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 - JOUR A1 - Danischewski, Julia L. A1 - You, Yi A1 - Bauer, Lauren A1 - Riedel, Jens A1 - Shelley, Jacob T. T1 - Use of Resonant Acoustic Fields as Atmospheric-Pressure Ion Gates N2 - Ion optics are crucial for spectrometric methods such as mass spectrometry (MS) and ion mobility spectrometry (IMS). Among the wide selection of ion optics, temporal ion gates are of particular importance for time-of-flight MS (TOF-MS) and drift-tube IMS. Commonly implemented as electrostatic ion gates, these optics offer a rapid, efficient means to block ion beams and form discrete ion packets for subsequent analysis. Unfortunately, these devices rely on pulsed high voltage sources and are not fully transparent, even in their open state, which can lead to ion losses and contamination. Here, a novel atmospheric-pressure ion gate based on a resonant acoustic field structure is described. This effect was accomplished through the formation of a resonant, standing acoustic wave of alternating nodes and antinodes. Alignment of an atmospheric-pressure gaseous ion beam with an antinode, i.e. a region of transient pressure, of the acoustic structure acted as a gate and blocked ions from impinging on ion-selective detectors, such as a mass spectrometer and a Faraday plate. The velocity of the ion stream and acoustic power were found to be critical parameters for gating efficiency. In the presence of an acoustic field (i.e., a closed gate), ion signals decreased by as much as 99.8% with a response time faster than the readout of the ion-measurement devices used here (ca. 75 ms). This work demonstrates the basis for a low-cost, acoustic ion gate, which is optically transparent and easily constructed with low-power, off-the-shelf components, that could potentially be used with MS and IMS instrumentation. KW - Acoustic Ion Manipulation PY - 2025 DO - https://doi.org/10.1021/acs.analchem.4c05493 SN - 1520-6882 VL - 97 IS - 5 SP - 2890 EP - 2898 PB - American Chemical Society AN - OPUS4-62648 LA - eng 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 - Blume, Simon T1 - Femtosecond Laser-induced XUV Spectroscopy (LIXS) for Elemental Analysis N2 - In a typical laser-induced breakdown spectroscopy (LIBS) setup, emissions from collisional excitation of the atoms in the later stages of the plasma are detected and provide information about the elemental fingerprint of the sample. However, precise measurements, in particular quantification efforts, suffer from fluctuations of the intensity of the detected emission lines due to matrix effects and plasma-flicker noise, as well as significant background noise. In contrast, the early stages of the plasma are dominated by electron-ion recombination and Bremsstrahlung, which lead to sharp and intense x-ray emissions with consistent intensity profiles between laser pulses and suppressed background noise, therefore improving the limit of detection, especially for lighter elements. These emissions are detected in laser-induced XUV spectroscopy (LIXS).[1] Introduction of a femtosecond laser (pulse length ~100 fs) to the LIXS setup fundamentally changes the laser energy absorption and ablation process. The laser pulse energy is absorbed and redistributed by multiphoton absorption and inverse Bremsstrahlung and operates on a time frame faster than the plasma formation. Additionally, the plasma formation itself is accelerated leading to signal generation in the XUV-range before generation of the undesired background emissions. Thus, utilization of a femtosecond laser allows for further suppression of broadband emissions from the plasma allowing for sharper separation of the emission lines and improved limit of detection. This work presents the results of the combination of a LIXS setup with a femtosecond laser and assess the capabilities of this system with a model sample of cathode material from a spent lithium-ion battery. T2 - AMACEE 2025 CY - Brno, Czech Republic DA - 26.8.2025 KW - LIXS KW - Femtosecond laser KW - Instrumentation PY - 2025 AN - OPUS4-64118 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Palásti, Dávid jenö T1 - Interferometric sensing in the UV range – Investigation and comparison of the all-reflective spatial heterodyne spectrometer designs N2 - Spatial heterodyne spectrometers (SHS) are optical interferometric devices, working in the UV and visible spectral ranges [1]. The most common SHS setup is similar to the Michelson interferometer, both utilizes a beam splitter in the incoming beam path. In case of the SHS the split beams are not aimed towards orthogonal mirrors, but reflective optical gratings, set under a selected angle. These optical gratings diffract the beams, the direction of every wavelength will depend on the grating constant and the angle of the gratings. The wavefronts belonging to different wavelengths are going to cross each other under a unique angle, resulting in a spatial interference, which is recorded by a digital camera. This relatively compact setup provides high resolution and light throughput, which properties were harnessed for tasks requiring good line separation and/or high sensitivity [2]. However, SHS are only applicable on wavelengths for which an adequate transmissive beam splitter is available like the visible range, but not the far UV. To overcome this limitation, different all-reflective designs were introduced [3]. These instruments utilize symmetric optical gratings for the splitting and recombination of the beams. Although these SHS devices solve the main limitations of the traditional ones, they come with their fair share of drawbacks as well, such as more complex arrangement and the requirement for more delicate tuning. The behaviour of the traditional SHS is well documented [4,5], but in regards of the all-reflective ones we have much less available information. In this current study we utilized computational modelling to predict the behaviour of the all-reflective SH spectrometers, with special attention to the effects of the different alignment errors. Later we utilize this knowledge to fine tune an SHS for sensing (LIBS, Raman) in the UV region. Furthermore, we are introducing two new all-reflective SHS setups and compering them to their older counterparts. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - SHS KW - Spectroscopy PY - 2025 AN - OPUS4-63556 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blume, Simon T1 - Isotopic analysis of lithium via acousto-optically gated high-repetition laser-induced breakdown spectroscopy and spatial heterodyne spectroscopy N2 - Acousto-optically gating the emission signal from a laser-induced breakdown spectroscopy (LIBS) plasma negates some of the line-broadening effects, therefore, improving the signal line shape. However, the remaining influences disallow the differentiation of the contributions of the individual lithium isotopes, even when utilizing a high-resolution spatial heterodyne spectrometer (SHS). Nevertheless, isotopic analysis of lithium with LIBS is still feasible, because lithium exhibits a strong self-absorption dip in the emission signal, which is likewise characterized by the isotopic shift and even benefits from the broad emission lines typically observed in LIBS. The isotopic ration can be resolved from the absorption dip via high-resolution SHS. T2 - SciX 2024 CY - Raleigh, NC, USA DA - 20.10.2024 KW - LIBS KW - SHS KW - Isotopic analysis KW - Lithium PY - 2024 AN - OPUS4-62012 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Palásti, Dávid jenö T1 - The effects of the laser pulse profile on the plasma emission properties N2 - Intense laser pulses create plasmas upon radiation on targets, and the properties of such plasmas are generally determined by both the properties of the target and the laser pulse. In terms of laser intensity, the irradiance and even more importantly the fluence are the critical parameters [1]. Since most lasers emit pulses of a constant pulse duration dictated by the design of the resonator and Q-switch, these two parameters are usually used interchangeably in studies. However, with the emergence of fiber laser based light sources [2], which are capable not just to freely tune the pulse duration, but to generate variable and high pulse repetition rates, up to the MHz range, a new and interesting optimization aspect is given to the laser spectroscopy community. In our study a low alloy steel standard sample (BAS 403/1) was investigated using a variable pulse duration and pulse repetition rate MOPA laser with 80W power of  = 1064 nm emission (JPT M7, VONJAN Technology GmbH, Wessling, Germany). In our experiments the laser was set to pulses with low individual energy (0.4 mJ) at 200 kHz pulse repetition rate, while the pulse duration was varied between 50 and 500 ns. The plasma emission was recorded by an LTB Demon spectrometer in several spectral regions, which included iron, chromium and manganese lines. Utilizing the variable pulse duration of this laser source, it was possible to assess the effects of changing the fluence, while the irradiance was kept at the same value. Among the investigated parameters are the emission intensity, peak width and self-absorption characteristics of major and minor components, as well as the plasma temperature. While the effects for the peak intensity are quite well correlated with the fluence, its interplay with other peak parameters appear to be more complicated. T2 - AMACEE 2025 CY - Brno, Czech Republic DA - 26.08.2025 KW - LIBS KW - Fiberlaser KW - Plasma properties PY - 2025 AN - OPUS4-64218 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas T1 - On-line monitoring of polyhydroxyalkanoate extraction process using compact NMR spectroscopy N2 - Portable benchtop NMR spectrometers enable real-time process and reaction monitoring in contrast to conventional laboratory based off-line gas chromatography or high-field NMR measurements. In this study, benchtop NMR spectroscopy is demonstrated as a process analytical technology (PAT) tool for the application of the solvent extraction step in downstream processing of polyhydroxyalkanoate (PHA) biopolymers. These are one of the few thermoplastic polymers synthesized 100 % via biotechnological routes which fully biodegrade in common natural environments. This makes them excellent candidate materials for sustainable replacement of conventional plastic materials. Online NMR experiments were conducted using a fully automated setup, employing commercially available PTFE tubing as a flow-cell assembly. Extraction was carried out in a thermostated stirred batch reactor in lab-scale. Single-scan NMR spectra allowed continuous monitoring of the extraction of the PHA copolymer poly-(hydroxybutyrate-co-hydroxyhexanoate) containing 13.5 mol-% hydroxyhexanoate from Ralstonia eutropha biomass. Extractions were performed in chloroform and acetone across ground lyophilized cell loadings ranging from 20 to 120 g/L. The reproducibility and reliability of compact NMR spectroscopy closely matched with high-field NMR measurements. A strong correlation was observed between online low-field NMR data and offline gas chromatography (GC) analysis. The study highlights the versatility of compact NMR for process monitoring, facilitating endpoint determination and enhancing extraction efficiency by optimizing process parameters. Steady-state conditions were achieved within 6 to 10 minutes for chloroform and acetone, respectively, underscoring the method’s value in supporting downstream process development and optimization for PHA recovery. T2 - 20. Herbstkolloquium Arbeitskreis Prozessanalytik CY - Frankfurt am Main, Germany DA - 03.12.2025 KW - Polyhydroxyalkanoate KW - Process Analytical Technology KW - Downstream processing KW - Benchtop-NMR PY - 2025 AN - OPUS4-65065 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Miliūtė, Aistė A1 - Bustamante, Joana A1 - Karafiludis, Stephanos A1 - Zöllner, Moritz A1 - Eddah, Mustapha A1 - Emmerling, Franziska A1 - Mieller, Björn A1 - George, Janine A1 - Stawski, Tomasz M. T1 - Synthesis and phase purity of the negative thermal expansion material ZrV2O7 N2 - Synthesis of pure, homogeneous, and reproducible materials is key for the comprehensive understanding, design, and tailoring of material properties. In this study, we focus on the synthesis of ZrV2O7, a material known for its negative thermal expansion properties. We investigate the influence of solid-state and wet chemistry synthesis methods on the purity and homogeneity of ZrV2O7 samples. Our findings indicate that different synthesis methods significantly impact the material's characteristics. The solid-state reaction provided high-purity material through extended milling time and repeated calcination cycles, while the sol-gel reaction enabled a “near-atomic” level of mixing and, therefore, homogenous phase-pure ZrV2O7. We confirmed purity via X-ray diffraction and Raman spectroscopy, highlighting differences between phase-pure and multiphase ceramics. These analytical techniques allowed us to distinguish subtle differences in the structure of the material. Based on ab initio simulated phonon data, we were able to interpret the Raman spectra and visualise Raman active atom vibrations. We show that phase purity enables the unbiased characterisation of material properties such as negative thermal expansion. KW - NTE KW - Sol-gel KW - Solid-state KW - Ab-initio KW - XRD KW - Raman PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-624013 DO - https://doi.org/10.1039/d4tc04095c SN - 2050-7534 SP - 1 EP - 13 PB - Royal Society of Chemistry (RSC) AN - OPUS4-62401 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Karafiludis, Stephanos A1 - Kochovski, Z. A1 - Scoppola, E. A1 - Retzmann, Anika A1 - Hodoroaba, Vasile-Dan A1 - ten Elshof, J. E. A1 - Emmerling, Franziska A1 - Stawski, Tomasz Maciej T1 - Nonclassical Crystallization Pathway of Transition Metal Phosphate Compounds N2 - Here, we elucidate nonclassical multistep crystallization pathways of transition metal phosphates from aqueous solutions. We followed precipitation processes of M-struvites, NH4MPO4·6H2O, and M-phosphate octahydrates, M3(PO4)2·8H2O, where M = Ni, Co, or NixCo1–x, by using in situ scattering and spectroscopy-based techniques, supported by elemental mass spectrometry analyses and advanced electron microscopy. Ni and Co phosphates crystallize via intermediate colloidal amorphous nanophases, which change their complex structures while agglomerating, condensing, and densifying throughout the extended reaction times. We reconstructed the three-dimensional morphology of these precursors by employing cryo-electron tomography (cryo-ET). We found that the complex interplay between metastable amorphous colloids and protocrystalline units determines the reaction pathways. Ultimately, the same crystalline structure, such as struvite, is formed. However, the multistep process stages vary in complexity and can last from a few minutes to several hours depending on the selected transition metal(s), their concentration, and the Ni/Co ratio. KW - Non-classical crystallization theory KW - Transition metals KW - Phosphates KW - Amorphous phases KW - Intermediate phases PY - 2023 DO - https://doi.org/10.1021/acs.chemmater.3c02346 SN - 1520-5002 VL - 35 IS - 24 SP - 10645 EP - 10657 PB - American Chemical Society (ACS) CY - Washington D.C. AN - OPUS4-59135 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -