TY - CONF A1 - Kern, Simon A1 - Michalik-Onichimowska, Aleksandra A1 - Riedel, Jens A1 - Panne, Ulrich A1 - King, R. A1 - Maiwald, Michael ED - Herwig, Christoph T1 - “Click” analytics for “click” chemistry – a simple method for calibration-free evaluation of online NMR spectra T2 - Tagungsband 11. Interdisziplinäres Doktorandenseminar N2 - Currently, research in chemical manufacturing moves towards flexible plug-and-play approaches focusing on modular plants, capable of producing small scales on-demand with short down-times between individual campaigns. This approach allows for efficient use of hardware, a faster optimization of the process conditions, and thus, an accelerated introduction of new products to the market. Driven mostly by the search for chemical syntheses under biocompatible conditions, so-called “click” chemistry rapidly became a growing field of research. The resulting simple one-pot reactions are so far only scarcely accompanied by an adequate optimization via comparably straightforward and robust analysis techniques. Here we report on a fast and reliable calibration-free online high field NMR monitoring approach for technical mixtures. It combines a versatile fluidic system, continuous-flow measurement with a time interval of 20 s per spectrum, and a robust, automated algorithm to interpret the obtained data. All spectra were acquired using a 500 MHz NMR spectrometer (Varian) with a dual band flow probe having a 1/16-inch polymer tubing working as a flow cell. Single scan 1H NMR spectra were recorded with an acquisition time of 5 s, relaxation delay of 15 s. As a proof-of-concept, the thiol-ene coupling between N-boc cysteine methyl ester and allyl alcohol was conducted in non-deuterated solvents while its time-resolved behaviour was characterised with step tracer experiments. Through the application of spectral modeling the signal area for each reactant can be deconvoluted in the online spectra and thus converted to the respective concentrations or molar ratios. The signals which were suitable for direct integration were used herein for comparison purposes of both methods. T2 - 11. Interdisziplinäres Doktorandenseminar CY - Berlin, Germany DA - 12.03.2017 KW - Process Monitoring KW - Online NMR Spectroscopy KW - Indirect Hard Modeling KW - Process Control KW - Process Analytical Technology KW - CONSENS KW - Click Chemistry PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-435531 SP - 33 EP - 35 PB - Gesellschaft Deutscher Chemiker (GDCh) CY - Frankfurt a. M. AN - OPUS4-43553 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Michalik-Onichimowska, Aleksandra A1 - Kern, Simon A1 - Riedel, Jens A1 - Panne, Ulrich A1 - King, R. A1 - Maiwald, Michael T1 - ‘‘Click” analytics for ‘‘click” chemistry – A simple method for calibration–free evaluation of online NMR spectra JF - Journal of Magnetic Resonance N2 - Driven mostly by the search for chemical syntheses under biocompatible conditions, so called "click" chemistry rapidly became a growing field of research. The resulting simple one-pot reactions are so far only scarcely accompanied by an adequate optimization via comparably straightforward and robust analysis techniques possessing short set-up times. Here, we report on a fast and reliable calibration-free online NMR monitoring approach for technical mixtures. It combines a versatile fluidic system, continuous-flow measurement of 1H spectra with a time interval of 20 s per spectrum, and a robust, fully automated algorithm to interpret the obtained data. As a proof-of-concept, the thiol-ene coupling between N-boc cysteine methyl ester and allyl alcohol was conducted in a variety of non-deuterated solvents while its time-resolved behaviour was characterized with step tracer experiments. Overlapping signals in online spectra during thiol-ene coupling could be deconvoluted with a spectral model using indirect hard modeling and were subsequently converted to either molar ratios (using a calibrationfree approach) or absolute concentrations (using 1-point calibration). For various solvents the kinetic constant k for pseudo-first order reaction was estimated to be 3.9 h-1 at 25 °C. The obtained results were compared with direct integration of non-overlapping signals and showed good agreement with the implemented mass balance. KW - Online NMR Spectroscopy KW - Reaction Monitoring KW - Automated Data Evaluation KW - Thiol-ene click chemistry KW - Click Chemistry KW - Process Analytical Technology PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-393232 UR - http://www.sciencedirect.com/science/article/pii/S1090780717300575 DO - https://doi.org/10.1016/j.jmr.2017.02.018 VL - 277 SP - 154 EP - 161 PB - Elsevier Inc. CY - Oxford AN - OPUS4-39323 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Saloga, Patrick E. J. A1 - Smales, Glen Jacob A1 - Clark, Adam H. A1 - Thünemann, Andreas T1 - Zinc Phosphate Nanoparticles Produced in Saliva JF - European Journal of Inorganic Chemistry N2 - This paper reports the formation of zinc phosphate nanoparticles from the artificial digestion of zinc chloride. Initially, the formation of amorphous primary particles with a mean radius of 1.1 nm is observed, alongside the formation of larger, protein stabilized aggregates. These aggregates, with a radius of gyration of 37 nm, are observed after 5 minutes of exposure to artificial saliva and are shown to be colloidally stable for a minimum time of two weeks. The initially formed primary particles are thought to consist of amorphous zinc phosphate, which is then transformed into crystalline Zn3(PO4)2·4H2O over the course of two weeks. Our results demonstrate that the interaction of inorganic salts with bodily fluids can induce the formation of de novo nanoparticles, which in turn, provides insights into how zinc‐enriched foods may also facilitate the formation of nanoparticles upon contact with saliva. As such, this may be considered as an undesirable (bio)mineralization. KW - SAXS KW - Digestion KW - Zinc phosphate PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-514239 DO - https://doi.org/10.1002/ejic.202000521 IS - 38 SP - 3654 EP - 3661 PB - Wiley-VCH Verlag GmbH & Co. KGaA CY - Weinheim AN - OPUS4-51423 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Balderas-Xicohtencatl, R. A1 - Villajos Collado, José Antonio A1 - Casabán, J. A1 - Wong, D. A1 - Maiwald, Michael A1 - Hirscher, M. T1 - ZIF‑8 Pellets as a Robust Material for Hydrogen Cryo-Adsorption Tanks JF - Applied Energy Materials N2 - Cryoadsorption on the inner surface of porous materials is a promising solution for safe, fast, and reversible hydrogen storage. Within the class of highly porous metal−organic frameworks, zeolitic imidazolate frameworks (ZIFs) show high thermal, chemical, and mechanical stability. In this study, we selected ZIF-8 synthesized mechanochemically by twin-screw extrusion as powder and pellets. The hydrogen storage capacity at 77 K and up to 100 bar has been analyzed in two laboratories applying three different measurement setups showing a high reproducibility. Pelletizing ZIF-8 increases the packing density close to the corresponding value for a single crystal without loss of porosity, resulting in an improved volumetric hydrogen storage capacity close to the upper limit for a single crystal. The high volumetric uptake combined with a low and constant heat of adsorption provides ca. 31 g of usable hydrogen per liter of pellet assuming a temperature−pressure swing adsorption process between 77 K − 100 bar and 117 K − 5 bar. Cycling experiments do not indicate any degradation in storage capacity. The excellent stability during preparation, handling, and operation of ZIF-8 pellets demonstrates its potential as a robust adsorbent material for technical application in pilot- and full-scale adsorption vessel prototypes. KW - Hydrogen adsorption storage KW - Metal−organic frameworks KW - ZIF-8 KW - Cryoadsorption KW - Hydrogen Storage KW - MefHySto PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-569473 DO - https://doi.org/10.1021/acsaem.2c03719 SN - 2574-0962 SP - 1 EP - 8 PB - ACS Publications CY - Washington DC AN - OPUS4-56947 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Würth, Christian A1 - Grauel, Bettina A1 - Pons, Monika A1 - Frenzel, Florian A1 - Rissiek, P. A1 - Rücker, Kerstin A1 - Haase, Markus A1 - Resch-Genger, Ute T1 - Yb- and Er concentration dependence of the upconversion luminescence of highly doped NaYF4:Yb,Er/NaYF4:Lu core/shell nanocrystals prepared by a water-free synthesis JF - Nano Research N2 - High sensitizer and activator concentrations have been increasingly examined to improve the performance of multi-color emissive upconversion (UC) nanocrystals (UCNC) like NaYF4:Yb,Er and first strategies were reported to reduce concentration quenching in highly doped UCNC. UC luminescence (UCL) is, however, controlled not only by dopant concentration, yet by an interplay of different parameters including size, crystal and shell quality, and excitation power density (P). Thus, identifying optimum dopant concentrations requires systematic studies of UCNC designed to minimize additional quenching pathways and quantitative spectroscopy. Here, we quantify the dopant concentration dependence of the UCL quantum yield (ΦUC) of solid NaYF4:Yb,Er/NaYF4:Lu upconversion core/shell nanocrystals of varying Yb3+ and Er3+ concentrations (Yb3+ series: 20%‒98% Yb3+; 2% Er3+; Er3+ series: 60% Yb3+; 2%‒40% Er3+). To circumvent other luminescence quenching processes, an elaborate synthesis yielding OH-free UCNC with record ΦUC of ~9% and ~25 nm core particles with a thick surface shell were used. High Yb3+ concentrations barely reduce ΦUC from ~9% (20% Yb3+) to ~7% (98% Yb3+) for an Er3+ concentration of 2%, thereby allowing to strongly increase the particle absorption cross section and UCNC brightness. Although an increased Er3+ concentration reduces ΦUC from ~7% (2% Er3+) to 1% (40%) for 60% Yb3+. Nevertheless, at very high P (> 1 MW/cm2) used for microscopic studies, highly Er3+-doped UCNC display a high brightness because of reduced saturation. These findings underline the importance of synthesis control and will pave the road to many fundamental studies of UC materials. KW - Upconverion KW - Nanoparticle KW - Lanthanides KW - Quantum yield PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551346 DO - https://doi.org/10.1007/s12274-022-4570-5 SP - 1 EP - 8 PB - Springer AN - OPUS4-55134 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kraft, Sebastian A1 - Schille, J. A1 - Bonse, Jörn A1 - Löschner, U. A1 - Krüger, Jörg T1 - X‑ray emission during the ablative processing of biological materials by ultrashort laser pulses JF - Applied Physics A N2 - The ablative laser processing with ultrashort pulsed laser beams may cause secondary emission of hazardous X-rays. While the effect has recently been proven to be considered in working safety regulations when processing technical materials, such as metals, the X-ray emission rates during the ablative processing of biological tissue materials are widely unexplored yet. Therefore, biological materials like water, isotonic saline solution, pig eyes, and human teeth were ablated with ultrashort laser pulses of 1030 nm wavelength, 600 fs pulse duration and 5 kHz pulse repetition rate, aiming to mimic typical surgery situations. Simultaneously, in-situ X-ray dose rate measurements were performed at a short distance from the plasma to display potential X-ray emission. For all four studied biological materials, our measurements prove the secondary emission of laser-induced X-rays. KW - Ultrashort pulsed laser KW - Laser-induced X-ray emission KW - Ophthalmology KW - Dentistry KW - Secondary hazard PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-569960 DO - https://doi.org/10.1007/s00339-023-06440-4 SN - 0947-8396 VL - 129 IS - 3 SP - 1 EP - 8 PB - Springer AN - OPUS4-56996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Dietrich, P. A1 - Thissen, A. A1 - Kulak, N. A1 - Kjaervik, Marit A1 - Unger, Wolfgang T1 - XPS surface chemical analysis of aqueous solutions with EnviroESCA T2 - SPECS Application Notes N2 - Water and aqueous reagents are essential in any biological process or system. But apart from a few special low vapor-pressure cases, liquids have not been accessible to any technique requiring UHV conditions. EnviroESCA opens up this exciting field of applications. In this paper first results from water based samples are presented as a proof of concept to demonstrate the special capabilities of EnviroESCA analyzing liquid samples. The following solutions were investigated under near ambient pressure conditions: i.) water, ii.) brine, iii.) an oil in water dispersion, iv.) aqueous iron(II) sulfate heptahydrate, and v.) a suspension of nano silver particles in water. KW - Surface Analysis KW - Near Ambient Pressure XPS KW - Aqueous Solutions PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-394603 UR - http://www.enviro.specs.de/cms/upload/bilder/EnviroESCA/Applications/Liquids/Application-Note_EnviroESCA_Aqueous_Solutions.pdf N1 - BAM Mitarbeiter Beitrag im Acknowledgement definiert. IS - #000394 SP - 1 PB - SPECS CY - Berlin AN - OPUS4-39460 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fritzsche, Sven A1 - Jaenisch, Gerd-Rüdiger A1 - Pavasaryte, Lina A1 - Funk, Alexander T1 - XCT and DLW: Synergies of Two Techniques at Sub-Micrometer Resolution JF - Applied Science N2 - Direct Laser Writing (DLW) and X-ray computed tomography (XCT) both offer unique possibilities in their respective fields. DLW produces full three-dimensional (3D) polymer structures on the microscale with resolutions below 100 nm. The fabricated structures can be analysed by XCT or X-ray microscopy (XRM), which incorporates additional X-ray lenses, in three dimensions down to a minimal basic spatial resolution of about 500 nm or 50 nm, respectively. In this work, two different DLW structures are analysed via XCT. Internal defects are detected and analysed for the purpose of quality control. Defects and structures with sizes down to 1.5 µm are successfully analysed. A 3D reconstruction and internal, hidden features of the fabricated structures are shown and discussed. In a first-of-its-kind study, we demonstrate the detectability of a single-voxel line inside a fabricated structure that would not be detectable with SEM or light microscopy. Furthermore, the direct fabrication on a PET substrate is shown to overcome the high X-ray absorbance of commonly used glass substrates. Attenuation spectra of SZ2080 and glass substrates are compared to a fabrication route direct on a 170 µm PET foil. The practical aspects of XCT measurements for DLW structures on different substrates will be discussed. KW - Non-destructive testing KW - Two-photon polymerization KW - X-ray microscopy KW - XCT KW - 2PP KW - Direct laser writing PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-560525 DO - https://doi.org/10.3390/app122010488 VL - 12 IS - 20 SP - 1 EP - 15 PB - MDPI CY - Basel AN - OPUS4-56052 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tammas-Williams, S. A1 - Zhao, H. A1 - Léonard, Fabien A1 - Derguti, F. A1 - Todd, I. A1 - Prangnell, P.B. T1 - XCT analysis of the influence of melt strategies on defect population in Ti-6Al-4V components manufactured by Selective Electron Beam Melting JF - XCT analysis of the influence of melt strategies on defect population in Ti-6Al-4V components manufactured by Selective Electron Beam Melting N2 - Selective Electron Beam Melting (SEBM) is a promising powder bed Additive Manufacturing technique for near-net-shape manufacture of high-value titanium components. However without post-manufacture HIPing the fatigue life of SEBM parts is currently dominated by the presence of porosity. In this study, the size, volume fraction, and spatial distribution of the pores in model samples have been characterised in 3D, using X-ray Computed Tomography, and correlated to the process variables. The average volume fraction of the pores (b0.2%) was measured to be lower than that usually observed in competing processes, such as selective laser melting, but a strong relationship was found with the differentbeamstrategies used to contour ,and infill by hatching, a part section. The majority of pores were found to be small spherical gas pores, concentrated in the infill hatched region; this was attributed to the lower energy density and less focused beam used in the infill strategy allowing less opportunity for gas bubbles to escape the melt pool. Overall, increasing the energy density or focus of the beam was found to correlate strongly to a reduction in the level of gas porosity. Rarer irregular shaped pores were mostly located in the contour region and have been attributed to a lack of fusion between powder particles. KW - Titanium KW - Additive Manufacture KW - Selective Electron Beam Melting KW - Pores KW - X-ray computed tomography PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-416577 UR - http://www.sciencedirect.com/science/article/pii/S104458031500039X?via%3Dihub DO - https://doi.org/10.1016/j.matchar.2015.02.008 VL - 102 SP - 47 EP - 61 CY - Materials Characterization AN - OPUS4-41657 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hernández-Nava, E. A1 - Tammas-Williams, S. A1 - Smith, C. A1 - Léonard, Fabien A1 - Withers, P. J. A1 - Todd, I. A1 - Goodall, R. T1 - X-ray tomography characterisation of lattice structures processed by selective electron beam melting JF - Metals N2 - Metallic lattice structures intentionally contain open porosity; however, they can also contain unwanted closed porosity within the structural members. The entrained porosity and defects within three different geometries of Ti-6Al-4V lattices, fabricated by Selective Electron Beam Melting (SEBM), is assessed from X-ray computed tomography (CT) scans. The results suggest that horizontal struts that are built upon loose powder show particularly high (~20 x 10⁻³ vol %) levels of pores, as do nodes at which many (in our case 24) struts meet. On the other hand, for struts more closely aligned (0° to 54°) to the build direction, the fraction of porosity appears to be much lower (~0.17 x 10⁻³%) arising mainly from pores contained within the original atomised powder particles. KW - Cellular solids KW - Aqdditive manufacturing KW - Computed tomography KW - Titanium alloys PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-413689 UR - http://www.mdpi.com/2075-4701/7/8/300 DO - https://doi.org/10.3390/met7080300 SN - 2075-4701 VL - 7 IS - 8 SP - Article 300, 1 EP - 12 PB - MDPI AN - OPUS4-41368 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -