TY - CONF A1 - Heilmann, Maria T1 - Synthesis of Bimetallic Nickel Nanoparticles as Catalysts for the Sabatier Reaction N2 - Nanoparticles (NP) have become important materials for a variety of chemical technologies. The enhance surface-area-to-volume ratio of NPs is very high, making them excellent for use as catalyst, in analytical assays, and for antimicrobial applications. Nickel NPs have exhibited immense potential as important catalyst for the Sabatier reaction, i.e. converting waste to energy via transformation of CO2 into CH4, and could replace the rare earth elements such as Ru, PT, or Rh. In this work we describe the solvothermal synthesis of monometallic and bimetallic nickel nanoparticles. Monodisperse monometallic Ni nanoparticles were synthesized using Oleylamin as solvent and reducing agent. The nanoparticles were investigated using small angle scattering (SAXS), scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX), showing that the catalytically active sites are accessible. However, Ni has a high propensity to undergo oxidation, and becoming deactivated by coke formation. Hence, we further explore the preparation of bimetallic NPs, where a second metal is added to stabilize the Ni. Bimetallic Cu-Ni NPs were synthesized by simultaneous solvothermal reduction. These bimetallic NPs exhibit excellent catalytic properties are promising candidates to be used as catalysts for efficient energy storage. T2 - Joint Polish-German Crystallographic Meeting CY - Wroclaw, Poland DA - 24.02.2020 KW - Nanoparticles KW - Synthesis KW - Catalysis PY - 2020 AN - OPUS4-51663 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - May the force be with you - in situ investigation of mechanochemical reactions N2 - The past decade has seen a reawakening of solid-state to chemical synthesis, driven by the search for new, cleaner synthetic methodologies. Mechanochemistry has advanced to a widely applicable technique. T2 - SALSA's "Make and Measure 2019 CY - Berlin, Germany DA - 25.10.2019 KW - Mechanochemistry KW - Metal–organic frameworks PY - 2019 AN - OPUS4-50138 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Mechanochemistrry - a time resolved perspective on unconventional crystallization N2 - Green chemsistry apporoach for the synthesis of metal organic frameworks. T2 - IFW BAM Workshop CY - Berlin, Germany DA - 25.11.2019 KW - Mechanochemistry KW - XRD KW - Metal-organic-frameworks PY - 2019 AN - OPUS4-50110 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heilmann, Maria T1 - Synthesis of bimetallic nickel nanoparticles for catalysis N2 - We present the synthesis of monodisperse monometallic Ni nanoparticles (NPs) and bimetallic NiCu respectively NiCo NPs. The NPs were investigated using SAXS, STEM, EDX, and XANES, showing that the NPs are size tunable and stable while the surface is not entirely covered. Nickel NPs have exhibited immense potential as important catalyst for the Sabatier reaction, i.e. converting waste to energy via transformation of CO2 into CH4. T2 - 11th Joint BER II and BESSY II User Meeting CY - Berlin, Germany DA - 04.12.2019 KW - Nanoparticles KW - Catalysis KW - Synthesis PY - 2019 AN - OPUS4-50172 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kulow, Anicó T1 - X-ray fluorescence imaging with coded apertures N2 - Our aim is to develop a new simple and inexpensive method for full field X-ray fluorescence imaging . We combine an energy dispersive array detector with a coded aperture to obtain high resolution images . To obtain the information from the recorded image a reconstruction step is necessary . The reconstruction methods we have developed , were tested on simulated data and then applied to experimental data . The first tests were carried out at the BAM line @ BESSY II. This method enables the simultaneous detection of multiple elements , which is important e.g. in the field of catalysis. T2 - Adlershofer Forschungsforum CY - Berlin, Germany DA - 11.11.2019 KW - X-ray KW - Fluorescence KW - Imaging KW - Spectroscopy KW - Coded aperture PY - 2019 AN - OPUS4-49695 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kulow, Anicó T1 - Full field X-ray fluorescence imaging with coded apertures N2 - Our aim is to develop a new simple and inexpensive method for full field X-ray fluorescence imaging. We combine an energy-dispersive array detector with a coded aperture. To obtain the information from the recorded image, a reconstruction step is necessary. First tests were carried out at the BAMline at BESSY II. This method enables the simultaneous detection of multiple elements, which is important e.g. in the field of catalysis. T2 - BESSY Usermeeting CY - Berlin, Germany DA - 05.12.2019 KW - X-ray KW - Fluorescence KW - Imaging KW - Coded Apertures PY - 2019 AN - OPUS4-49964 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Altmann, Korinna A1 - Braun, U. A1 - Herper, D. A1 - Knefel, M. A1 - Bednarz, M. A1 - Bannick, C.-G. T1 - Smart filters for the analysis of microplastic in beverages filled in plastic bottles N2 - The occurrence of microplastic (MP) in food products, such as beverages in plastic bottles, is of high public concern. Existing analytical methods focus on the determination of particle numbers, requiring elaborate sampling tools, laboratory infrastructure and generally time-consuming imaging detection methods. A comprehensive routine analysis of MP in food products is still not possible. In the present work, we present the development of a smart filter crucible as sampling and detection tool. After filtration and drying of the filtered-off solids, a direct determination of the MP mass content from the crucible sample can be done by thermal extraction desorption gas chromatography mass spectroscopy (TED-GC/MS). The new filter crucible allows a filtration of MP down to particle sizes of 5 µm. We determined MP contents below 0.01 µg/L up to 2 µg/L, depending on beverages bottle type. This may be directly related to the bottle type, especially the quality of the plastic material of the screw cap. Dependent on the plastic material, particle formation increases due to opening and closing operations during the use phase. However, we have also found that some individual determinations of samples were subjected to high errors due to random events. A conclusive quantitative evaluation of the products is therefore not possible at present. KW - Microplastic KW - TED-GC/MS KW - Plastic bottles KW - Bbeverages KW - Filter crucible PY - 2021 DO - https://doi.org/10.1080/19440049.2021.1889042 SN - 1944-0057 VL - 38 IS - 4 SP - 691 EP - 700 PB - Taylor & Francis AN - OPUS4-52323 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Repräsentative Untersuchungsstrategien für ein integratives Systemverständnis von spezifischen Einträgen von Kunststoffen in die Umwelt (RUSEKU) N2 - Der Vortrag wurde im Rahmen der Abschlusskonferenz des Forschungsschwerpunktes "Plastik in der Umwelt" des BMBF gehalten. Er fasst die Ergebnisse des Verbundprojektes RUSEKU zusammen. Es wurde die Herstellung verschiedener Testmaterialien für die Mikroplastik (MP) Analytik beschrieben. Im weiteren geht es um verschiedene Ansätze MP kostengünstig und schnell zu detektieren, z.B. mit Nahinfrarotspektroskopie. Nanoplastik konnte mit der Transmissionselektronenmikroskopie sichtbar gemacht werden. Für die praxisnahe Beprobung von Gewässern wurde die Fraktionierte Filtration entwickelt. Integrale Beprobungen können mit dem Sedimentationskasten erfolgen. Als Beispiele für die Beprobung realer Gewässer wurde das urbane Abwassersystem Kaiserslautern, Getränkewasser und Waschmaschinenwasser gezeigt. T2 - Abschlusskonferenz des Forschungsschwerpunktes "Plastik in der Umwelt" des BMBF CY - Online meeting DA - 20.04.2021 KW - Mikroplastik KW - TED-GC/MS KW - Probennahme KW - RUSEKU PY - 2021 AN - OPUS4-52546 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Eisentraut, Paul T1 - Fast quantitative detection of microplastics using TED-GC/MS, an innovative thermoanalytical method N2 - Im Vortrag wird die BAM vorgestellt und die Motivation für Engagement im Feld der Mikroplastikanalysen dargelegt. Die Herausforderungen bei der Analyse werden aufgezeigt und der Umgang mit ihnen. Das Arbeitsprinzip der TED-GC/MS sowie Leistungsparameter werden erläutert sowie das Vorgehen zur Identifikation und Quantifizierung von Polymeren in er Umwelt. An ausgewählten Beispielen werden interessante Ergebnisse präsentiert und die Mikroplastikreferenzmaterialien der BAM vorgestellt. N2 - In the talk, the BAM is introduced and the motivation for our engagement in the field of microplastic analysis is explained. The challenges in the analysis of microplastics are shown and how we deal with them. The working principle of TED-GC/MS and its performance parameters are presented, as well as the procedure for identifying and quantifying polymers in environmental samples. Interesting results are shown using selected examples. Finally, BAM's microplastic reference materials are highlighted. T2 - National Environmental Monitoring Conference CY - Online meeting DA - 02.08.2021 KW - Microplastic KW - TED-GC/MS KW - Environmental analysis PY - 2021 AN - OPUS4-53081 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna A1 - Hodoroaba, Vasile-Dan T1 - CUSP inter-laboratory comparisons N2 - In this breakout session first, an introduction is given on the planning and organisation of an inter-laboratory comparison (ILC) under the pre-standardisation plattform VAMAS within the newly formed technical working area TWA 45 Micro and Nano Plastics in the Environment. An update with the ILCs on micro- and nanoplastic performed so far is also given. In the third part, the requirements for a reference materials are presented. The needs from the different H2020 micro- and nanoplastic projects are collected and compiled in an ILC matrix for joint activities as the next steps. T2 - The European Research Cluster to Understand the Health Impact of Micro- and Nanoplastics (CUSP) Launching Event CY - Online meeting DA - 10.06.2021 KW - Microplastic KW - Nanoplastic KW - Inter-laboratory comparison KW - VAMAS KW - Reference material PY - 2021 AN - OPUS4-52808 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Mikroplastik an der BAM: TED-GC/MS und Referenzmaterialien N2 - Thema ist die Funktionsweise der TED-GC/MS als Methode für die Mikroplastik-Detektion sowie die Herstellung dazugehöriger Referenzmaterialien an der BAM T2 - 25. Kolloquium Massenspektrometrie von Polymeren CY - Online meeting DA - 17.06.2021 KW - Mikroplastik KW - TED-GC/MS KW - Referenzmaterial PY - 2021 AN - OPUS4-52835 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Dittmann, Daniel T1 - Aktivkohle-Charakterisierung als weiterer Schlüssel für das Verständnis der Spurenstoffadsorption in der 4. Reinigungsstufe N2 - Aktivkohle ≠ Aktivkohle, Adäquate Materialcharakterisierung - Voraussetzung für Adsorptionsprognosen und Wasserspezifische Auswahl von Aktivkohleprodukten. Ausblick: Publikationen zu Aktivkohlecharakterisierung und Adsorptionsprognose in Vorbereitung T2 - Wasser 2021 - Jahrestagung der Wasserchemischen Gesellschaft CY - Online meeting DA - 10.05.2021 KW - Aktivkohle KW - Thermogravimetrie KW - Zersetzungsgasanalyse KW - Proximatanalyse PY - 2021 AN - OPUS4-52742 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Braun, U. T1 - Detection of plastics in soil N2 - Soil acts as a final sink for pollutants. Microplastics from different sources such as plastic mulching, littering, compost, sewage sludge, sedimentary deposition, and tyre abrasion are expected to be found in soil. However, representative and comprehensive information is missing on the sources, transport, and fate. Therefore, a reliable analysis method for microplastics in soils needs to be developed. The presented work describes the development of a procedure for microplastics analysis in soils. A representative sampling based on the on-site conditions and a sample preparation method was established and comprised of a drying step, the separation of microplastic particles > 1 mm, and a density separation for particles < 1 mm. The detection of the large microplastic particles (> 1 mm) was conducted with Attenuated Total Reflection - Fourier Transform infrared Spectroscopy (ATR-FTIR) , while Thermal Extraction Desorption - Gas Chromatography / Mass Spectrometry (TED-GC/MS) was applied for particles < 1 mm, gaining information on the type of polymer and mass fraction. Based on the established method, 14 environmental soil samples ? with different exposure of microplastics from agriculture, industrial sites, roads, and floods were investigated. Due to the arbitrary microplastic particle distribution among the samples for large microplastics, it was reasoned that the found particles were unrepresentative. In contrast, microplastic particles < 1 mm were discovered in a high mass in soil samples exposed to plastic mulching or fertilization with sewage sludge or compost (0 – 115 mg/kg). On average, microplastic contents detected in soil samples taken from a construction site and an inner-city lake were higher (13 – 238 mg/kg). As expected, microplastic content in soil sampled in proximity to roads was more pronounced in the upper soil layers. In contrast, very remote sampling sites, expectably uncontaminated, did not lead to the detection of microplastic regarding to thermoanalytical detection method. In a proof of concept experiment several in vivo and in vitro ecotoxicological tests were applied to evaluate the effect of microplastics (tyre abrasion, polystyrene containing hexabromocyclododecane) in natural soils. In summary, while no effects of the examined probes could be detected on higher levels of biological organization after exposures to earthworm E. andrei, significant changes in several oxidative stress related biomarkers were observed. T2 - SETAC Europe 2022 CY - Kopenhagen, Denmark DA - 15.05.2022 KW - Microplastic KW - TED-GC/MS KW - Soil PY - 2022 AN - OPUS4-55872 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Harmonisation efforts of the CUSP projects N2 - The talk is about harmonisation approaches within CUSP. First the five H2020 projects for research on risk assessment regarding microplastics topic were presented. Secondly, harmonisation process were discussed. T2 - VAMAS SC 47 Meeting CY - Turin, Italy DA - 19.10.2022 KW - Microplastics KW - Harmonisation KW - Nanoplastics KW - H2020 KW - Risk assessment PY - 2022 AN - OPUS4-56077 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mönch, Bettina A1 - Kraus, Werner A1 - Köppen, Robert A1 - Emmerling, Franziska T1 - The different conformations and crystal structures of dihydroergocristine N2 - The identification of different forms of dihydroergocristine (DHEC) was carried out by crystallization from different organic solvents. DHEC was identified as potential template for molecularly imprinted polymers (MIPs) for the epimeric specific analysis of ergot alkaloids (EAs) in food. DHEC was crystallized from different solvents in order to mimic the typical MIP synthesis conditions. Four new solvatomorphs of DHEC were obtained. All solvatomorphs contain a water molecule in the crystal structure, whereas three compounds contain an additional solvent molecule. Based on the conformation of DHEC a comparison with typical EA molecules was possible. The analysis showed that DHEC is a suitable template for MIPs for EAs. PY - 2016 DO - https://doi.org/10.1016/j.molstruc.2015.10.008 SN - 0022-2860 SN - 1872-8014 SN - 0377-046X VL - 1105 SP - 389 EP - 395 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-35009 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stroh, Julia A1 - Schlegel, Moritz-Caspar A1 - Schmidt, Wolfram A1 - Nguyen, Thi Yen A1 - Meng, Birgit A1 - Emmerling, Franziska T1 - Time-resolved in situ investigation of Portland cement hydration influenced by chemical admixtures N2 - Numerous admixtures are used in the building practice to customize the properties of the cement paste during application. The influences of admixtures on the course of cement hydration and formation of hydrate phases have to be considered. Polycarboxylate ether (PCE) based polymeric superplasticizers (SPs) are known to retard the setting of the cement paste. The extent of the retardation differs depending on the molecular structure of the SP. Additionally, the presence of a stabilizing agent (SA) in the cement paste has a retarding side effect on the setting. The initial cement hydration processes and the detailed mechanisms of the retardation influenced by PCEs, as well as their interactions with particular SAs, are insufficiently understood. Up to now, only the results of phenomenological studies were taken into account to describe this retardation process. A detailed structure analysis monitoring the change of the phase composition during the hydration was never applied. Both SP and SA affect the adsorption of the sulphate ions on the clinker particles, causing changes in the formation of ettringite during the initial hydration, and are therefore a crucial part of the setting process itself. Here, the initial hydration of cement influenced by the interaction of SP and SA was monitored in situ by synchrotron X-ray diffraction. The high time resolution of the measurements allowed a continuous detection of the hydrates formed. The hydration was followed from the starting point of water addition and for couple of hours afterwards. The hydration of the levitated cement pellets containing starch as SA was initialized by adding aqueous solutions of different commercial SPs. Changes in the ettringite formation were detected in comparison to the reference hydration of pure cement. KW - Synchrotron KW - Portland cement Initial hydration KW - Superplasticizer KW - Stabilizer KW - XRD PY - 2016 DO - https://doi.org/http://dx.doi.org/10.1016/j.conbuildmat.2015.12.097 IS - 106 SP - 18 EP - 26 PB - Elsevier AN - OPUS4-35467 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - de Oliveira Guilherme Buzanich, Ana A1 - Radtke, Martin A1 - Reinholz, Uwe A1 - Riesemeier, Heinrich A1 - Emmerling, Franziska ED - de Oliveira Guilherme Buzanich, Ana T1 - Time- and spatial-resolved X-ray absorption fine structure (XAFS) spectroscopy in a single-shot: new analytical possibilities for in situ material characterization N2 - A new concept that comprises both time- and lateral-resolved X-ray absorption fine-structure information simultaneously in a single shot is presented. This uncomplicated set-up was tested at the BAMline at BESSY-II (Berlin, Germany). The primary broadband beam was generated by a double multilayer monochromator. The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by either an energy-sensitive area detector, the so-called color X-ray camera, or by an area-sensitive detector based on a CCD camera, in θ-2θ geometry. The first tests were performed with thin metal foils and some iron oxide mixtures. A time resolution of lower than 1 s together with a spatial resolution in one dimension of at least 50 µm is achieved. KW - Single-shot XAFS KW - Time resolution KW - Spatial resolution KW - Divergent XAFS PY - 2016 DO - https://doi.org/10.1107/S1600577516003969 SN - 1600-5775 VL - 23 SP - 769 EP - 776 PB - International Union of Crystallography AN - OPUS4-38370 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - In situ analysis of mechanochemical reactions using combined X-ray diffraction and Raman spectroscopy N2 - Mechanochemistry is increasingly used for synthesizing various materials including metal organic compounds and cocrystals. Although this synthesis approach offers a fast and pure synthesis in high yields, there is a lack in understanding the mechanisms of milling reactions. The necessary data can only be obtained in in situ experiments, which were only recently established for milling reactions. Herein, we present a novel setup enabling a combined in situ investigation of mechanochemical reactions using synchrotron XRD and Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. Besides well-known MOFs like ZIF-8, the formation process of new metal phosphonates and model cocrystals could be studied in detail. The syntheses pathway of the different compounds could be revealed. The results prove that the presented method combination is applicable for a wide range of materials and will provide the necessary understanding to tune and optimize mechanochemically synthesized compounds. T2 - 3oth Meeting of the European Crystallographic Association CY - Basel, Switzerland DA - 28.08.2016 KW - Mechanochemistry KW - In situ PY - 2016 AN - OPUS4-38363 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Nguyen, Thi Yen T1 - Direct evidence of polyamorphism in paracetamol N2 - While polymorphism is a common phenomenon in the crystallization processes of organic compounds, polyamorphism has gained importance only recently. Using sophisticated sample environments and applying in situ scattering methods and vibrational spectroscopy, the complete crystallization process of organic compounds from solution can be traced and characterized. Diffuse scattering from amorphous intermediates can be investigated by analyzing the atomic pair Distribution function (PDF) to gain further insights into molecular pre-orientation. The crystallization behavior of Paracetamol was studied exemplarily under defined, surface-free conditions. Based on the choice of the solvent, the formation of different polymorphs is promoted. The thermodynamically stable form I and the metastable orthorhombic form II could be isolated in pure form directly from solution. For both polymorphs, the crystallization from solution proceeds via a distinct amorphous precursor phase. PDF analyses of these different amorphous states indicate a specific pre-orientation of the analyte molecules introduced by the solvent. The resulting crystalline polymorph is already imprinted in these proto-crystalline precursors. Direct experimental evidence for the polyamorphism of paracetamol is provided. T2 - Annual CM1402 crystallize COST meeting CY - Coimbra, Portugal DA - 06.04.2016 KW - Paracetamol KW - Crystallization KW - In situ analysis KW - Active pharmaceutical ingredient (API) PY - 2016 AN - OPUS4-35873 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Fischer, Franziska T1 - Polymorphism of mechanochemically synthesized Cocrystals: an in situ study N2 - In situ investigations using PXRD coupled with Raman spectroscopy permit the evaluation of the formation pathways of milling reactions. The liquid-assisted grinding cocrystallisation of theophylline with benzamide leading to polymorphic compounds was investigated. The dipole moment of the solvent used in the synthesis determines the structure of the polymorphic product. A detailed investigation allows determining the kinetically and thermodynamically favored product. In situ observations of the formation pathway during the grinding process of both polymorphs show that the thermodynamically favored cocrystal is formed in a two-step mechanism with the kinetic cocrystal as intermediate. The evaluation of the mechanochemical formation pathways reveals the importance of in situ investigations for an in depth understanding of mechanochemical synthesis mechanisms. Our study demonstrates that the choice of the solvent in the LAG synthesis is decisive for the controlled formation of a desired polymorphic final product. T2 - CGOM/ BACG 47th Annual British Association of Crystal Growth Conference CY - Leeds, UK DA - 28.06.2016 KW - Cocrystal KW - Mechanochemistry KW - Milling PY - 2016 AN - OPUS4-36764 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Emmerling, Franziska A1 - Tumanov, N. A1 - Tumanova, N. A1 - Fischer, Franziska A1 - Morelle, F. A1 - Ban, V. A1 - Robeyns, K. A1 - Filinchuk, Y. A1 - Wouters, J. A1 - Leyssens, T. T1 - Exploring polymorphism and stoichiometric diversity in naproxen/proline cocrystals N2 - We present naproxen/proline cocrystals discovered when combining enantiopure and racemic naproxen and proline. Using liquid-assisted grinding as the main method to explore the variety of crystal forms in this system, we found 17 cocrystals, of which the structures of only four of them were previously known. The naproxen/proline system exhibited multiple polymorphs of 1 : 1 stoichiometry as well as more rare cocrystals with 1 : 2 and 2 : 3 stoichiometries, two cocrystal hydrates and one cocrystal solvate. In situ ballmilling, used to monitor liquid-assisted grinding reactions, revealed that the solvent dictates the reaction intermediates even if the final reaction product stays the same. Synchrotron X-ray diffraction data collected in situ upon heating allowed us to monitor directly the phase changes upon heating and gave access to pure diffraction patterns of several cocrystals, thus enabling their structure determination from powder X-ray diffraction data; this method also confirmed the formation of a conglomerate in the RS-naproxen/DL-proline system. Proline in cocrystals kept its ability to form charge-assisted head-to-tail N-H⋯O hydrogen bonds, typical of pure crystalline amino acids, thus increasing the percentage of strong chargeassisted interactions in the structure and consequently providing some of the cocrystals with higher melting points as compared to pure naproxen. The majority of drugs are chiral, and hence, these data are of importance to the pharmaceutical industry as they provide insight into the challenges of chiral cocrystallization. KW - In situ KW - Mechanochemistry KW - XRD PY - 2018 UR - https://pubs.rsc.org/en/Content/ArticleLanding/CE/2018/C8CE01338A#!divAbstract DO - https://doi.org/10.1039/c8ce01338a SN - 1466-8033 VL - 20 IS - 45 SP - 7308 EP - 7321 PB - Royal Society of Chemistry CY - London AN - OPUS4-46913 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Panne, Ulrich T1 - "Keine Dienstmagd" - Analytical Sciences in Action N2 - Analytical Sciences has developed from Ostwald’s “unentbehrlichen Dienstmagd” to a chemical discipline at the core of many of today’s fundamental and applied scientific problems and innovations. An atomic or molecular understanding of basic processes in chemistry, soft matter physics, materials and life science is enabled only through new analytical methods and instrumentation. Similar observations can be found for pressing sociopolitical conflicts of the future: A rational discussion of global climate change or new energy sources is only possible with reliable analytical results. Progress in Analytical Sciences is only possible if the underlying interdisciplinary character is acknowledged and valued. The talk will illustrate the scope of modern Analytical Science through examples from process analysis relevant to modern process intensification and industry 4.0 to bioanalysis and the use of synchrotron radiation to elucidate fundamental reactions materials. T2 - MChG Talk CY - Technische Universität München, Germany DA - 27.11.2018 KW - Analytical Sciences PY - 2018 AN - OPUS4-46940 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Mechanistic investigations of mechanosyntheses N2 - Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic, metal-organic, and inorganic compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms often remain unclear. In the last years, we have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy. A further development is the in situ coupling of synchrotron XRD, Raman spectroscopy, and thermography allowing the observation of mechanochemical reactions in real time. [5] Information on the crystalline, molecular, and temperature state of the materials during grinding could be collected. The chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. Furthermore, the presented setup allows the detection of crystalline, amorphous, eutectic as well as liquid intermediates. Based on these data, metastable polymorphs of cocrystals and coordination polymorphs could be isolated and struc-turally characterized. A multi-step diffusion mechanism was identified for most systems. Crystalline phases were obtained intermediately, suggesting that the synthesis is following Ostwald’s rules of stages. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses. T2 - Beilstein Symposium MECHANOCHEMISTRY: MICROSCOPIC AND MACROSCOPIC ASPECTS CY - Rüdesheim, Germany DA - 13.11.2018 KW - Mechanochemistry KW - Phosphonates KW - In situ PY - 2018 AN - OPUS4-46758 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Chapartegui, Ander T1 - MOFs as optical sensor elements against endocrine disrupting phthalates N2 - The development of optical sensing technologies for Endocrine Disrupting Chemicals (EDCs) was urgently needed to facilitate currently unmet demands on comprehensive monitoring of These substances, thus ensuring consumer safety. T2 - SALSA CY - Berlin, Germany DA - 01.05.2018 KW - MOF KW - Short chained phthalates PY - 2018 AN - OPUS4-46889 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Breitfeld, Steffen T1 - BaF-Coordination polymers: Mechanochemical syntheses of new coordination polymers with a direct Ba-F bond N2 - Metal organic frameworks (MOFs) and coordination polymers (CPs) Play an important role in different fields of applications like e.g. catalysis, separations, gas storages, sensors or optoelectronics. Moreover, particularly fluorinated metal-organic frameworks (FMOFs) are in the focus of interest during the last years. Due to the strong electronegativity of fluorine the FMOFs show beside an enhanced thermal stability excellent optical and electrical properties compared to non-fluorinated frameworks. In most cases fluorine is implemented using perfluorinated organic linkers at the synthesis, usually performed by solvothermal synthesis. However, only few examples are known so far where fluorine is coordinated directly to the metal cation. Recently we reported about successful mechanochemical syntheses and characterization of fluorine-containing coordination polymers of alkaline earth metals by milling M(OH)2 (M: Ca, Sr, Ba) with fluorinated benzene dicarboxylic acids. In the present study, it was shown that it is possible to connect fluorine directly to Barium using a mechanochemical synthesis route. A new phase pure barium coordination polymer, BaF-benzene-dicarboxylate (BaF(p-BDC)0.5), was synthesized by milling starting either from barium hydroxide or from barium acetate as sources for barium cations. In both cases the second reactant was 1,4-benzenedicarboxylic acid (H2(p-BDC)). Ammonium fluoride was used as fluorinating agent directly at milling. Although single crystals are not accessible so far and the structure was not solved yet, both the 19F MAS NMR spectrum and the FT IR spectrum give strong evidence that fluorine as well as 1,4-benzenedicarboxylate are connected to barium. This is the first mechanochemical synthesis of coordination polymers where fluorine is directly coordinated to the metal cation. The new compound BaF(p-BDC)0.5 was characterized by X-ray powder diffraction, FT IR- and 19F, 1H-13C CP MAS NMR spectroscopies, DTA-TG and elemental analysis. T2 - Konferenz CY - Oberjoch, Germany DA - 22.07.20108 KW - Mechanochemical syntheses KW - Coordination polymers KW - Direct fluorine-metal bond KW - Alkaline earth metal PY - 2018 AN - OPUS4-46897 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Chapartegui, Ander T1 - Metal-Organic Frameworks as turn on fluorescent optical sensors against endocrine disrupting phthalate plasticizers N2 - The development of quick and simple optical sensing technologies for Endocrine Disrupting Chemicals (EDCs) is needed to facilitate monitoring of these substances to ensure consumer safety. Optical sensing was achieved against phthalates acting as EDC that have host guest interaction with an intercalated Metal-organic framework (MOF), resulting in a fluorescence emission upon excitation. The fluorescent turn-on signal was generated by using a fluorophore with a structural component that has little fluorescence unless excimers are formed. Strategies to engineer functional MOF structures suitable for sensing EDC phthalates were developed, and the characterization of the MOFs with and without present phthalates was done by single crystal XRD, PXRD, RAMAN and Thermogravimetry. Extensive photo-physical characterization of host-guest complexes of different phthalates and the MOF as well as the resulting exciplex fluorescence was performed. Photo physical characterization revealed an analyte specific fluorescence fingerprint that allows discerning even minute changes in chemical structures of the analyte and therefore paving the way for sensing tools in real world analytical applications. The presented capability of MOFs to sense EDCs is envisioned to complement established methods from analytical chemistry such as mass spectrometry based methods which can’t be used on site and are often associated with infrastructural capacity constraints T2 - EURoptrode CY - Naples, Italy DA - 25.03.2018 KW - MOF KW - Short chained Phthalates PY - 2018 AN - OPUS4-46890 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - New insights in mechanochemical processes using real-time in situ investigations N2 - Mechanochemistry is increasingly used for synthesizing various materials including metal organic compounds and cocrystals. Although this synthesis approach offers a fast and pure synthesis in high yields, there is a lack in understanding the mechanisms of milling reactions. The necessary data can only be obtained in in situ experiments, which were only recently established for milling reactions. Herein, we present a novel setup enabling a combined in situ investigation of mechanochemical reactions using synchrotron XRD and Raman spectroscopy. T2 - ECM31 CY - Oviedo, Spain DA - 18.08.2018 KW - Mechanochemistry KW - In situ PY - 2018 AN - OPUS4-46990 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Breitfeld, Steffen T1 - High energy ball milling of a new representative of coordination polymers without organofluorine linkers N2 - Metal organic frameworks and coordination polymers play an important role in different fields of applications. Moreover, particularly fluorinated metal-organic frameworks (FMOFs) are in the focus of interest during the last years. In most cases, fluorine is implemented using perfluorinated organic linkers at the synthesis, usually performed by solvothermal synthesis. However, only few examples are known so far where fluorine is coordinated directly to the metal cation. Recently, we reported about mechanochemical syntheses and characterization of fluorine-containing coordination polymers of alkaline earth metals by milling M(OH) (M: Ca, Sr, Ba) with fluorinated benzene dicarboxylic acids 2 and we reported about mechanochemical syntheses of alkaline earth metal fluorides with ammonium fluoride. Now we are reporting about a combination of both synthesis routes. That is the first mechanochemical synthesis of coordination polymers where fluorine is coordinated directly to the metal cation. T2 - Konferenz CY - Berlin, Germany DA - 30.11.2017 KW - Metal organic frameworks KW - Coordination polymer KW - Mechanochemical syntheses KW - Direct fluorine-metal bond KW - Alkaline earth metal PY - 2017 AN - OPUS4-46898 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - THES A1 - Kazlagić, Anera T1 - Provenancing of cement by the means of isotope techniques N2 - Concrete is the most important human-made material because it serves as the basis of our built environment. Since the properties of concretes are dominated by their key compound, cement, devising a way to determine the cement’s origin, known as provenancing, is of great importance for answering different provenance-related questions. These questions range from liability issues when damage occurs to concrete-made structures, to forensic investigations where cement particles are found at crime scenes. This thesis showcases the use of isotope techniques to answer these provenance-related questions. Conventional 87Sr/86Sr and 143Nd/144Nd isotope and elemental ratios consisting of Ca, Sr, K, Mn, Mg, and Ti are used as fingerprints for ordinary Portland cement (OPC) provenancing. The first part of this thesis describes research previously conducted in fingerprinting cementitious materials, providing an overview of provenance studies of cement and the main approaches commonly used. In several studies, the origin of clinker for certain locations was determined via different approaches. However, clinker is an intermediate product, which is available only at the production site and therefore, the practical relevance is rather limited. Furthermore, the use of Sr and Nd isotope systems, together with elemental fingerprints are presented as state of the art in the field. Therein, the principal approach for the overall study is sketched. For the second part of the study, a sample preparation technique for Sr isotopes in Portland cement was developed. The aim was to find the most appropriate sample preparation procedure for cement provenancing and selection was realised by comparing the 87Sr/86Sr isotope ratios of differently treated OPCs with those of the corresponding clinkers. Based on these findings, the third part of the study focused on the measurements of Sr and Nd isotope ratios, together with elemental ratios, to establish a reliable technique for OPC provenancing. The outcomes of this final stage are then used to establish a procedure for fingerprinting cements. This becomes possible with the use of Sr and Nd isotope ratios and geochemical profiles. To perform isotope ratio measurements and obtain reliable data, it was necessary to establish a quality control procedure. Thus, an interlaboratory comparison (ILC) was organised to characterise 87Sr/86Sr isotope ratios in geological and industrial reference materials by applying the conventional method for 87Sr/86Sr isotope ratios. As reference material, four cements (VDZ 100a, VDZ 200a, VDZ 300a, IAG OPC-1), one limestone (IAG/CGL ML-3) and one slate (IAG OU-6) were selected, thus covering a wide range of Sr isotope signatures. KW - Isotope ratio KW - Strontium KW - Neodymium KW - Ordinary Portland cement PY - 2023 SP - 1 EP - 148 CY - Berlin AN - OPUS4-59172 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kohlbrecher, J. A1 - Breßler, Ingo T1 - Updates in SASfit for fitting analytical expressions and numerical models to small-angle scattering patterns N2 - Small-angle scattering is an increasingly common method for characterizing particle ensembles in a wide variety of sample types and for diverse areas of application. SASfit has been one of the most comprehensive and flexible curve-fitting programs for decades, with many specialized tools for various fields. Here, a selection of enhancements and additions to the SASfit program are presented that may be of great benefit to interested and advanced users alike: (a) further development of the technical basis of the program, such as new numerical algorithms currently in use, a continuous integration practice for automated building and packaging of the software, and upgrades on the plug-in system for easier adoption by third-party developers; (b) a selection of new form factors for anisotropic scattering patterns and updates to existing form factors to account for multiple scattering effects; (c) a new type of a very flexible distribution called metalog [Keelin (2016). Decis. Anal. 13, 243–277], and regularization techniques such as the expectation-maximization method [Dempster et al. (1977). J. R. Stat. Soc. Ser. B (Methodological), 39, 1–22; Richardson (1972) J. Opt. Soc. Am. 62, 55; Lucy (1974). Astron. J. 79, 745; Lucy (1994). Astron. Astrophys. 289, 983–994], which is compared with fits of analytical size distributions via the non-linear least-squares method; and (d) new structure factors, especially for ordered nano- and meso-scaled material systems, as well as the Ornstein–Zernike solver for numerical determination of particle interactions and the resulting structure factor when no analytical solution is available, with the aim of incorporating its effects into the small-angle scattering intensity model used for fitting with SASfit. KW - Small-angle scattering KW - Numerical models KW - Structure factors KW - Regularization KW - SAXS KW - SANS PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565069 DO - https://doi.org/10.1107/S1600576722009037 SN - 0021-8898 SN - 1600-5767 VL - 55 IS - 6 SP - 1677 EP - 1688 PB - Wiley-Blackwell CY - Oxford AN - OPUS4-56506 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Pauw, Brian Richard T1 - McSAS3: live demo of a Monte Carlo data analyis package for scattering studies N2 - McSAS3 is a refactored software package for fitting large batches of (X-ray or Neutron) scattering data. It uses a Monte-Carlo acceptance-rejection algorithm to optimize model parameters - ideal for analysis of size-disperse scatterers. The refactored code can exploit multiprocessing, traceably stores (multiple) results in the output file, and allows for re-histogramming of previous optimizations. Besides analysis of large batches, it can also be integrated in automated data processing pipelines. The live demonstration will show how to use the software, what its limitations are, and what outcomes can look like for batches of results. T2 - SAS Analysis Course 2023 CY - Didcot, UK DA - 05.06.2023 KW - Scattering KW - Software KW - Analysis KW - Demonstration KW - McSAS3 KW - MOUSE KW - Monte Carlo KW - Automated analysis PY - 2023 AN - OPUS4-57630 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Engelhard, Carsten T1 - Advances in Analytical Chemistry and Mass Spectrometry to Support a Sustainable and Circular Economy N2 - Recent advances in analytical chemistry have significantly supported efforts to realize a sustainable circular economy and circular chemistry. By enabling rapid materials analysis and characterization of materials transformation throughout their life cycle, analytical methods are playing a key role in supporting waste reduction, resource recovery, pollution monitoring, and sustainable manufacturing. In this presentation, recent developments in analytical chemistry and analytical instrumentation to support a sustainable and circular economy will be reviewed and selected contributions from our laboratories will be discussed. For example, high-resolution mass spectrometry combined with chromatography is an indispensable tool for the identification and characterization of plastics. To support the transition from linear to circular chemistry, whichs prioritizes reuse, recycling, and resource efficiency, accurate and detailed chemical information about plastic materials is essential. Here, targeted and non-targeted screening approaches help to characterize, for example, the quality and safety of recycled plastics. In addition, green analytical chemistry has emerged as a topic of interest, emphasizing the use of solvent-free and low-energy methods to minimized environmental impact during analysis. Here, ambient desorption/ionization high-resoluton mass spectrometry (ADI-MS) is considered a very attractive tool because it dos not require chromatography or large amounts of solvent, reduces sample preparation time, and produces virtually no chemical waste. Here, a solvent-free, plasma-based ADI-MS method is presented, which was carefuly developed for the direct identification and fast screening of per- and polyfluoroalkyl substances (PFAS). PFAS are a large class of thousands of synthetic chemicals that are used worldwide. However, growing environmental and human health concerns in the last two decades have led to more stringent regulatory requirements and the development of quantitative analytical methods for PFAS detection. Today, standardized and powerful methods exist, e.g., for the determination PFAS in water, sludge, compost, soil, and drinking water. While liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) is often used, sample preparation, solvent consumption, and total analysis times can be challenging. Here, ADI-MS is considered interesting, because it requires only minimal sample preparation and little solvent consumption. In this work, a plasma-based pin-to-capillary flowing atmospheric-pressure afterglow source (FAPA) is used for the direct desorption/ionization of PFAS from thin-layer chromatography (TLC) plates. Selected PFAS samples were directly probed on functionalized TLC surfaces without a preceding planar chromatography step. In addition, direct analysis of PFAS mixtures and selected matrices was performed with little solvent consumption, no sample preparation and short analysis time. T2 - XXII European Conference on Analytical Chemistry (EUROANALYSIS) CY - Barcelona, Spain DA - 31.08.2025 KW - Mass Spectrometry KW - Extractables & Leachables KW - Non-Targeted Analysis KW - PFAS KW - FAPA-MS PY - 2025 AN - OPUS4-65275 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Badde, Aurelia A1 - Illerhaus, Bernhard T1 - Three dimensional computerized microtomography in the analysis of sculpture N2 - The Alte Nationalgalerie, Staatliche Museen zu Berlin (SMB) and the Federal Institute for Materials Research and Testing (BAM) tested the accomplishment of the three dimensional computerized microtomography (3D-µCT) - a new flat panel detector computerized tomography (CT) system at the BAM with extended energy range, with high voltage X-ray tubes (330 and 225 kV), with micrometer focal spot size and micrometer resolution and enlarged object size (up to 70 cm diameter) - for examining plaster statues. The high spatial and density resolution of the tomograph enable detailed insights into the individual work processes of the investigated cast plaster statues. While initiated in support of the conservation process, computed tomography (CT) analysis has assisted in revealing relative chronologies within the series of the cast works of art, thus serving as a valuable tool in the art-historical appraisal of the oeuvres. The image-processing systems visualize the voids and cracks within and the cuts through the original cast works. Internal structures, armoring, sculptural reworking as well as restorative interventions are virtually reconstructed. The authors are currently employing the 3D-µCT systems at the BAM into the detection of defects in Carrara marble sculpture. Microcracks, fractures, and material flaws are visualized at spatial resolution down to 10 µm. Computerized reconstruction of ultrasound tomography is verified by analyzing correlations in the results obtained from the complementary application of these two non-destructive testing (NDT) methods of diagnosis. KW - Cast plaster statues KW - Three dimensional microtomography KW - Carrara marble sculpture KW - Condition assessment KW - Visualization KW - Internal structures KW - Material flaws KW - Ultrasound computed tomography KW - Correlation KW - Validation PY - 2008 DO - https://doi.org/10.1002/sca.20080 SN - 0161-0457 SN - 1932-8745 VL - 30 IS - 1 SP - 16 EP - 26 PB - Wiley CY - Hoboken, NJ AN - OPUS4-17578 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wachtendorf, Volker A1 - Geburtig, Anja T1 - Alterungseffekte bei Polymerwerkstoffen messen N2 - Bei der Auswahl von Werkstoffen spielt deren Alterung oft eine untergeordnete Rolle, stattdessen wird häufig der ungealterte Ausgangszustand optimiert. Materialien altern aber unterschiedlich. Der Effekt der molekularen Alterung spiegelt sich in den Eigenschaften mehr oder weniger stark und in unterschiedlichem zeitlichen Verlauf wider. Da es kein physikalisch-chemisches Modell dafür gibt, sind Alterungseffekte empirisch zu bestimmen. KW - Alterung KW - Polymerwerkstoff KW - Eigenschaftsänderung PY - 2012 DO - https://doi.org/10.1002/nadc.201290356 SN - 1439-9598 SN - 1521-3854 VL - 60 IS - 10 SP - 1018 EP - 1022 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-26666 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - PE-Rezyklat Einsatz in Gefahrgutbehältern? N2 - In diesem Vortrag geht es darum zu beschreiben, ob Rezyklat für PE Behälter gefüllt mit Gefahrgut Anwendung finden darf. Kanister aus Neuware und Rezyklat wurden verschiedenen Untersuchungen unterzogen. Es wurde der Feststoff und Leachable getestet. Methoden sind TED-GC/MS und GC-HRMS. Proben der Leachable wurden nach 1 und 4 Wochen genommen und die Peakanzahl vergleichen dargestellt. Als Lösemittel wurden Wasser, Ethanol, EtOAc, Ammoniak und HNO3 verwendet. T2 - Fachaustausch Projekt GeSKAR CY - Dessau, Germany DA - 10.01.2025 KW - Gefahrgutbehälter KW - Rezyklat PY - 2025 AN - OPUS4-62396 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Giesen, C. A1 - Müller, Larissa A1 - Panne, Ulrich A1 - Jakubowski, Norbert T1 - History of inductively coupled plasma mass spectrometry-based immunoassays N2 - The analysis of biomolecules requires highly sensitive and selective detection methods capable of tolerating a complex, biological matrix. First applications of biomolecule detection by ICP-MS relied on the use of heteroelements as a label for quantification. However, the combination of immunoassays and ICP-MS facilitates multiparametric analyses through elemental tagging, and provides a powerful alternative to common bioanalytical methods. This approach extends the detection of biomarkers in clinical diagnosis, and has the potential to provide a deeper understanding of the investigated biological system. The results might lead to the detection of diseases at an early stage, or guide treatment plans. Immunoassays are well accepted and established for diagnostic purposes, albeit ICP-MS is scarcely applied for the detection of immune-based assays. However, the screening of biomarkers demands high throughput and multiplex/multiparametric techniques, considering the variety of analytes to be queried. Finally, quantitative information on the expression level of biomarkers is highly desirable to identify abnormalities in a given organism. Thus, it is the aim of this review to introduce the fundamentals, and to discuss the enormous strength of ICP-MS for the detection of different immunoassays on the basis of selected applications, with a special focus on LA-ICP-MS. KW - ICP-MS KW - LA-ICP-MS KW - Immunoassay KW - Elemental tagging KW - Multiplexing PY - 2012 DO - https://doi.org/10.1016/j.sab.2012.06.009 SN - 0584-8547 SN - 0038-6987 N1 - Geburtsname von Müller, Larissa: Wäntig, L. - Birth name of Müller, Larissa: Wäntig, L. VL - 76 SP - 27 EP - 39 PB - Elsevier CY - Amsterdam AN - OPUS4-27686 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wawrzyn, Eliza A1 - Schartel, Bernhard A1 - Seefeldt, Henrik A1 - Karrasch, Andrea A1 - Jäger, Christian T1 - What reacts with what in bisphenol A polycarbonate/silicon rubber/bisphenol A bis(diphenyl phosphate) during pyrolysis and fire behavior? N2 - The pyrolysis and flame retardancy of a bisphenol A polycarbonate/silicon rubber/bisphenol A bis(diphenyl phosphate) (PC/SiR/BDP) blend were investigated and compared to those of PC/BDP and PC/SiR. The impact modifier SiR consists mainly of poly(dimethylsiloxane) (PDMS > 80 wt %). The pyrolysis of PC/SiR/BDP was studied by thermogravimetry (TG), TG–FTIR to analyze the evolved gases, and a Linkam hot stage cell within FTIR as well as 29Si NMR and 31P NMR to analyze the solid residue. The fire performance was determined by PCFC, LOI, UL 94, and a cone calorimeter under different external irradiations. The fire residues were studied by using ATR-FTIR as well as the additional binary systems PC + PDMS, PC + BDP, and BDP + PDMS, focusing on the specific chemical interactions. The decomposition pathways are revealed, focusing on the competing interaction between the components. Fire retardancy in PC/SiR/BDP is caused by both flame inhibition in the gas phase and inorganic-carbonaceous residue formation in the condensed phase. The PC/SiR/BDP does not work as well superimposing the PC/SiR and PC/BDP performances. PDMS reacts with PC and BDP, decreasing BDP's mode of action. Nevertheless, the flammability (LOI > 37%, UL 94 V-0) of PC/SiR/BDP equals the high level of PC/BDP. Indeed, SiR in PC/SiR/BDP is underlined as a promising impact modifier in flame-retarded PC/impact modifier blends as an alternative to highly flammable impact modifiers such as acrylonitrile–butadiene–styrene (ABS), taking into account that the chosen SiR leads to PC blends with a similar mechanical performance. KW - PC KW - BDP KW - PDMS KW - Flame retardancy KW - Flammability KW - Decomposition KW - Pyrolysis PY - 2012 DO - https://doi.org/10.1021/ie201908s SN - 0888-5885 SN - 1520-5045 VL - 51 IS - 3 SP - 1244 EP - 1255 PB - American Chemical Society CY - Washington, DC AN - OPUS4-25460 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wawrzyn, Eliza A1 - Schartel, Bernhard A1 - Ciesielski, M. A1 - Kretzschmar, B. A1 - Braun, Ulrike A1 - Döring, M. T1 - Are novel aryl phosphates competitors for bisphenol A bis(diphenyl phosphate) in halogen-free flame-retarded polycarbonate/acrylonitrile-butadiene-styrene blends? N2 - The reactivity of the flame retardant and its decomposition temperature control the condensed-phase action in bisphenol A polycarbonate/acrylonitrile–butadiene–styrene/polytetrafluoroethylene (PC/ABSPTFE) blends. Thus, to increase charring in the condensed phase of PC/ABSPTFE + aryl phosphate, two halogen-free flame retardants were synthesized: 3,3,5-trimethylcyclohexylbisphenol bis(diphenyl phosphate) (TMC-BDP) and bisphenol A bis(diethyl phosphate) (BEP). Their performance is compared to bisphenol A bis(diphenyl phosphate) (BDP) in PC/ABSPTFE blend. The comprehensive study was carried out using thermogravimetry (TG); TG coupled with Fourier transform infrared spectrometer (TG-FTIR); the Underwriters Laboratory burning chamber (UL 94); limiting oxygen index (LOI); cone calorimeter at different irradiations; tensile, bending and heat distortion temperature tests; as well as rheological studies and differential scanning calorimeter (DSC). With respect to pyrolysis, TMC-BDP works as well as BDP in the PC/ABSPTFE blend by enhancing the cross-linking of PC, whereas BEP shows worse performance because it prefers cross-linking with itself rather than with PC. As to its fire behavior, PC/ABSPTFE + TMC-BDP presents results very similar to PC/ABSPTFE + BDP; the blend PC/ABSPTFE + BEP shows lower flame inhibition and higher total heat evolved (THE). The UL 94 for the materials with TMC-BDP and BDP improved from HB to V0 for specimens of 3.2 mm thickness compared to PC/ABSPTFE and PC/ABSPTFE + BEP; the LOI increased from around 24% up to around 28%, respectively. BEP works as the strongest plasticizer in PC/ABSPTFE, whereas the blends with TMC-BDP and BDP present the same rheological properties. PC/ABSPTFE + TMC-BDP exhibits the best mechanical properties among all flame-retarded blends. KW - Polycarbonate (PC) KW - Aryl phosphate KW - Flame retardancy KW - Pyrolysis KW - PC/ABS PY - 2012 DO - https://doi.org/10.1016/j.eurpolymj.2012.06.015 SN - 0014-3057 SN - 1873-1945 VL - 48 IS - 9 SP - 1561 EP - 1574 PB - Elsevier CY - Oxford AN - OPUS4-26292 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Müller, Larissa A1 - Jakubowski, Norbert A1 - Hösl, Simone A1 - Scheler, C. A1 - Roos, P. H. A1 - Linscheid, M. W. T1 - Comparison of different chelates for lanthanide labeling of antibodies and application in a Western blot immunoassay combined with detection by laser ablation (LA-)ICP-MS N2 - We have developed lanthanide labeling strategies for antibodies to adapt conventional biochemical workflows like Western blot immunoassays for detection by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis with a special interest to apply the multi-element capabilities of ICP-MS for the design of multiplexed immunoassays. In this paper the lanthanide labeling of antibodies with MeCAT was investigated and the reaction conditions were optimized for application in a Western blot immunoassay analyzed by LA-ICP-MS. Furthermore, the MeCAT labeling strategy was compared with two other commercially available labeling reagents, MAXPAR™ and SCN-DOTA. As a proof-of-principle experiment chemically induced alterations of cytochrome P450 protein expression were investigated and the suitability of the differentially labeled antibodies for Western blot immunoassays of a complex liver microsomal protein fraction was tested. Limits of detection (LODs) in the lower fmol range were reached in the Western blot application using MeCAT and MAXPAR™ as element labeling reagents, whereas even sub-fmol LODs can be achieved in a dot blot experiment for the pure antibodies. PY - 2012 DO - https://doi.org/10.1039/c2ja30068k SN - 0267-9477 SN - 1364-5544 N1 - Geburtsname von Müller, Larissa: Wäntig, L. - Birth name of Müller, Larissa: Wäntig, L. N1 - Geburtsname von Hösl, Simone: Hardt, S. - Birth name of Hösl, Simone: Hardt, S. VL - 27 IS - 8 SP - 1311 EP - 1320 PB - Royal Society of Chemistry CY - London AN - OPUS4-26256 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Karrasch, Andrea A1 - Wawrzyn, Eliza A1 - Schartel, Bernhard A1 - Jäger, Christian T1 - Solid-state NMR on thermal and fire residues of bisphenol A polycarbonate/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate)/(PC(SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) - Part 1: PC charring and the impact of BDP and ZnB N2 - Structural changes in the condensed phase of bisphenol A polycarbonate (containing 0.45 wt% poly (tetrafluoroethylene))/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) during thermal treatment in nitrogen atmosphere and in fire residues were investigated by solid-state NMR. H-1, B-11, C-13 and P-31 NMR experiments using direct excitation with a single pulse and H-1-P-31 cross-polarization (CP) were carried out including 31P(1 H) and C-13{P-31}double-resonance techniques (REDOR: Rotational Echo Double Resonance) on a series of heat-treated samples (580 K-850 K). Because many amorphous phases occur in the solid residues, and solid-state NMR spectroscopy addresses the most important sites carbon, phosphorus and boron, this paper is the key analytical approach for understanding the pyrolysis and flame retarding phenomenon in the condensed phase of PC/SiR/BDP and PC/SiR/BDP/ZnB. For the system PC/SiR/BDP it is shown that (i) at temperatures around 750-770 K (main decomposition step) carbonaceous charring of PC occurs and arylphosphate structures are still present, reacted in part with the decomposing PC; (ii) for higher temperatures from 770 K the phosphorus remaining in the solid phase increasingly converts to amorphous phosphonates and inorganic orthophosphates with a minor amount of crystalline orthophosphates; and (iii) H-1-P-31{H-1} CP REDOR and H-1-C-13{P-31} CP REDOR NMR experiments suggest that the phosphates and phosphonates are bound via oxygen to aromatic carbons, indicating the interaction with the carbonaceous char. When ZnB is added to the system PC/SiR/BDP, (i) ZnB leads to a slightly enhanced PC decomposition for temperatures below 750 K; (ii) alpha-Zn-3(PO4)(2) and borophosphate (BPO4) are formed in small amounts at high temperatures suggesting a reaction between BDP and ZnB during thermal decomposition; and (iii) most of the borate remains in the solid residues, forming an amorphous pure borate network, with the BO3/BO4 ratio increasing with higher temperatures. The NMR data of thermal and fire residues are highly correlated, underlining the importance of this work for understanding the pyrolysis and flame retardancy mechanisms in the condensed phase during the burning of the PC/SiR blends. (C) 2010 Elsevier Ltd. All rights reserved. KW - Flame retardance KW - NMR KW - Polycarbonate (PC) blends KW - Bisphenol-A bis(diphenyl)phosphate (BDP) KW - Zinc borate PY - 2010 DO - https://doi.org/10.1016/j.polymdegradstab.2010.07.034 SN - 0141-3910 SN - 1873-2321 VL - 95 IS - 12 SP - 2525 EP - 2533 PB - Applied Science Publ. CY - London AN - OPUS4-22647 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Radunz, Sebastian A1 - Kraus, Werner A1 - Bischoff, F. A. A1 - Emmerling, Franziska A1 - Resch-Genger, Ute A1 - Tschiche, Harald T1 - Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes N2 - We report on the temperature- and structural-dependent optical properties and photophysics of a set of boron dipyrromethene (BODIPY) dyes with different substitution patterns of their meso-aryl subunit. Single-crystal Xray diffraction analysis of the compounds enabled a classification of the dyes into a sterically hindered and a unhindered group. The steric hindrance refers to a blocked rotational motion of the aryl subunit around the bond connecting this moiety to the meso-position of the BODIPY core. The energy barriers related to this rotation were simulated by DFT calculations. As follows from the relatively low rotational barrier calculated to about 17 kcal/mol, a free rotation is only possible for sterically unhindered compounds. Rotational barriers of more than 40 kcal/mol determined for the sterically hindered compounds suggest an effective freezing of the rotational motion in These molecules. With the aid of temperature-dependent spectroscopic measurements, we could show that the ability to rotate directly affects the optical properties of our set of BODIPY dyes. This accounts for the strong temperature dependence of the fluorescence of the sterically unhindered compounds which show a drastic decrease in fluorescence quantum yield and a significant shortening in fluorescence lifetime upon heating. The optical properties of the sterically hindered compounds, however, are barely affected by temperature. Our results suggest a nonradiative deactivation of the first excited singlet state of the sterically unhindered compounds caused by a conical intersection of the potential energy surfaces of the Ground and first excited state which is accessible by rotation of the meso-subunit. This is in good agreement with previously reported deactivation mechanisms. In addition, our results suggest the presence of a second nonradiative depopulation pathway of the first excited singlet state which is particularly relevant for the sterically hindered compounds. KW - Fluorescence KW - Sensor KW - Switch KW - pH KW - BODIPY KW - Dye KW - Probe KW - Synthesis KW - Photophysics KW - Mechanism PY - 2020 DO - https://doi.org/10.1021/acs.jpca.9b11859 SN - 1089-5639 VL - 124 IS - 9 SP - 1787 EP - 1797 PB - American Chemical Society AN - OPUS4-50639 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - de Olivera, Paulo A1 - Michalchuk, Adam A1 - Marquardt, Julien A1 - Feiler, Torvid A1 - Prinz, Carsten A1 - Torresi, R. A1 - Camargo, P. A1 - Emmerling, Franziska T1 - Investigating the role of reducing agents on mechanosynthesis of Au nanoparticles N2 - Control over the bottom up synthesis of metal nanoparticles (NP) depends on many experimental factors, including the choice of stabilising and reducing agents. By selectively manipulating these species, it is possible to control NP characteristics through solution-phase synthesis strategies. It is not known, however, whether NPs produced from mechanochemical syntheses are governed by the same rules. Using the Au NPs mechanosynthesis as a model system, we investigate how a series of common reducing agents affect both the reduction kinetics and size of Au NPs. It is shown that the relative effects of reducing agents on mechanochemical NP synthesis differ significantly from their role in analogous solution-phase reactions. Hence, strategies developed for control over NP growth in solution are not directly transferrable to environmentally benign mechanochemical approaches. This work demonstrates a clear need for dedicated, systematic studies on NP mechanosynthesis. KW - Mechanochemistry KW - Metal nanoparicels PY - 2020 DO - https://doi.org/10.1039/d0ce00826e VL - 22 IS - 38 SP - 6261 EP - 6267 PB - Royal Society of Chemistry AN - OPUS4-51757 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kulla, Hannes A1 - Haferkamp, Sebastian A1 - Akhmetova, Irina A1 - Röllig, Mathias A1 - Maierhofer, Christiane A1 - Rademann, Klaus A1 - Emmerling, Franziska T1 - In situ investigations of mechanochemical one-pot syntheses N2 - We present an in situ triple coupling of synchrotron X-ray diffraction with Raman spectroscopy, and thermography to study milling reactions in real time. This combination of methods allows a correlation of the structural evolution with temperature information. The temperature information is crucial for understanding both the thermodynamics and reaction kinetics. The reaction mechanisms of three prototypical mechanochemical syntheses, a cocrystal formation, a C@C bond formation (Knoevenagel condensation), and the formation of a manganese-phosphonate, were elucidated. Trends in the temperature development during milling are identified. The heat of reaction and latent heat of crystallization of the product contribute to the overall temperature increase. A decrease in temperature occurs via release of, for example, water as a byproduct. Solid and liquid intermediates are detected. The influence of the mechanical impact could be separated from temperature effects caused by the reaction. KW - In situ studies KW - Mechanochemistry KW - Raman spectroscopy KW - Thermography KW - X-ray diffraction PY - 2018 DO - https://doi.org/10.1002/anie.201800147 SN - 1433-7851 SN - 1521-3773 VL - 57 IS - 20 SP - 5930 EP - 5933 PB - Wiley-VCH CY - Weinheim AN - OPUS4-44946 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Haferkamp, Sebastian A1 - Emmerling, Franziska T1 - Insights into the mechanochemical Knoevenagel condensation N2 - Mechanochemistry paves the way to simple, fast, and green syntheses, but there is a lack in understanding of the underlying mechanisms. Here, we present a universal strategy for simultaneous real-time in situ analysis, combining X-ray diffraction, Raman spectroscopy, and thermography. T2 - Bessy User Meeting 2019 CY - Berlin, Germany DA - 05.12.2019 KW - Mechanochemistry PY - 2019 AN - OPUS4-50122 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Braun, Ulrike A1 - Bannick, C.G. A1 - Szewzyk, R. A1 - Ricking, M. A1 - Schniegler, S. A1 - Obermaier, N. A1 - Barthel, A. K. A1 - Altmann, Korinna A1 - Eisentraut, Paul T1 - Development and testing of a fractionated filtration for sampling of microplastics in water N2 - A harmonization of sampling, sample preparation and detection is pivotal in order to obtain comparable data on microplastics (MP) in the environment. This paper develops and proposes a suitable sampling concept for waterbodies that considers different plastic specific properties and influencing factors in the environment. Both artificial water including defined MP fractions and the discharge of a wastewater treatment plant were used to verify the derived sampling procedure, sample preparation and the subsequent analysis of MP using thermal extraction-desorption gas chromatography - mass spectrometry (TED-GC-MS). A major finding of this paper is that an application of various particle size classes greatly improves the practical handling of the sampling equipment. Size classes also enable the TED-GC-MS to provide any data on the MP size distribution, a substantial sampling property affecting both the necessary sampling volume and the optimal sampling depth. In the artificial water with defined MP fractions, the recovery rates ranged from 80 to 110%, depending on the different MP types and MP size classes. In the treated wastewater, we found both Polyethylene and polystyrene in different size classes and quantities. KW - Microplastics KW - Sampling KW - Sampling techniques KW - Water PY - 2019 DO - https://doi.org/10.1016/j.watres.2018.10.045 SN - 0043-1354 VL - 149 SP - 650 EP - 658 PB - Elsevier AN - OPUS4-47200 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, G. A1 - Emmerling, Franziska A1 - Kemnitz, E. T1 - Strontium-coordination polymers based on tetrafluorophthalic and phthalic acids: mechanochemical synthesis, ab initio structures determination, and spectroscopic characterization N2 - Two strontium-based dicarboxylate systems [Sr(oBDC-F4)(H2O)2] (1) and [{Sr(oBDC)(H2O)2)·H2O] (2) were synthesized mechanochemically via milling of Sr(OH)2·8H2O with tetrafluorophthalic acid (H2oBDC-F4) or phthalic acid (H2oBDC), respectively. The new structures were determined ab initio from the powder X-ray diffraction (PXRD) data. Both compounds 1 and 2 crystallize in the monoclinic space group P21 /c as two-dimensional coordination polymers (2D-CPs). The determined structures were validated by extended X-ray absorption (EXAFS) data. Compounds 1 and 2 show different thermal stabilities. The fluorinated CP 1 is decomposed at 300 °C while the nonfluorinated CP 2 transforms into a new phase after thermal treatment at 400 °C. The two hydrated CPs exhibit small surface areas which increase after the thermal posttreatment for 1 but remains unchanged for the dehydrated sample of 2. Dynamic vapor sorption (DVS) experiments indicate that both the dehydrated and hydrated samples of 2 depict no significant differences in their adsorption isotherms. The DVS of water indicates that the phase transition after thermal posttreatment of 2 is irreversible. KW - Mechanochemistry KW - XRD KW - NMR PY - 2017 DO - https://doi.org/10.1039/c7dt02564e SN - 1477-9226 SN - 1477-9234 VL - 46 IS - 37 SP - 12574 EP - 12587 PB - The Royal Society of Chemistry CY - Cambridge AN - OPUS4-42261 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heilmann, Maria T1 - Synthesis of bimetallic nickel nanoparticles as catalysts for the Sabatier reaction N2 - Nanoparticles (NPs) have become important materials for a variety of chemical technologies. The enhanced surface-area-to-volume ratio of NPs, making them excellent for use as catalyst, in analytical assays, and for antimicrobial applications. Nickel NPs have exhibited immense potential as important catalyst for the Sabatier reaction, i.e. converting waste to energy via transformation of CO2 into CH4, and could replace the rare earth elements such as Ru, PT, or Rh. In this work we describe the solvothermal synthesis of monometallic and bimetallic nickel nanoparticles. Monodisperse monometallic Ni NPs were synthesized using Oleylamin as solvent and reducing agent. The nanoparticles were investigated using small angle scattering (SAXS), scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX), showing that the NPs are stable while the surface is not entirely covered. However, Ni has a high propensity to undergo oxidation, and becoming deactivated by coke formation. Hence, we further explore the preparation of bimetallic NPs, where a second metal is added to stabilize the Ni. Bimetallic Cu-Ni NPs were synthesized by simultaneous solvothermal reduction. These bimetallic NPs exhibit excellent catalytic properties are promising candidates to be used as catalysts for efficient energy storage. T2 - Adlershofer Forschungsforum 2019 CY - Berlin, Germany DA - 11.11.2019 KW - Nanoparticles KW - Catalysis KW - Synthesis PY - 2019 AN - OPUS4-50173 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gugin, Nikita A1 - Villajos Collado, José Antonio A1 - Dautain, O. A1 - Maiwald, Michael A1 - Emmerling, Franziska T1 - Optimizing the Green Synthesis of ZIF-8 by Reactive Extrusion Using In Situ Raman Spectroscopy N2 - We report the scale-up of a batch solid synthesis of zeolitic imidazolate framework-8 (ZIF-8) for reactive extrusion. The crystalline product forms in the extruder directly under the mixture of solid 2-methylimidazole and basic zinc carbonate in the presence of a catalytic amount of liquid. The process parameters such as temperature, liquid type, feeding rate, and linker excess were optimized using the setup specifically designed for in situ Raman spectroscopy. Highly crystalline ZIF-8 with a Brunauer–Emmett–Teller (BET) surface area of 1816 m2 g–1 was quantitatively prepared at mild temperature using a catalytic amount of ethanol and a small excess of the linker. Finally, we developed a simple and comprehensive approach to evaluating the environmental friendliness and scalability of metal–organic framework (MOF) syntheses in view of their large-scale production. KW - Mechanochemistry KW - In situ Raman KW - Large-scale processing KW - Metal−organic frameworks KW - Twin-screw extrusion (TSE) PY - 2023 DO - https://doi.org/10.1021/acssuschemeng.2c07509 SN - 2168-0485 VL - 11 IS - 13 SP - 5175 EP - 5183 PB - ACS Publications AN - OPUS4-57366 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lee, P.-W. A1 - Kaynak, T. A1 - Al-Sabbagh, Dominik A1 - Emmerling, Franziska A1 - Schalley, C. T1 - Effect of Perfluorinated Side-Chain Length on the Morphology, Hydrophobicity, and Stability of Xerogel Coatings N2 - Superhydrophobic surfaces can be quickly formed with supramolecular materials. Incorporating low-molecular-weight gelators (LMWGs) with perfluorinated chains generates xerogel coatings with low surface energies and high roughness. Here, we examine and compare the properties of the xerogel coatings formed with eight different LMWGs. These LMWGs all have a trans-1,2-diamidocyclohexane core and two perfluorinated ponytails, whose lengths vary from three to ten carbon atoms (CF3 to CF10). Investigation of the xerogels aims to provide in-depth information on the chain length effect. LMWGs with a higher degree of fluorination (CF7 to CF10) form superhydrophobic xerogel coatings with very low surface energies. Scanning electron microscopy images of the coatings show that the aggregates of CF5 and CF7 are fibrous, while the others are crystal-like. Aggregates of CF10 are particularly small and further assemble into a porous structure on the micrometer scale. To test their stabilities, the xerogel coatings were flushed multiple times with a standardized water flush test. The removal of material from the surface in these flushes was monitored by a combination of the water contact angle, contact angle hysteresis, and coating thickness measurements. A new method based on image processing techniques was developed to reliably determine the change of the coating thickness. The CF7, CF9, and CF10 surfaces show consistent hydrophobicity and coating durability after repetitive flushing tests. The length of the perfluorinated side chains thus has a significant effect on the morphology of the deposited xerogel coatings, their roughness, and, in consequence, their hydrophobicity and mechanical durability. KW - Coating materials KW - Amorphous materials KW - Hydrophobicity KW - Materials Stability PY - 2021 DO - https://doi.org/10.1021/acs.langmuir.1c02341 SN - 1520-5827 VL - 37 IS - 49 SP - 14390 EP - 14397 PB - ACS Publications AN - OPUS4-54071 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmitt, M. A1 - Altmann, Korinna A1 - Fengler, Petra A1 - Gehde, M. T1 - Air-based polyethylene fragmentation with high yield to form microplastic particles as reference material candidates N2 - Microplastic particles with sizes between 1 to 1000 μm are widely distributed worldwide. Origin, transport pathways and fate are poorly known, as sampling, sample preparation and detection methods are major challenges. In addition, reference materials that mimic environmental particles are lacking. Most challenging is the yield of MP particle production and the need for resource-intensive grinding with liquid nitrogen. In this paper, a machine is designed to produce aged microplastic particles as reference material candidates with high yield. The machine is based on ultraviolet aging of a thin foil and mechanical fragmentation using clean air. An example of aging and fragmentation of high density polyethylene with additional physical and chemical characterization of shape, size, aging state by carbonyl index and density is presented. KW - Microplastics KW - Degradation of polyethylene KW - Air fragmentation KW - Microplastics reference material PY - 2023 DO - https://doi.org/10.1002/appl.202200121 SP - 1 EP - 18 PB - Wiley online library AN - OPUS4-57203 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wiesner, Yosri T1 - Erfassung von Degradationsprodukten und Additiven sowie temperaturspezifische Pyrolyseprodukte mittels TED-GC/MS N2 - Im der Präsentation werden, neben der Möglichkeit der Mikroplastikquantifizierung, auf weitere Anwendungsfelder der Methode TED-GC/MS eigegangen. Dies beinhaltet die Erfassung von Degradationsprodukten UV/O2 geschädigter Polymere und die Detektion von Additiven. Die Optimierung der Methode betreffend Messzeit und materialspezifischer Messanforderung sind ebenfalls Gegenstand. T2 - Kolloquium Massenspektrometrie von Polymeren CY - Berlin, Germany DA - 09.05.2023 KW - TED-GC/MS KW - Polymere KW - Degradation KW - Additive PY - 2023 AN - OPUS4-57480 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, Gudrun A1 - Emmerling, Franziska A1 - Kemnitz, Erhard T1 - Barium coordination polymers based on fluorinated and fluorine-free benzene-dicarboxylates: Mechanochemical synthesis and spectroscopic characterization N2 - A series of new Ba-based coordination polymers (CPs) were mechanochemically synthesized by milling Ba-hydroxide samples with perfluorinated and fluorine-free benzene-dicarboxylic acids, including tetrafluoroisophthalic acid (H2mBDC-F4), tetrafluorophthalic acid (H2oBDC-F4), isophthalic acid (H2mBDC) and phthalic acid (H2oBDC). The new fluorinated CPs: [Ba(mBDC-F4)$0.5H2O] (1) and [Ba(oBDC-F4)·1.5H2O] (2) are compared to their nonfluorinated counterparts: [Ba(mBDC)·2.5H2O] (3), and [Ba(oBDC)·1H2O] (4). These materials are thoroughly characterized using powder X-ray diffraction. The products obtained by milling are all hydrated but vary in their water contents. Compositions and local structures are investigated by elemental analysis, thermal analysis, MAS NMR and attenuated total reflectioninfrared spectroscopy. These materials exhibit high thermal stabilities but small surface areas that remain unchanged even after thermal treatments. KW - Mechanochemical synthesis KW - Barium KW - Fluorine KW - Coordination polymers KW - PXRD KW - MAS NMR spectroscopy PY - 2018 UR - https://www.sciencedirect.com/science/article/pii/S1293255817310798 DO - https://doi.org/10.1016/j.solidstatesciences.2018.03.013 SN - 1293-2558 SN - 1873-3085 VL - 79 SP - 99 EP - 108 PB - Elsevier AN - OPUS4-44880 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Eitzen, L. A1 - Paul, S. A1 - Braun, Ulrike A1 - Altmann, Korinna A1 - Jekel, M. A1 - Ruhl, A. T1 - The challenge in preparing particle suspensions for aquatic microplastic research N2 - The occurrence of small particles consisting of organic polymers, so-called microplastic (MP), in aquatic Environments attracts increasing interest in both public and science. Recent sampling campaigns in surface Waters revealed substantial numbers of particles in the size range from a few micrometers to a few millimeters. In order to validate sample preparation, identification and quantification and to investigate the behavior of MP particles and potential toxic effects on organisms, defined MP model particles are needed. Many studies use spherical compounds that probably behave differently compared to irregularly shaped MP found in environmental samples. However, preparation and handling of MP particles are challenging tasks and have been systematically investigated in the present study. Polystyrene (PS) as a commonly found polymer with a density slightly above that of water was selected as polymer type for milling and fractionation studies. A cryogenic ball mill proved to be practical and effective to produce particles in the size range from 1 to 200 μm. The yield of small particles increased with increasing pre-cooling and milling durations. Depending on the concentration and the size, PS particles do not completely disperse in water and particles partly creep vertically up along glass walls. Stabilized MP suspensions without use of surfactants that might harm organisms are needed for toxicological studies. The stabilization of PS particle suspensions with ozone treatment reduced the wall effect and increased the number of dispersed PS particles but increased the dissolved organic carbon concentration and changed the size Distribution of the particles. KW - Reference material KW - Microplastic PY - 2018 DO - https://doi.org/10.1016/j.envres.2018.09.008 SN - 0013-9351 SN - 1096-0953 VL - 168 SP - 490 EP - 495 PB - Elsevier AN - OPUS4-46462 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -