometimes ignoring the innovations and breakthroughs in the development of its empowering technology sectors such as battery powered compact high repetition rate lasers with tuneable pulse rate and length, low priced cameras with millions of small sized pixels and extremely fast shutter and readout times, optical modulators, galvonometer scanners, and simple robotics. In this talk we will showcase some examples on how the implantation of all these new tools can lead to extremely affordable and compact instrumentation with unprecedented acquisition speed and a spectral resolution sufficient to resolve atomic isotope lines. T2 - Institute Seminar CY - Rostock, Germany DA - 09.01.2024 KW - LIBS KW - Sorting KW - Automatisation PY - 2024 AN - OPUS4-62136 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Laser-Induced Plasma for Spectroscopy and More N2 - An overview of personal experience with laser-induced plasma (LIP) will be given. The combination of LIP with laser-induced fluorescence, atomic absorption, Raman spectroscopy and spatial heterodyne spectroscopy for elemental and isotopic analysis will be discussed. Unusual applications of LIP will be covered, such as LIP-based lasers and LIP-based chemical reactors. T2 - 2024 Winter Conference on Plasma Spectrochemistry CY - Tucson, Arizona, USA DA - 15.01.2024 KW - Laser induced plasma KW - Laser ablation KW - LIP-LIF KW - LIP-AAS PY - 2024 AN - OPUS4-59431 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Laser induced gas breakdown in reactive mixtures N2 - Plasma-chemical approach is used for synthesis of various gaseous, liquid, and solid substances since 1960th. Nowadays, the method of plasma enhanced chemical vapor deposition (PECVD) is used for production of thin films, protective coatings, carbon-based nanostructures, high purity isotopic materials, biomaterials, and other products. Plasma for PECVD is typically created in various electrical discharges, e.g. DC and AC glow discharges or discharges operated at audio (10-20 kHz), radio (13.56 MHz), and microwave (2.45 GHz) frequencies. Plasma induced by a laser, a laser induced plasma (LIP), is rarely used to deposit materials from the gas phase as in PECVD. This work is aimed at reviving interest to this latter technology and showing its efficiency and potential. We run several pilot experiments. First, LIP is excited in BCl3 or BF3 plus H2 or CH4 to evaluate the efficiency of deposition of solid boron and boron carbide, the materials, which are largely used for refractory coatings. Second, we investigate a possibility of synthesis of fluorochlorosilanes SiFxCl4-x (x = 1, 2, 3) by LIP induced in SiF4 + SiCl4 gas mixtures. Using fluorochlorosilanes with different combinations of F and Cl in the SiFxCly molecule may add flexibility in processes of silicon deposition and etching. Third, LIP is excited in reactive mixture MoF6+H2+BF3 or on a Mo target ablated into H2/BF3 atmosphere. The goal is obtaining superhard molybdenum borides MoB, Mo2B, or MoB2. The gases used and solid deposits are analyzed by optical emission spectroscopy (OES), IR and mass spectrometry (MS). We also model the plasma and perform static equilibrium chemistry calculations to see if the desired reaction products are thermodynamically favorable. Dynamic calculations of the expanding plasma plume are performed using a hydrodynamic code combined with the open source chemical software. T2 - SciX 2021, The Federation of Analytical Chemistry and Spectroscopy Societies (FACSS) CY - Providence, RI, USA DA - September 26, 2021 KW - Laser ablation KW - Laser induced plasma deposition KW - Emission spectroscopy KW - Surface coating KW - Plasma chemistry KW - Hydrodynamic model PY - 2021 AN - OPUS4-53560 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Riedel, Jens T1 - Is LIBS ready for the future? N2 - Recent years have brought up many challenges for an analytical tracing of material flows. While planetary boundaries force end of life material into circular recycling pathways, geopolitical tension creates demands regarding the origin of raw materials. The analytical demands on any instrumentation to tackle the arising challenges of this scenario are straight forward: No sample preparation, precision in the percentage region, and high throughput at comparably low cost. All these demands make LIBS a perfect candidate, why it is time for a re-evaluation of how it exploits the potential possibilities arising from todays’ technology. While being a relatively young technique, the vast majority of conducted LIBS experiments still relies on well established instrumentation, sometimes ignoring the innovations and breakthroughs in the development of its empowering technology sectors such as battery powered compact high repetition rate lasers with tuneable pulse rate and length, low priced cameras with millions of small sized pixels and extremely fast shutter and readout times, optical modulators, galvonometer scanners, and simple robotics. In this talk we will showcase some examples on how the implantation of all these new tools can lead to extremely affordable and compact instrumentation with unprecedented acquisition speed and a spectral resolution sufficient to resolve atomic isotope lines. T2 - FACCS SCiX CY - Raleigh, NC, USA DA - 20.10.2024 KW - LIBS KW - Isotopes KW - Instrumentation PY - 2024 AN - OPUS4-61970 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. A1 - Mendez, Cristina A1 - Bordel, Nerea T1 - Investigation of LIBS-RF Plasma for Analytical Spectroscopy N2 - Laser breakdown spectroscopy (LIBS) is a common tool for applications in various fields of science and technology. Originally an atomic analysis technique, LIBS was later extended to molecular analysis due to the transient nature of the laser-induced plasma, which develops from a hot dissociation stage on a nanosecond to several microsecond scale to a relatively cold recombination stage on a scale of 10 to 100 microseconds after breakdown. Molecules formed during the recombination stage or incompletely dissociated after ablation can be efficiently detected, allowing the analysis of "difficult" elements or even molecular isotopes. However, with a small amount of ablated material and a short lifetime of the luminous plasma, analytical signals, especially molecular ones, can be very weak. Several methods have been proposed for reheating the plasma and increasing its lifetime, for example, a two-pulse LIBS or a LIBS combined with microwave radiation or with an electric spark discharge. Here we propose another one, LIBS combined with a capacitively coupled RF discharge at 13.6 MHz. The advantages of this combination are an increase in the lifetime of atomic and molecular emission and operation in a low-pressure atmosphere, which significantly reduces pressure line broadening and allows high-resolution spectroscopy. Another major advantage is operating in a chemically controlled atmosphere that can predictably drive desired chemical reactions. In this presentation, we will show the first results obtained with RF-LIBS combination. These will include separate and joint characterization of LIBS and RF plasmas and evaluation of its potential for elemental and molecular analysis and for plasma enhanced chemical vapor deposition. T2 - SciX 2023 CY - Sparks, USA DA - 08.10.2023 KW - Laser induced breakdown spectroscopy KW - Capacitively coupled discharge KW - RF-LIBS combination KW - Plasma reheating PY - 2023 AN - OPUS4-58592 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Völker, Tobias T1 - Interlaboratory comparison for quantitative chlorine analysis in cement pastes with LIBS N2 - Concrete structures often show severe damage during their lifetime. One such damage is pitting corrosion of the steel reinforcement caused by chloride ingress into the porous concrete structure. Laser-induced breakdown spectroscopy (LIBS) is a promising method in civil engineering, which is used for detection of chlorine in concrete structures in addition to conventional methods of wet chemistry. To assess LIBS as a trustful analytical technique, its accuracy and robustness is carefully tested. The presentation will outline the results of the interlaboratory comparison of chlorine quantification in cement paste samples, which was carried out by 12 laboratories in 10 countries. Two sets of samples with chloride content ranging from 0.06-1.95 wt.% in the training set and 0.23-1.51 wt.% in the test sample set (“unknowns”), with additional variations in the type of cement and chlorine source (salt type) were sent to the laboratories. The overall result demonstrates that LIBS is suitable for the quantification of the investigated sample compositions: average relative bias was mostly below 15 %. Considering that the laboratories did not receive instructions on how to perform the analysis or how to process the data, the results can be evaluated as a true status quo of the LIBS technique for this type of analysis. T2 - XII Laser Induced Breakdown Spectroscopy (LIBS 2022) CY - Bari, Italy DA - 04.09.2022 KW - LIBS KW - Chlorine KW - Cement pastes KW - Interlaboratory comparison PY - 2022 AN - OPUS4-55680 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael T1 - Integrated and networked systems and processes – A perspective for digital transformation of our chemical and pharmaceutical production N2 - Chemical and pharmaceutical companies have to find new paths to survive successfully in a changing environment, while also finding more flexible ways of product and process development to bring their products to market more quickly – especially high-quality high-end products like fine chemicals or pharmaceuticals. The potential of digital technologies belongs to these. A current approach uses flexible and modular chemical production units, which can produce different high-quality products using multi-purpose equipment with short downtimes between campaigns and reduce the time to market of new products. At the same time, we need to move towards knowledge-based production that takes into account all essential equipment, process and control data from plants and laboratories and makes valuable expertise available and transferable. The potential of data from production together with its contextual information is often not yet consistently used today for a comprehensive understanding of production. By giving examples this paper outlines a possible more holistic approach to digitalisation and the use of machine-based methods in the production of specialty chemicals and pharmaceuticals through the introduction of integrated and networked systems and processes. T2 - GDCh Science Forum 2021 - GDCh Wissenschaftsforum 2021 CY - Online meeting DA - 29.08.2021 KW - Process analytical technology KW - Online NMR spectroscopy KW - Process industry KW - Industry 4.0 KW - Digital transformation KW - Autonomous chemistry PY - 2021 AN - OPUS4-53171 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Improved Data Processing for Accurate Plasma Diagnostics with Implications for Calibration-Free LIBS N2 - Many LIBS papers report the determination of plasma temperature using the Boltzmann plot method or the determination of electron density using the Stark line broadening relation. This requires measuring the integrated intensities of the spectral lines and the linewidth under the assumption of optical thinness. It is taken for granted that this can be easily done either by working with the raw spectra or by fitting the appropriate function to the observed spectral lines. However, extracting the necessary information from raw spectral data is not as easy as it might seem. The quality of such extraction will depend to a decisive extent on the type of spectral instrument used. The spectrum emitted by the plasma is distorted by the device; an example is shown in Fig. 1. The elimination of this distortion belongs to the class of inverse problems, the successful solution of which fundamentally depends on the quality of the available information. When it comes to spectroscopy, the quality of information primarily means high spectral resolution and low noise. Not all spectrometers used in LIBS can provide the quality needed to solve the inverse problem; this casts doubt on many published plasma measurements. This communication will be devoted to the general shortcomings of spectral data processing and the inaccuracies in determining the plasma parameters resulting from these shortcomings. The analysis is based on the use of synthetic spectra generated by plasma with known temperature, particle density and electron density. The estimation of errors caused by inadequate processing of spectral data is made by comparing the initial and measured plasma parameters from the spectra. Recommendations will be made for which analytic function best approximates the observed spectral lines, and how data processing errors affect the accuracy of calibration-free LIBS will be discussed. These issues were only partially covered in previously published works, for example [1, 2]. T2 - Colloquium Spectroscopicum Internationale XLIII, The 5th Asian Symposium on Laser Induced Breakdown Spectroscopy June 26-30, 2023 CY - Tokushima, Japan DA - 26.06.2023 KW - Laser induced breakdown spectroscopy KW - Calibration-free LIBS KW - Data processing PY - 2023 AN - OPUS4-58589 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Improved Data Processing for Accurate Plasma Diagnostics and Calibration-Free LIBS N2 - Many applications of LIBS require the measurement of plasma temperature and electron density, which in turn requires knowledge of the integrated line intensity and the shape of the spectral lines. While the integral intensity is preserved as light passes through the spectrometer, the shape emitted by an individual atom or ion is greatly distorted. This is due, firstly, to the transfer of light through the plasma (self-absorption), secondly, to the influence of the instrumental function of the spectrometer, and, thirdly, to the aberrations of the optical system. In addition, processing of spectral information, such as background removal, noise reduction, deconvolution, and line fitting, introduces additional errors in the reconstructed linewidth and line integral, which leads to erroneous temperature and electron density values. This communication will be devoted to the general shortcomings of spectral data processing and the resulting inaccuracies in determining the plasma parameters. The analysis is based on the use of synthetic spectra generated by plasma with known temperature and particle density. The estimation of errors caused by inadequate processing of the spectral data is made by comparing the initial and determined plasma parameters. As a result, an improved data processing method will be proposed that takes into account the spectrum distortion by the instrumental function and integration on the pixel detector. The former is accounted for by convolution (instead of deconvolution) of the estimated line profile using a predetermined slit function, and the latter is achieved by piecewise integration of the line profile by the pixel detector, taking into account the pixel size and uniform or non-uniform pixel separation. Recommendations will be made for which analytic function best approximates the observed spectral lines and examples will be given for the application of this routine to calibration-free LIBS using both synthetic and experimental data. T2 - SciX 2023 CY - Sparks, USA DA - 08.10.2023 KW - Laser induced plasma KW - Calibration-free analysis KW - Plasma modeling KW - Emission spectroscopy PY - 2023 AN - OPUS4-58591 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Importance of Spectral Resolution for Accurate Plasma Diagnostics with Implications for Calibration-Free LIBS N2 - In the LIBS literature, almost every second article reports the determination of the plasma temperature using the Boltzmann plot method or the determination of the electron density using the Stark line broadening relation. The first requires the measurement of the integrated intensities of the spectral lines, and the second requires the measurement of the linewidth, under the same assumption of optical thinness. It is taken for granted that this can be easily done either by working with the raw spectra or by fitting an appropriate function to the observed spectral lines. As a rule, reported data are not verified either by an alternative method (e.g., Thomson scattering) or by computer simulations using synthetic spectra. However, the question of how to extract the necessary information from the raw spectral data is not as simple as it might seem. The quality of such an extraction will depend critically on the type of spectral instrument used, its resolution, and the noise superimposed on the data. The problem is that we do not see the spectrum emitted by the plasma, but the spectrum distorted by the measurement; an exaggerated example of such a distortion is shown in Fig. 1. The elimination of this distortion belongs to the class of inverse problems, the so-called ill-posed problems, whose successful solution crucially depends on the quality of the information available. When it comes to spectroscopy, quality of information primarily means high spectral resolution and low noise. Not all spectrometers used in LIBS can provide the quality needed to solve the inverse problem; this casts doubt on many published plasma measurements. The current presentation will be devoted to general shortcomings in the processing of spectral data and inaccuracies in the determination of plasma parameters resulting from these shortcomings. The analysis is based on the use of synthetic spectra produced by plasma with known characteristics, i.e., temperature, species densities, and electron density. The estimation of errors caused by inadequate processing of spectral data is made by comparing the initial and reconstructed plasma parameters. Recipes will be given for which the analytic function best approximates the observed spectral lines, and how data processing errors affect accuracy of calibration-free LIBS will be discussed. These issues were only partially covered in previously published works, for example [1, 2, 3]. T2 - EMS LIBS 2023 CY - Porto, Portugal DA - 04.09.2023 KW - Laser induced breakdown spectroscopy KW - Calibration-free analysis KW - Data processing PY - 2023 AN - OPUS4-58590 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blume, Simon T1 - Femtosecond vs. Nanosecond Laser-induced XUV Spectroscopy (LIXS) N2 - In contrast to laser-induced breakdown spectroscopy (LIBS), measuring after a delay as long as a few microseconds, laser-induced XUV spectroscopy (LIXS) takes advantage of emissions from the very first instant of the pristine plasma. This process exhibits stable and intense line and recombination emissions in the XUV-range. Therefore, common challenges for precise measurements (e.g. quantification efforts) in LIBS caused by signal intensity fluctuations due to matrix effects and plasma-flicker noise are improved, as shown for ns-pulses. A femtosecond laser (pulse length ~100 fs) interacts fundamentally different with matter than a nanosecond laser. Of the many photons needed for ionization of the sample, less are absorbed via inverse Bremsstrahlung and more in a Franck-Condon multiphoton absorption (MPA) process. In combination with the higher peak power, and therefore higher initial plasma temperature (> 10 eV), atoms are selectively ionized to a higher degree while at the same time thermal dissipation and equilibration is reduced. This specificity in excitation leads to a reduced background and the highly ionized atoms overwhelmingly emit the desired XUV-radiation. Thus, fs-LIXS promises to lead to “cleaner” spectra with sharper separation of the emission lines. The capabilities of a fs-LIXS setup in comparison to ns-LIXS will be discussed. Samples of pure elements (Al, Si, Ni, Fe, Mg), as well as composite samples (CaF, LiF, PTFE, polypropylene) serve as model systems to demonstrate these capabilities. T2 - EMSLIBS 2025 CY - Senlis, France DA - 26.01.2026 KW - Femtosecond KW - LIXS KW - XUV KW - Elemental analysis PY - 2026 AN - OPUS4-65470 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael T1 - Erfahrungsaustausch Labor-Robotik N2 - Die BAM setzt in ihren analytischen Labors zunehmend Labor-Robotik ein, um gefähliche oder zeitraubende Routineaufgaben zu automatisieren. Durch Automation kann auch die Reproduzierbarkeit solcher Anwendungen erhöht werden. Im Beitrag werden einige aktuelle Beispiele aus den Analytiklabors diskutiert, wie z. B. die Anwendung für die Herstellung und RFA-Analytik von Gläsern, eine Feinwäge-Robotik für 10-L-Gaszylinder im Rahmen der Herstellung von Primärnormalen oder die Automatisierung von Probenpräsentationen für optische Spektroskopie und chemical Imaging. Auch wird kurz auf den Einsatz von Speicherprogrammierbaren Steuerungen in der modularen Laborautomation und die Virtualisierung von analytischen Laborrechnern eingengangen. T2 - Industrienetzwerk Smartes Labor am Institut für Energie- und Umwelttechnik e.V. (IUTA) CY - Duisburg, Germany DA - 09.11.2022 KW - Laborautomation KW - Labor-Robotik KW - Automatisierung KW - Smartes Labor PY - 2022 AN - OPUS4-56227 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schmidt, Anita T1 - Eine sichere Zukunft für Lithium-Ionen Batterien N2 - Eine sichere Zukunft hat eine Technologie dann, wenn sie die Gesellschaft auch von ihrer Sicherheit überzeugen kann. Dies ist insbesondere für Lithiumbatterien von hoher Bedeutung. Die BAM trägt auf den verschiedene Ebenen auf vielfältige Art und Weise dazu bei, diese Sicherheit zu untersuchen und zu verbessern. T2 - 4. Batterieforum Berlin Brandenburg CY - Potsdam, Germany DA - 22.11.2024 KW - LIthiumbatterien KW - Sicherheit PY - 2024 AN - OPUS4-62328 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Deposition of Titanium Oxides by Nanosecond Laser Ablation: Simulation and Experiment N2 - Surface modification of titanium by laser ablation is investigated theoretically and experimentally. The modification consists in texturing the surface and redeposition of chemically transformed material from the ablation plasma. The redeposition is driven by the hydrodynamic flow in the plasma. Such surface modification improves the biocompatibility of titanium implants. T2 - 2022 Winter Conference on Plasma Spectrochemistry CY - Tucson, Arizona, USA DA - 17.01.2022 KW - Laser ablation KW - Laser induced plasma deposition KW - Surface coating KW - Titanium dioxide KW - Emission spectroscopy KW - Hydrodynamic model KW - Plasma chemistry PY - 2022 AN - OPUS4-54289 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Karafiludis, Stephanos A1 - Stawski, Tomasz T1 - Deciphering the non-classical Crystallization of transition metal phosphates (TMP) N2 - A crucial aspect of ensuring sustainable raw material utilization to meet global demand lies in the efficient recovery and reuse of critical elements and compounds. Phosphate, PO43-, and many transition metals e.g. Ni and Co are listed as critical raw materials (CRMs) due to their indispensable role in numerous industrial processes. However, these elements can also exert harmful environmental impacts, with phosphorus being a major contributor to anthropogenic eutrophication and transition metal ions acting as toxic pollutants, particularly in ground- and wastewaters. Typically, separate pathways have been considered to extract hazardous substances such as transition metals or phosphate, independently from each other. Here, we report the crystallization pathways of transition metal phosphate (TMP) compounds, M-struvite and M-phosphate octahydrate with M = Ni2+, Co2+, NixCo1-x2+, NH4MPO4∙6H2O, M3(PO4)2∙8H2O from aqueous solutions. The co-precipitation of these particular TMP compounds from industrial and agricultural wastewaters has high potential as a P- and 3d metal recovery route. For efficient extraction and transformation of the TMPs, a comprehensive understanding of their nucleation and crystallization pathways from aqueous solutions is required. While the crystallization mechanisms of magnesium or calcium phosphate-bearing phases have been researched for many decades (e.g. struvite, apatite), investigations into TMP materials are relatively scarce and often focus on the adsorption of transition metals on the surface instead of their actual incorporation in minerals. In our study, we investigated in detail the precipitation process of several Co and Ni phosphates using ex- and in-situ spectroscopic-, spectrometric- and diffraction-/scattering-based techniques. We show that the crystallization behavior of TMPs, indeed deviates from a classical crystallization paradigm and follows a non-classical multi-step pathway. Our work extends the understanding of TMP crystallization by elucidating the formation of amorphous precursors preceding the final crystalline phase This time-dependent transition of the transition metal precursor phases can be observed by electron-imaging/tomography depicting a progressively changing amorphous solids until their ultimate reconfiguration to a crystal (Figure 1). Here, the two-metallic NixCo1-x-mixtures deviated anomalously in their reaction kinetics, crystallization outcome and participation of both metals from their pure endmembers. By measuring the crystallization with in-situ X-ray scattering and pH using a flow-through setup geometry, a complex prolonged interplay among nucleating entities e.g. and amorphous or crystalline solids could be observed in the metal phosphate mixtures reaching equilibrium after almost two and a half hours (Figure 2). Our results provide a holistic perspective on the crystallization behavior of transition metal phosphate phases, shedding light on their unique nucleation and growth kinetics involving structural and chemical transformations of the intermediate phases. T2 - Granada Münster Discussion Meeting 2023 CY - Münster, Germany DA - 29.11.2023 KW - Non-classical crystallization theory KW - Transition metals KW - Phosphates PY - 2023 AN - OPUS4-59007 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Riedel, Jens T1 - Current Transformations and Challenges through the Eyes of a Scientist at a German Federal Research Agency N2 - Innovative research, harmonized standards, certification of reference products, policy advice and regulatory action. To most researchers, federal research agencies (FRAs) are abstract chimeras as these tasks appear cryptic and unrelated or even entirely incompatible with each other. Instead of one body, they are pictured as a loose conglomerate of individual institutes, agencies, and offices. The German federal institute for materials research and testing (BAM), is currently undergoing a change process to tear down the walls between these disjunct facilities. Apart from an organizational streamlining, such an infrastructure ideally allows for a holistic approach to tackle complex problems. This presentation will shed some light onto the challenges and opportunities arising. Recent years have been dominated by pivotal changes, crises, and challenges. Many scientists see an increasing circularity in material flows and a fossil fuel phase out to be the only feasible way to proceed. By all this, the material world is faced with a plethora of the above mentioned complicate and complex problems. Parallel to these analog challenges, paradigm-changing advancements in robotics, semantic-data technology, and artificial intelligence, currently empower the digital world with unprecedented speed. Using the example of lithium-ion batteries, the talk will showcase modern FRAs as nutritious ecosystem for a holistic approach towards accelerating all future research and development processes. It will give a glimpse of the complex interplay of different stakeholders like industry, politics, researchers, and end-users but also a simultaneous work on simulation, research and development, characterization, standardization, and regularization. After a brief introduction into these different facets of our institute, a deep dive will be given into the development of novel spectroscopic techniques (e.g. laser induced breakdown spectroscopy (LIBS), glow discharge optical emission spectroscopy, and Raman scattering), directly addressing the demands identified by the above stakeholders. Since by design, a future applicability is already included into this chemical characterization methodologies, all the presented techniques all share the same characteristics to be relatively inexpensive, fast, robust and do not need laborious sample preparation. T2 - Institute Seminar CY - Troy, NY, USA DA - 29.10.2024 KW - Federal research KW - Transformation KW - Analytical Chemistry KW - Instrumentation PY - 2024 AN - OPUS4-61971 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schmid, Thomas A1 - Hodoroaba, Vasile-Dan T1 - Correlative Analysis by Raman and other Micro & Nanospectroscopic Imaging Techniques N2 - In the present talk the basics of the Raman spectroscopy and particularly of Raman microscopy are explained. Advantages and disadvantages of the method are highlighted through selected case studies. In the second part of the lecture examples of correlative imaging with electron, X-ray, ion and optical microscopies from micro- to the nanoscale are highlighted. T2 - Charisma School on Raman Harmonisation CY - Turin, Italy DA - 19.10.2022 KW - Raman KW - Correlative Imaging KW - Microscopy KW - Hyperspectral imaging PY - 2022 UR - https://amdgroup.inrim.it/events/vamas-sc-meeting-47/program-sc47 AN - OPUS4-56094 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Back Deposition of Titanium Oxides under Laser Ablation of Titanium: Simulation and Experiment N2 - Titanium is widely used in medicine for implants and prostheses, thanks to its high biocompatibility, good mechanical properties, and high corrosion resistance. Pure titanium, however, has low wear resistance and may release metallic titanium into surrounding tissues. Structuring and coating its surface with oxide layers are necessary for high wear resistance and improved biocompatibility. In this work, a combination of theoretical and experimental methods was used to study processes responsible for deposition of titanium oxides during ablation of titanium in air. The deposition process was modeled via the Navier-Stokes equations that accounted for the material removal and accumulation of the deposit on the ablation surface. The chemical part was based on the equilibrium model embedded into the hydrodynamic code. Simulations showed that the most active zone of production of condensed titanium oxides were at plasma periphery whereas a zone of strong condensation of titanium metal was above the molten pool. In experiment, a pulsed Yb fiber laser was scanned across a titanium surface. The temperature and composition of the plasma were inferred from plasma emission spectra. The post-ablation surface was analyzed by SEM, TEM, STEM, AFM, and XRD. The developed model well reproduced the main features of experimental data. It was concluded that the deposition of condensed metal oxides from the plasma is a principal mechanism of formation of nanoporous oxide layer on the metal surface. The method of surface structuring and modification by nanosecond laser ablation can be developed into a useful technology that may find applications in medicine, photonics, and other areas. T2 - SciX 2022, The Federation of Analytical Chemistry and Spectroscopy Societies (FACSS) CY - Cincinnati, OH, USA DA - 02.10.2022 KW - Surface coating KW - Laser ablation KW - Plasma modeling PY - 2022 AN - OPUS4-55969 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 - CONF A1 - Riedel, Soraya T1 - Application of 3,3’,5,5’-Tetramethylbenzidine (TMB) in Amperometric Immunoassays for Mycotoxin Detection N2 - Electrochemical methods make great promise to meet the demand for user-friendly on-site devices for monitoring important parameters. Food industry often runs own lab procedures, e.g., for mycotoxin analysis, but it is a major goal to simplify analysis, linking analytical methods with miniaturized technologies. Enzyme-linked immunosorbent assays, with photometric detection of the horseradish peroxidase (HRP) substrate 3,3’,5,5’-tetramethylbenzidine (TMB), form a good basis for sensitive detection. To provide a straight-forward approach for the miniaturization of the detection step, we have studied the pitfalls of the electrochemical TMB detection. By cyclic voltammetry, it could be shown that TMB electrochemistry is strongly dependent on the pH and the electrode material. It was found that screen-printed gold electrodes and a very low pH value (pH 1) are well-suited to perform the electrochemical detection of TMB, due to the reversible character of the redox reaction under these conditions. Under these conditions, a good signal stability over several measuring cycles is achieved, providing the basis for analyzing multiple samples. In contrast to this, for carbon screen-printed electrodes, it was found that the signal response has changed after the electrochemical reaction with TMB at pH 1. At moderately acidic conditions (pH 4), neither with carbon nor with gold electrodes a reproducible electrochemical detection of TMB could be achieved. Based on these findings, we created a smartphone-based, electrochemical, immunomagnetic assay for the detection of ochratoxin A (OTA) and ergometrine in food samples. A competitive assay is performed on magnetic beads using HRP and TMB/H2O2 to generate the signal. Enzymatically oxidized TMB is quantified after addition of H2SO4 by amperometry with screen-printed gold electrodes in a custom-made wall-jet flow cell. The results are in good correlation with the established photometric detection method, providing a solid basis for sensing of further analytes in HRP-based assays using the newly developed miniaturized smartphone-based, electrochemical, immunomagnetic assay. T2 - 73rd Annual Meeting of the ISE CY - Online meeting DA - 12.09.2022 KW - Cylic Voltammetry KW - Immunoassay KW - Mycotoxins KW - Amperometry KW - Electrochemistry PY - 2022 N1 - Geburtsname von Riedel, Soraya: Höfs, S. - Birth name of Riedel, Soraya: Höfs, S. AN - OPUS4-55793 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Winckelmann, Alexander T1 - Anwendung von hochauflösender optischer Spektrometrie zur Lithium-Isotopenanalyse N2 - Optische Spektrometrie wird als Alternative zur Massenspektrometrie im Bereich der Lithium-Isotopenanalyse vorgestellt. T2 - 11. Analytische Tage CY - Idstein, Germany DA - 11.05.2023 KW - Lithium KW - Isotopenanalyse KW - Atomabsorptionsspektrometrie KW - Massenspektrometrie PY - 2023 AN - OPUS4-57543 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - You, Yi T1 - Advanced Repetition-Rate Modulation and Computational Strategies for Background-Free LIBS Using Non-Gated Spectrometers N2 - Laser-induced breakdown spectroscopy (LIBS) is recognized for its rapid, direct elemental analysis capabilities. However, its general adoption is constrained by the reliance on expensive, high-power consumption, gated cameras such as intensified charge-coupled devices (CCDs). These devices, while sensitive, are expensive and possess low frame rates, limiting their efficacy in dynamic or challenging environments. Our study proposes an innovative approach that leverages non-gated spectrometers in conjunction with the framework of correlation spectroscopy to isolate analyte signals responsive to a specific repetition-rate modulation pattern, thereby yielding spectra with zero background. We utilized a diode-pumped solid-state laser, with repetition rates ranging from 10 Hz to 30 kHz, to induce plasma in aqueous solutions containing various alkaline and earth-alkaline metals. With a non-gated single-grating linear CCD spectrometer, we found that the continuum signal plateaued at approximately 7 kHz. In contrast, atomic emissions from the dissolved analytes showed continued increases. Notably, atomic emissions from the solvent (water) were observable only above 8.5 kHz, at a significant high rate of increase. Through computational synthesis of a modulation pattern, we determined an optimized scheme that effectively discriminates continuum and analyte signals; this pattern was optimized with a genetic algorithm. The spectral matrix correlating signal intensity with laser repetition rate and wavelength was used as the input of the model. Meanwhile, the fitness function that extracts the background-free spectra was built in-house and inspired by the Gardner transform, which exploits the power of Fourier transform, allowing for flagging and splitting analyte signal from other undesired features. This approach bypasses the limitations associated with gated cameras, while providing a cost-effective alternative for robust LIBS applications. This advancement is particularly relevant in field, portable and remote applications, aligning with the ongoing demand for accessible, high-performance analytical tools in diverse scientific fields. T2 - SCIX 2024 Conference CY - Raleigh, NC, USA DA - 20.10.2024 KW - LIBS KW - Data Processing KW - High Repetition Rate KW - Repetition Rate Modulation KW - Data-Oriented Experimental Design PY - 2024 AN - OPUS4-62137 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Riedel, Jens T1 - Acoustic Ion Manipulation: Electric-field-free Approach to Gate, Focus, and Separate Ions at Atmospheric Pressure N2 - Approaches to control the motion and direction of ionized particles and mole-cules are an essential aspect of ion-based spectrometries, such as mass spec-trometry (MS) and ion mobility spectrometry (IMS). A wide variety of ion optics exist to reflect, focus, separate, gate, and filter ions based on physical proper-ties. Notably all rely on electric and magnetic fields to alter the trajectory of ionized atoms and molecules. While these optics are quite efficient at low pressures due to the large mean free path, diffusion and electrostatic repulsion between ions dominate at higher pressures. Conventional ion optics, that use electric or magnetic fields, can guide ions at atmospheric pressure (AP), but require high field strengths to overcome the dominating aerodynamic effects. Here, we describe a remarkable phenomenon whereby low-power acoustic fields are used to move, shape, gate, and separate beams of gaseous ions at atmospheric pressure. We refer to this approach as Acoustic Ion Manipulation (AIM). Gaseous ions at AP are directed towards and separated by the presence of the acoustic field. To better understand the phenomenon, an ion-detector array provided a measure of bulk ion movement, while mass spectrometry (MS) offered chemical-specific information. As one example of an AIM setup, a standing acoustic wave was formed with two ultrasonic speakers and placed between an ionization source and ion detector. Ion beams preferentially travel through regions of stable pressure gradients (i.e. nodes) and deflect from un-stable regions (i.e. antinodes). Shadowgraphy revealed that the ions are sepa-rated from a neutral gas stream. Specific examples of ion focusing, gating, and separation (based on ion size) will be shown. In addition, experimental findings will be used to postulate a theory to develop a better understand of the behav-ior of gas-phase ions in acoustic fields. This discovery could have profound im-pacts in IMS/MS instrumentation as well as materials processing and charac-terization. T2 - 56. Jahrestagung der DGMS CY - Göttingen, Germany DA - 04.03.2025 KW - Acoustic Ion Manipulation KW - Mass spectrometry KW - Ultrasound PY - 2025 AN - OPUS4-64208 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - You, Yi T1 - Acoustic Ion Manipulation (AIM) N2 - The precise control of gaseous ions is a cornerstone in ion-based spectrometry and other disciplines such as materials processing. Traditional high-pressure ion optics rely on electrostatic and magnetic fields that often demand the use of intense electric fields, radio frequency activation, complex geometrical arrangements, or partially transmissive grids. Consequently, the efficiencies of such devices tend to be low or they require large footprints, as ion motions under ambient conditions are governed aerodynamically by collisions and fluid dynamics. However, from a different perspective and holistic reasoning, the limitations posed by collisions, aerodynamics, and other factors that hinder ion control in the open-air suggested an innovative direction for ion manipulation. Our study introduces a novel method that employs low-power standing acoustic waves to effectively manipulate ion beams. We observe that ions distinctively prefer traveling through areas of static pressure within the acoustic field, identified as "nodes." In contrast, neutral gases are unaffected by the acoustic field structure and continue to move along a straight trajectory. We have named this method Acoustic Ion Manipulation (AIM). Initial studies demonstrated selective and efficient manipulations of ion with AIM, including gating, redirection, regional dispersion, and focusing. This technique broadens the scope of ion manipulation strategies at high pressures while enriching our fundamental understanding of ion-acoustic kinetics. The potential applications of this method are vast, promising significant advancements in the fields of analytical chemistry, environmental science, and beyond. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Acoustic ion manipulation KW - Mass spectrometry PY - 2025 AN - OPUS4-64110 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - A Long Way of Plasma Modeling: Personal Experience N2 - Modeling is an important tool for understanding a physical phenomenon. It helps to interpret results of experiments and optimize experimental parameters for obtaining a desirable result. Modeling laser induced plasma is beneficial for many scientific and industrial fields, e.g., analytical chemistry, pulsed laser deposition, plasma enhanced chemical vapor deposition, laser welding, additive manufacturing etc. In this presentation, a personal experience in development of a physical model of laser induced plasma will be given in a chronological sequence starting from early 2000th and until now. Over the time, the model evolved from its simple analytical form that described plasma emission spectra to its current numerical form that describes plasma dynamics, chemistry, and interaction with a substrate surface. Several examples will be given for the application of the model to practical problems such as spectroscopic chemical analysis, plasma enhanced chemical vapor deposition, and surface modification by laser ablation. T2 - XII World Conference on Laser Induced Breakdown Spectroscopy CY - Bari, Italy DA - 05.09.2022 KW - Laser induced plasma KW - CFD computational fluid dynamic KW - Plasma modeling KW - Plasma chemistry PY - 2022 AN - OPUS4-55669 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -