TY - CONF A1 - Kjaervik, Marit A1 - Dietrich, P. A1 - Thissen, A. A1 - Schwibbert, Karin A1 - Defedov, A. A1 - Wöll, C. A1 - Unger, Wolfgang T1 - Exploring the capabilities of NAP-XPS: Application to metal-organic frameworks, nanoparticles and biofilms N2 - Near-ambient pressure XPS makes it possible to characterise samples not compatible to ultra-high vacuum, and enables the study of liquid-solid, gas-liquid and gas-solid interfaces. NAP-XPS meas-urements of biofilms, suspended nanoparticles and metal-organic frameworks were performed with EnviroESCA developed by SPECS. An interesting application is surface characterisation of biofilms, which are bacterial communities embedded in a self-produced polysaccharide matrix. Various model systems ranging from pure polysaccharides of alginate to biofilms harvested directly from the growth medium have been char-acterised in humid conditions[1]. NAP-XPS also makes it possible to characterise nanoparticles in solution. Silver nanoparticles in aqueous solution were characterised and the Ag 3d-spectrum compared to spectra obtained of dried nanoparticles in UHV-conditions[2]. The binding energy of the Ag 3d-core level peak was shifted by 0,6 eV towards higher binding energy for suspended nanoparticles compared to the dried sample measured in UHV. This can be assigned to a change in surface potential at the water-nanoparticle interface. Metal-organic frameworks (MOFs) are suitable materials for gas storage of small molecules due to their nanoporous, crystalline structure. However, instability in humidity remains an issue for many types of MOFs. XPS-measurements of the MOF-structure HKUST-1 were performed in various NAP-conditions to assess the stability of the sample and its interaction with the gas molecules as water, methanol and pyridine. T2 - 5th AP-XPS Workshop CY - Berlin, Germany DA - 11.12.18 KW - Biofilms KW - E. coli KW - NAP-XPS KW - Metal organic frameworks KW - Nanoparticles PY - 2018 AN - OPUS4-47060 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian A1 - Goedecke, Caroline A1 - Sojref, Regine T1 - Transformation of the antidiabetic drug metformin N2 - For years there have been more and more reports on the presence of drugs in the aquatic environment. Due to the demographic change, the consumption of pharmaceuticals has risen sharply. After taking the drugs, they are partly metabolized in the human body. However, the metabolism is not complete so that both the metabolites and non-metabolized amounts of the parent compounds are excreted. These compounds reach the waste water and afterwards the sewage treatment plants. In sewage treatment plants transformation products can be formed by the oxidative conditions during wastewater treatment processes. The transformation products may have a higher toxicity than the actual environmental pollutants and are often only partly removed during the waste water treatment. Since a lot of these compounds are still unknown, the transformation products are not detected by target analysis used in sewage treatment plants and are often released undetected in the aquatic ecosystems. The released substances may be subject to additional transformation processes in the environment. Pharmaceuticals produced in high amounts can be already detected in the μg/L range in water bodies worldwide. Metformin and its major transformation product guanylurea are one of the main representatives. Metformin is the drug of choice for treating type 2 diabetes. The drug therapy for diabetes mellitus has increased significantly in recent years. In the year 2015 1500 tons of metformin were prescribed in Germany (for statutory insured persons). Metformin is not metabolized in the human body and is excreted unchanged therefore concentrations between 57 μg/L and 129 μg/L are found in German waste water treatment plants influents. In this work the transformation of the antidiabetic drug metformin is investigated. The degradation of metformin is initialize by commercial water treatment techniques like UV-radiation or noncommercial techniques like heterogenous photocatalysis based on titanium dioxide. The degradation of metformin and resulting transformation products are analyzed by LC-MS/MS and LC-HRMS. T2 - SPEA 10 CY - Almeria, Spain DA - 04.06.2018 KW - Metformin KW - Photocatalysis PY - 2018 AN - OPUS4-47030 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kricheldorf, H. R. A1 - Scheliga, F. A1 - Weidner, Steffen T1 - Syntheses of Cyclic Polymers via the ROPPOC Approach N2 - Different strategies for the synthesis of polylactides were presented with special focus on Ring-opening Polymerization (ROP) and simultaneous ROP and Polycondensation (ROPPOC) mechanism. The mechanism of the formation of cyclic Polyesters is discussed in detail and established theories about the formation of cycles in polycondensation reactions are critically reviewed. T2 - DSM Competence Meeting CY - Dalfsen, The Netherlands DA - 12.11.2018 KW - Polylactide KW - MALDI-TOF mass spectrometry KW - Polycondensation KW - Cycles PY - 2018 AN - OPUS4-47027 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kabelitz, Anke A1 - Emmerling, Franziska A1 - de Oliveira Guilherme Buzanich, Ana A1 - Kraehnert, R. A1 - Kraffert, K. A1 - Schmack, R. T1 - In-situ characterisation of nucleation, growth, crystallisation and dissolution of nanoscaled iron oxides N2 - We present the synthesis of four mesoporous templated iron oxides: Ferrihydrite, Hematite, Maghemite, Magnetite/Maghemite and the influence of water on the crystallization mechanism and the kinetics. The absence of water stabilize the ferrihydrite structure. By monitoring the dissolution in situ by using a QCMB and ex situ microscopy we got details in the dissolution mechanism of ferrihydrite. T2 - Final Meeting of the CRC 1109 & Edith Flanigen Award Ceremony 2018 CY - Berlin, Germany DA - 10.10.2018 KW - Mesoporous KW - Iron oxide KW - Mechanism PY - 2018 AN - OPUS4-47010 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kabelitz, Anke A1 - Dinh, H. A. A1 - Emmerling, Franziska T1 - A02: In situ WAXS studies on the crystallization of Al 13 keggin clusters in water N2 - Polynuclear aluminium species (Al13 keggin cluster) find application in different areas like water purification [1], contaminant transport [2], and as pilling clays with high specific surface areas[3], due to their strong binding ability to aggregates and high positive charge. In the present contribution, we report on the in situ investigation of the Al13 sulfate synthesis by synchrotron wide-angle X-ray scattering (WAXS). Al13 cluster were crystallized by precipitating hydrolyzed aluminum solutions by the addition of sodium sulfate. The measurements were performed using a custom-made acoustic levitator as sample holder. The study provides information about the intermediates during the crystallization process. From the data, a mechanism was derived indicating the influence of the crystallization process. T2 - Final Meeting of the CRC 1109 & Edith Flanigen Award Ceremony 2018 CY - Berlin, Germany DA - 10.10.2018 KW - Crystallization KW - WAXS KW - Keggin Cluster PY - 2018 AN - OPUS4-47005 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ringleb, F. A1 - Andree, Stefan A1 - Heidmann, B. A1 - Bonse, Jörn A1 - Eylers, K. A1 - Ernst, O. A1 - Boeck, T. A1 - Schmid, M. A1 - Krüger, Jörg T1 - Femtosecond laser-assisted fabrication of chalcopyrite micro-concentrator photovoltaics N2 - Micro-concentrator solar cells offer an attractive way to further enhance the efficiency of planar-cell technologies while saving absorber material. Here, two laser-based bottom-up processes for the fabrication of regular arrays of CuInSe2 and Cu(In,Ga)Se2 microabsorber islands are presented, namely one approach based on nucleation and one based on laser-induced forward transfer. Additionally, a procedure for processing these microabsorbers to functioning micro solar cells connected in parallel is demonstrated. The resulting cells show up to 2.9% efficiency and a significant efficiency enhancement under concentrated Illumination. KW - Chalcopyrite KW - Femtosecond laser patterning KW - Laser-induced forward transfer KW - Micro-concentrator solar cell KW - Photovoltaics PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-470026 DO - https://doi.org/10.3762/bjnano.9.281 SN - 2190-4286 VL - 9 SP - 3025 EP - 3038 PB - Beilstein-Institut zur Förderung der Chemischen Wissenschaften CY - Frankfurt, M. AN - OPUS4-47002 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Crasselt, Claudia A1 - Schmidt, Wolfram A1 - Sturm, Heinz T1 - Influence of rheology modifying admixtures on hydration of cementitious suspensions N2 - The state of fresh concrete is predominantly determined by the rheological properties of the cement paste. In order to control performance spectra and requirements of novel concretes and to better understand macroscopic phenomena, comprehensive knowledge of the material behavior of fresh cement suspensions as well as of the complex relationships of mechanisms at the nano and micro scale are necessary. This work focuses on micro and nano rheology of suspensions of cementitious model systems and the influence of polycarboxylate-based admixtures on the rheology. The phenomena are driven by multiple parameters such as adsorption and particle interactions. Hence, the first part examines the interaction between polycarboxylate ether (PCE) and synthesized clinker phases and hydration products as model systems with regard to early hydration products. T2 - 6th International Symposium on Nanotechnology in Construction CY - Hong Kong, China DA - 02.12.2018 KW - Cement KW - Early hydration KW - Polycarboxylate ether (PCE), PY - 2018 AN - OPUS4-46980 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - In-situ investigations of mechanochemical reactions N2 - Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic[1], metal-organic[2], and inorganic[3] compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms remain often unclear. In the last years, have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy.[4] Here, we present an 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. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses. T2 - ACS Conference Boston CY - Boston, USA DA - 19.08.2018 KW - Mechanochemistry KW - In situ KW - Kinetic PY - 2018 AN - OPUS4-46989 LA - eng 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 - Emmerling, Franziska T1 - In situ investigations of mechanochemical reactions N2 - Presentation of the recent results in the context of in situ investigations of reactions using X-ray diffraction. T2 - Germany Brazil Workshop: New light on mechanisms of chemical reactions CY - Kiel, Germany DA - 31.07.2018 KW - In situ KW - XRD PY - 2018 AN - OPUS4-46991 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - In situ studies of mechanochemistry: a force of synthesis N2 - Recent results in the field of mechanisms and kinetics of mechanochemical reactions. T2 - Seminar GFZ Potsdam CY - Postdam, Germany DA - 28.03.2018 KW - In situ KW - XRD KW - Rietveld PY - 2018 AN - OPUS4-46992 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Synchrotron X-ray Investigations N2 - Summary of the techniques available at the BAMline and µspot BEamline. T2 - Workshop Humboldt University and Hebrew University of Jerusalem CY - Berlin, Germany DA - 09.10.2018 KW - In situ KW - XRD PY - 2018 AN - OPUS4-46993 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Akhmetova, Irina A1 - Haferkamp, Sebastian A1 - Schutjajew, Konstantin A1 - Roth, Christina A1 - Emmerling, Franziska T1 - In situ investigation of mechanochemical syntheses of manganese phosphonates with N-containing ligands N2 - Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. The exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades due to their structural diversity. We synthesized manganese phosphonates in milling reactions. The mechanochemical reactions were investigated in situ to reveal the underlying mechanisms. T2 - Joint BER II and BESSY II User Meeting CY - Berlin, Germany DA - 05.12.2018 KW - Metal phosphonates KW - Mechanochemistry KW - PXRD KW - In situ KW - Thermography PY - 2018 AN - OPUS4-46999 LA - eng 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 a fast and efficient method applicable for the synthesis of new organic[1], metal-organic[2], and inorganic[3] compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms remain often unclear. In the last years, have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy.[4] Here, we present an 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. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses. T2 - 5th International Conference "Fundamental Bases of Mechanochemical Technologies" CY - Novosibirsk, Russia DA - 25.06.2018 KW - Mechanochemistry KW - XRD KW - Kinetic KW - Coordination polymers PY - 2018 AN - OPUS4-46994 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - In situ characterization of nucleation, growth, crystallization and dissolution of nanoscaled iron oxides N2 - Nucleation and growths of iorn oxide nanoparticles studied in situ using XRD, XRF, SAXS and XANES. T2 - International CRC meeting CY - Berlin, Germany DA - 10.10.2018 KW - XRD KW - XANES PY - 2018 AN - OPUS4-46995 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Akhmetova, Irina A1 - Schutjajew, Konstantin A1 - Roth, Christina A1 - Emmerling, Franziska T1 - Mechanochemical synthesis of metal phosphonates N2 - The exploration of metal phosphonates chemistry has gained great interest during the last decades, because of their structural diversity. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reactions (OER). Here, we present the in situ investigation of mechanochemical syntheses of different manganese phosphonates by synchrotron X-ray diffraction. Nitrilotri(methylenephosphonic acid) and N,N-Bis(phosphonomethyl)glycine were chosen as ligands. The liquid-assisted milling process can be divided into three steps, including an amorphous stage. One of the products has not been obtained by classical solution chemistry before. These metal phosphonates and/or their derivatives are considered to be active in electrochemical energy conversion. The verification of their applicability is one of the topics of our resent research. T2 - Fundamental Bases of Mechanochemical Technologies CY - Novosibirsk, Russia DA - 25.06.2018 KW - Metal phosphonates KW - Mechanochemistry KW - PXRD KW - Thermography PY - 2018 AN - OPUS4-46996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Haferkamp, Sebastian A1 - Emmerling, Franziska A1 - Akhmetova, Irina A1 - Kulla, Hannes A1 - Rademann, Klaus T1 - In situ investigation of mechanochemical Knoevenagel condensations of benzaldehyde derivates N2 - Mechanochemistry is known for short reaction times, nearly quantitative conversions, and decreasing amount of solvents. Among organic syntheses, the Knoevenagel condensation is an important C-C bond forming reaction. We investigated the reaction of benzaldehyde derivates (nitro- and fluoro-derivates) with malononitrile syntheses by a combination of different in situ investigation techniques. T2 - BESSY II User Meeting CY - Berlin, Germany DA - 05.12.2018 KW - Mechanochemistry KW - In situ PY - 2018 AN - OPUS4-46997 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Akhmetova, Irina A1 - Emmerling, Franziska A1 - Schutjajew, Konstantin A1 - Roth, Christina T1 - In situ investigation of milling reactions and structure determination of the products using X-ray diffraction N2 - Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. By milling the reactants, various organic, inorganic, and metal-organic compounds can be obtained in high yields. Although mechanochemistry is widely used, the underlying mechanisms are not fully understood making mechanochemical reactions difficult to predict. Metal phosphonates are metal-organic compounds accessible by grinding. Because of their structural diversity, the exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reaction (OER). Here, we present the in situ investigation of the mechanochemical synthesis of a manganese(II)-phosphonate by synchrotron X-ray diffraction and thermography. The product has not been obtained by classical solution chemistry before and its crystal structure was determined from PXRD data. The milling process can be divided into different steps, with the product crystallization corresponding with the highest temperature rise. The activity of this metal phosphonate towards OER was measured and is presented here. T2 - International School of Crystallography - 52nd Course: Quantum Crystallography CY - Erice, Italy DA - 1.06.2018 KW - Metal phosphonates KW - Mechanochemistry KW - PXRD KW - OER KW - Thermography PY - 2018 AN - OPUS4-46998 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heilmann, Maria A1 - Bernardes, C. A1 - Minas da Piedade, M. A1 - Emmerling, Franziska T1 - Real Time In Situ Study of Simvastatin Crystallization on Levitated Droplets N2 - In this contribution we describe an in-situ study of the crystallization of simvastatin in three solvents. The studies were carried out by solvent evaporation at the µSpot beamline using acoustically levitated solution droplets in combination with simultaneous X-ray diffraction, Raman spectroscopy, and imaging analysis. T2 - 10th Joint BER II and BESSY II User Meeting CY - Berlin, Germany DA - 05.12.2018 KW - Crystallization KW - Simvastatin KW - In-Situ Characterization PY - 2018 AN - OPUS4-46965 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zietzschmann, F. A1 - Dittmar, S. A1 - Splettstößer, L. A1 - Hunsicker, J. A1 - Dittmann, Daniel A1 - Meinel, F. A1 - Rößler, A. A1 - Metzger, S. A1 - Jekel, M. A1 - Ruhl, A. S. T1 - Fast empirical lab method for performance projections of large-scale powdered activated carbon re-circulation plants N2 - Powdered activated carbon (PAC) for organic micro-pollutant (OMP) removal can be applied effectively on wastewater treatment plant (WWTP) effluents by using re-circulation schemes, accumulating the PAC in the system. This technique is complex because several factors are unknown: (i) the PAC concentration in the system, (ii) specific and average contact times of PAC particles, and (iii) PAC particle loadings with target compounds/competing water constituents. Thus, performance projections (e.g. in the lab) are very challenging. We sampled large-scale PAC plants with PAC sludge re-circulation on eight different WWTPs. The PAC plant-induced OMP removals were notably different, even when considering PAC concentrations in proportion to background organic sum parameters. The variability is likely caused by differing PAC products, varying water composition, differently effective plant/re-circulation operation, and variable biodegradation. Plant PAC samples and parts of the PAC plant influent samples were used in laboratory tests, applying multiples (0.5, 1, 2, 4) of the respective large-scale “fresh” PAC doses, and several fixed contact times (0.5, 1, 2, 4, 48 h). The aimwas to empirically identify suitable combinations of lab PAC dose (as multiples of the plant PAC dose) and contact time, which represent the PAC plant performances in removing OMPs (for specific OMPs at single locations, and for averages of different OMPs at all locations). E.g., for five well adsorbing, little biodegradable OMPs, plant performances can be projected by using a lab PAC dose of twice the respective full-scale PAC dose and 4 h lab contact time (standard deviation of 13 %-points). KW - Adsorption KW - Powdered activated carbon KW - Organic micro-pollutant KW - Trace organic contaminant PY - 2019 DO - https://doi.org/10.1016/j.chemosphere.2018.10.055 VL - 215 SP - 563 EP - 573 PB - Elsevier Ltd. AN - OPUS4-46957 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Panne, Ulrich A1 - Gornushkin, Igor B. A1 - Riedel, Jens A1 - Schneider, Rudolf A1 - Emmerling, Franziska 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 - Kjaervik, Marit A1 - Dietrich, P. A1 - Thissen, A. A1 - Schwibbert, Karin A1 - Unger, Wolfgang T1 - Depth-dependent analysis of model biofilms by combining laboratory- and synchrotron-based X-ray photoelectron spectroscopy N2 - Synchrotron XPS in the soft-X-ray regime is suitable for the detection of light elements commonly found in biological samples. Various model systems of biofilms have been developed and characterised at synchrotron- and lab-based facilities. By obtaining the chemical composition at various information depths, the vertical distribution of iodine in an artificial biofilm have been determined. T2 - Tenth Joint BER II and BESSY II User Meeting CY - Berlin, Germany DA - 05.12.2018 KW - Biofilms KW - HAXPES KW - XPS KW - Iodine KW - Synchrotron-XPS PY - 2018 AN - OPUS4-46929 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Greiser, Sebastian A1 - Gluth, Gregor A1 - Sturm, Patrick A1 - Jäger, Christian T1 - 29Si{27Al}, 27Al{29Si} and 27Al{1H} double-resonance NMR spectroscopy study of cementitious sodium aluminosilicate gels (geopolymers) and gel-zeolite composites N2 - The influence of starting materials and synthesis route on the properties and the structure of cementitious sodium aluminosilicate gels is not fully understood, partly due their amorphous nature and the fact that they often contain residual reactants, which can make the results of single-pulse NMR spectroscopy applied to these materials difficult to interpret or ambiguous. To overcome some of these limitations, 29Si{27Al} TRAPDOR NMR as well as 27Al{29Si} and 27Al{1H} REDOR NMR spectroscopy were applied to materials synthesized by the one-part alkali-activation route from three different amorphous silica starting materials, including rice husk ash. The latter led to formation of a fully amorphous sodium aluminosilicate gel (geopolymer), while the materials produced from the other silicas contained amorphous phase and crystalline zeolites. Application of the double-resonance NMR methods allowed to identify hydrous alumina gel domains in the rice husk ash-based material as well as significantly differing amounts of residual silica in the three cured materials. Four-coordinated Al existed not only in the aluminosilicate gel framework but also in a water-rich chemical environment with only a small amount of Si in proximity, likely in the alumina gel or possibly present as extra-framework Al in the aluminosilicate gel. The results demonstrate how the employment of different silica starting materials determines the phase assemblage of one-part alkali-activated materials, which in turn influences their engineering properties such as the resistance against chemically/biologically aggressive media. KW - Alkali-activated materials KW - Solid-state NMR KW - Aluminium hydroxide KW - Rice husk ash PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-469353 DO - https://doi.org/10.1039/C8RA09246J SN - 2046-2069 VL - 8 IS - 70 SP - 40164 EP - 40171 PB - Royal Society of Chemistry AN - OPUS4-46935 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Simoes, R. A1 - Bernades, C. A1 - Joseph, A. A1 - Piedade, F. A1 - Kraus, Werner A1 - Emmerling, Franziska A1 - Diogo, H. A1 - da Piedade, M. T1 - Polymorphism in simvastatin: Twinning, disorder, and enantiotropic phase transitions N2 - : Simvastatin is one of the most widely used active pharmaceutical ingredients for the treatment of hyperlipidemias. Because the compound is employed as a solid in drug formulations, particular attention should be given to the characterization of different polymorphs, their stability domains, and the nature of the phase transitions that relate them. In this work, the phase transitions delimiting the stability domains of three previously reported simvastatin forms were investigated from structural, energetics, and dynamical points of view based on single crystal X-ray diffraction (SCXRD), hot stage microscopy (HSM), and differential scanning calorimetry (DSC) experiments (conventional scans and heat capacity measurements), complemented with molecular dynamics (MD) simulations. Previous assignments of the crystal forms were confirmed by SCXRD: forms I and II were found to be orthorhombic (P212121, Z′/Z = 1/4) and form III was monoclinic (P21, Z′/Z = 2/4). The obtained results further indicated that (i) the transitions between different forms are observed at 235.9 ± 0.1 K (form III → form II) and at 275.2 ± 0.2 K (form II → form I) in DSC runs carried out at 10 K min−1 and close to these values when other types of techniques are used (e.g., HSM). (ii) They are enantiotropic (i.e., there is a transition temperature relating the two phases before fusion at which the stability order is reversed), fast, reversible, with very little hysteresis between heating and cooling modes, and occur under single crystal to single crystal conditions. (iii) A nucleation and growth mechanism seems to be followed since HSM experiments on single crystals evidenced the propagation of an interface, accompanied by a change of birefringence and crystal contraction or expansion (more subtle in the case of form III → form II), when the phase transitions are triggered. (iv) Consistent with the reversible and small hysteresis nature of the phase transitions, the SCXRD results indicated that the molecular packing is very similar in all forms and the main structural differences are associated with conformational changes of the “ester tail”. (v) The MD simulations further suggested that the tail is essentially “frozen” in two conformations below the III → II transition temperature, becomes progressively less hindered throughout the stability domain of form II, and acquires a large conformational freedom above the II → I transition. Finally, the fact that these transitions were found to be fast and reversible suggests that polymorphism is unlikely to be a problem for pharmaceutical formulations employing crystalline simvastatin because, if present, the III and II forms will readily convert to form I at ambient temperature. KW - Polymorphism KW - Twinning KW - Disorder KW - Simvastatine PY - 2018 DO - https://doi.org/10.1021/acs.molpharmaceut.8b00818 SN - 1543-8384 SN - 1543-8392 VL - 15 IS - 11 SP - 5349 EP - 5360 PB - American Chemical Society CY - Washington, DC AN - OPUS4-46927 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Broadband dielectric spectroscopy to study soft matter systems N2 - The basics of broadband dielectric spectroscopy were introduced in detail. The analysis of the data was discussed. As application of broadband dielectric spectroscopy the alpha-relaxation (dynamic glass transition) and the chain dynamics of polymers were ilustrated. Further the application of dielectric spectroscopy to polymerbased nanocomposites and high preformance polymers was discussed in detail. T2 - Kolloquiumsvotrag am Karlsruher Instiut of Technology CY - Karlsruhe, Germany DA - 05.12.2018 KW - Broadband dielectric spectroscopy PY - 2018 AN - OPUS4-46910 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Breitfeld, Steffen A1 - Scholz, Gudrun A1 - Emmerling, Franziska A1 - Kemnitz, Erhard 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 - 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 - Chapartegui, Ander A1 - Emmerling, Franziska A1 - Schneider, Rudolf 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 - Chapartegui, Ander A1 - Emmerling, Franziska A1 - Schneider, Rudolf 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 - Sobol, Oded A1 - Böllinghaus, Thomas T1 - BAM’s role in materials science and hydrogen in metals: TOF-SIMS imaging N2 - Due to its low mass and high diffusivity in presence of compositional, thermal and mechanical gradients, hydrogen within a metallic microstructure can result in severe loss in ductility even at low concentrations and might lead eventually to a catastrophic and unpredictable failure of structural components during service. In this context, hydrogen mapping at the microscale is still considered among the most important challenges on the pathway towards a better understanding of the hydrogen transport and assisted cracking phenomena in metals, specifically in structural components, e.g. steels. Among the very few available techniques to localize hydrogen at the microscale, Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a reliable tool. Based on the assumption that deuterium influence the microstructure similarly to hydrogen, in the following contribution ToF-SIMS was applied as the main technique to detect and locally map the deuterium distribution in several alloys: lean 2101 and standard 2205 duplex stainless steel (DSS), AISI 304L austenitic stainless steel and titanium 6Al-4V alloy. These alloys were selected as case studies in this work due to the wide use of them in many applications and environments which frequently provide critical conditions for hydrogen absorption and assisted degradation. The innovative design of in-situ and ex-situ experiments enabled us to elucidate the permeation, transport and trapping of deuterium in the microstructure in sub-micron resolution for the first time. In addition to the novel experimental setups, further progress was gained by applying computational multivariate data analysis (MVA) on the raw data and data fusion with high resolution structural characterization methods (scanning electron microscopy and electron back-scattered diffraction – SEM/EBSD). This combination allowed us to correlate the deuterium distribution and the influence on the microstructure. T2 - 4th Symposium on Innovative Measurement and Analysis for Structural Materials CY - Tokyo, Japan DA - 13.11.2018 KW - ToF-SIMS KW - Duplex stainless steel KW - Austenitic stainless steel KW - Principal Component Analysis KW - Data-fusion PY - 2018 UR - https://unit.aist.go.jp/tia-co/project/SIP-IMASM/sympo/2018/index.html AN - OPUS4-46867 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sobol, Oded T1 - Hydrogen assisted cracking phenomena in duplex stainless steels elucidated by in- and ex-situ ToF-SIMS experiments N2 - In the presented research, the high potential and abilities of secondary ion mass spectrometry (ToF-SIMS) to detect and locally map the hydrogen distribution in two types of duplex stainless steels are shown. The research validates certain proposed mechanisms by combining ToF-SIMS with high-resolution scanning electron microscopy and electron-backscattered diffraction. The combination of data from several techniques on the same region was conducted in this field for the first time by applying data treatment of the ToF-SIMS raw data and data fusion approach. This powerful combination of methods allows reviewing of the occurring processes related to hydrogen assisted cracking. The step beyond the state of the art in this field was gained here by developing permeation and mechanical loading experiments within the ToF-SIMS during chemometric imaging of the hydrogen distribution in the microstructure. The research presents the necessary correlation between the hydrogen distribution and the resulted structural changes, the diffusion behavior in a duplex microstructure and stress induced diffusion of hydrogen by applying external load at the microscale. T2 - 6th WMRIF Early Career Scientist Summit CY - NPL Teddington UK DA - 18.06.2018 KW - ToF-SIMS KW - Duplex stainless steel KW - LDX KW - EBSD KW - Data-fusion PY - 2018 AN - OPUS4-46865 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Jörg T1 - Sekundärstrahlungsemission bei der UKP-Laser-Anwendung: Herausforderung für die Arbeitssicherheit N2 - Im Vortrag werden die Risiken, insbesondere die unerwünschte Erzeugung von Röntgenstrahlung, bei der Nutzung ultrakurzer Laserimpulse in der Materialbearbeitung beschrieben. Neue Anforderungen an den Arbeitsschutz werden dargestellt. T2 - SPECTARIS, Deutscher Industrieverband für optische, medizinische und mechatronische Technologien e.V., Veranstaltung Technische Kommission Photonik CY - Berlin, Germany DA - 27.11.2018 KW - Ultrakurze Laserimpulse KW - Materialbearbeitung KW - Röntgenstrahlung KW - Arbeitsschutz PY - 2018 AN - OPUS4-46859 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Jörg T1 - Femtosecond laser-assisted photovoltaic bottom-up strategies N2 - A promising technology in photovoltaics is based on micro-concentrator solar cells, where the photovoltaic active area is realized as an array of sub-millimeter sized thin-film solar cells. Different approaches to produce micro-sized precursors of CIGSe absorbers on molybdenum are presented using 30-fs laser pulses at 790 nm wavelength. On the one hand, a multi pulse surface structuring of the molybdenum or the underlying glass substrate and a subsequent physical vapor deposition (PVD) process were used for a site-selective aggregation of indium droplets. On the other hand, a single pulse laser-induced forward transfer (LIFT) was utilized to selectively deposit combined copper/indium/gallium precursor pixels on the molybdenum back contact of the solar cell. It was demonstrated that a postprocessing of the laser-generated micro-sized precursors results in an array of working CIGSe solar cells with an efficiency of 2.9% for 1 sun Illumination. T2 - Leibniz-Institut für Oberflächenmodifizierung (IOM), Institutskolloquium CY - Leipzig, Germany DA - 29.11.2018 KW - Femtosecond laser patterning KW - Laser-induced forward transfer KW - CIGSe KW - Micro solar cell KW - Light concentration PY - 2018 AN - OPUS4-46831 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Abad Andrade, Carlos Enrique A1 - Florek, S. A1 - Becker-Ross, H. A1 - Huang, M.-D. A1 - de Oliveira Guilherme Buzanich, Ana A1 - Radtke, Martin A1 - Lippitz, Andreas A1 - Hodoroaba, Vasile-Dan A1 - Schmid, Thomas A1 - Heinrich, Hans-Joachim A1 - Recknagel, Sebastian A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - Zirconium permanent modifiers for graphite furnaces used in absorption spectrometry: understanding their structure and mechanism of action N2 - The mechanism of action of zirconium permanent modifiers on graphite surfaces was investigated in order to understand its influence on the analytical signal in atomic and molecular absorption spectrometry (AAS/MAS). For this, the molecule formation of CaF was studied, which is used for the indirect analytical determination of fluorine in high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). The kinetics of this reaction was established by monitoring its molecular spectrum at different atomisation temperatures. An Arrhenius plot showed a pseudo-first order reaction with respect to fluorine (n = 1). An intermediate state was isolated, and its structure was elucidated by spectroscopic methods: scanning electron microscopy with energy dispersive X-ray spectroscopy (SEMEDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XANES and EXAFS), and Raman microspectroscopy. We propose here a mechanism, where ZrO2 acts as a heterogeneous catalyst: after a pyrolytic step, an intermediate state of ZrO(OCaF) is activated, and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. No evidence of the formation of zirconium carbide was found. Consequently, as the CaF formation is catalysed by a heterogeneous catalyst, surface modifications with ZrO2 nanoparticles and ZrO xerogels were investigated in order to increase the surface area. Their influence was evaluated in the molecule formation of CaF, CaCl, CaBr, and CaI. Graphite furnace modification with zirconium oxide nanoparticles proves to be the best choice for fluorine analysis with a signal enhancement of more than eleven times with respect a non-coated graphite furnace. However, the influence of zirconium modifications in the analytical signals of Cl, and I is lower than the F signals or even negative in case of the Br. Understanding zirconium modifiers as heterogeneous catalysts offers a new perspective to AAS and MAS, and reveals the potential of surface analytical methods for development of improved permanent modifiers and graphite furnace coatings. KW - Zirconium KW - HR-CS-MAS KW - Graphite furnace KW - Nanoparticles KW - Xerogel KW - Calcium monofluoride KW - Absorption spectrometry PY - 2018 UR - https://pubs.rsc.org/en/content/articlelanding/2018/ja/c8ja00190a DO - https://doi.org/10.1039/C8JA00190A SN - 0267-9477 VL - 33 IS - 12 SP - 2034 EP - 2042 PB - Royal Society of Chemistry AN - OPUS4-46775 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 - Heinrich, Thomas T1 - BAM and Division 6.1 N2 - This is a short overview of BAM and Division 6.1. We have insight into BAM's roles and responsibilities and the work we are doing in Division 6.1. T2 - Visit at CSEM Landquart CY - Landquart, Switzerland DA - 13.08.2018 KW - ToF-SIMS KW - AES KW - XPS KW - SEM PY - 2018 AN - OPUS4-46765 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kunz, Valentin A1 - Kjaervik, Marit A1 - Müller, Anja A1 - Hodoroaba, Vasile-Dan A1 - Unger, Wolfgang T1 - How to meet new challenges in advanced nanoparticle analytics N2 - Three current research projects performed at BAM’s Division for Surface Analysis and Interfacial Chemistry are presented that tackle important challenges with regard to the characterization of nanomaterials: 1) The characterization at ambient pressure, 2) the investigation of core-shell nanoparticles, and 3) the characterization of non-spherical particles by electron microscopy. 1) Surface analytical techniques such as Photoelectron Spectroscopy (XPS) or Secondary Ion Mass Spectrometry (SIMS) typically require measurements in ultra-high vacuum. However, for many applications (e.g. catalysis and nanotoxicology) it is important to know the surface chemical properties of nanomaterials at ambient conditions. Therefore, near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) was used to investigate nanoparticles in suspension. The used instrumental set-up allows to directly insert nanoparticle suspensions into the analysis chamber and to measure without prior sample preparation. Compared to dry reference samples measured under high-vacuum, a shift towards higher binding energies was observed for silver nanoparticles in water, indicating a change of surface potential at the water-nanoparticle interface. 2) To determine the dimensions of core-shell nanoparticles (shell thickness, core and total diameter), scanning transmission X-ray microscopy (STXM) was used. The analyzed model system consists of a polytetrafluorethylene (PTFE) core surrounded by a polystyrene (PS) shell, providing a strong X-ray absorption contrast at the C K-edge and a well-defined interface. The introduced STXM‐based methodology yields particle dimensions in agreement with scanning electron microscopy (SEM) results and provides additional information such as the position of the particle core, which cannot be extracted from a SEM micrograph. 3) The accurate measurement of size distributions of non-spherically shaped nanoparticles (representing most of the industrial nanoparticulate materials) is a challenging analytical task. High-resolution electron microscopy (TEM and SEM) is best suited to access the shape of individual nanoparticles. To fill the gap between ideal, monodisperse particles of spherical shape and complex real-world samples, BAM has started the work to develop reference nanoparticles of controlled shape, such as TiO2 platelets, bipyramids, and elongated particles. Results of a recent ISO inter-laboratory comparison will be shown with emphasis on the measurement parameters, descriptors and data analysis. T2 - NanoSafe Conference 2018 CY - Grenoble, France DA - 5.11.2018 KW - Nanoparticles PY - 2018 AN - OPUS4-46730 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sachse, René A1 - Hertwig, Andreas A1 - Hodoroaba, Vasile-Dan A1 - Krähnert, R. T1 - Multi-method analysis of pore-controlled mesoporous oxide materials N2 - Determining the porosity of catalytic layers is crucial for quality assurance. We present results of a multi-method study to determine thickness, porosity, dielectric function and other properties of pure and mixed iridium and titanium oxide layers used in electrocatalytic water splitting. T2 - European Optical Society Biennial Meeting (EOSAM) 2018 CY - Delft, The Netherlands DA - 08.10.2018 KW - Multi-method analysis KW - Mesoporous oxide materials KW - Electro catalytic water splitting KW - Electron probe X-ray microanalysis (EPMA) KW - Spectroscopic ellipsometry (SE) KW - Optical porosimetry PY - 2018 AN - OPUS4-46740 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna A1 - Eisentraut, Paul A1 - Goedecke, Caroline A1 - Ricking, Mathias A1 - Bannick, Claus-Gerhard A1 - Braun, Ulrike T1 - Freshwater compartments: Screening method for polymer identification and mass contents of microplastic particles using TED-GC-MS N2 - The pathways of plastics, especially of microplastic (MP), in environmental compartments, particularly in aquatic systems, are not well understood. The critical point is the lack of fast, harmonised methods for sampling, sample preparation and sample analysis. These three analytical steps are dependent on one another and must be optimised. In recent years, we developed a method for representative sampling and fast detection of MP in aqueous systems. The sampling in different freshwater bodies is performed in the field with a fractionated filtration system using mesh sizes of 500, 100 and 50 µm. For water with an intermediate or high content of suspended particular matter a minimum of 1000 L has to be filtered. In the lab, mesh sizes of 10 and 5 µm are used for further filtration. Subsequently, the water filtrates of the different particle size classes are sterilised, dried, weighed and homogenised, if necessary. Conventional methods for MP analysis are infrared and raman spectroscopy, giving information on the shapes and numbers of individually identified MP particles. Our focus is on the determination of mass contents of various polymers potentially contained in environmental samples. For qualitative and quantitative MP detection TED-GC-MS is used, a two-step method based on gas chromatography-mass spectrometry (GC-MS) with previous thermal extraction. This method not only enables us to screen the samples for characteristic marker-molecules, thus identifying single polymers, but furthermore allows the calculation of mass contents of individual polymers. In the present work, different freshwater compartments were exemplarily studied to identify containing polymers and calculate their mass content in MP particles. T2 - MICRO2018 CY - Lanzarote, Spain DA - 19.11.2018 KW - Microplastic KW - TED-GC-MS KW - Mass contents PY - 2018 AN - OPUS4-46739 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sobol, Oded A1 - Röhsler, Andreas A1 - Nolze, Gert A1 - Unger, Wolfgang A1 - Böllinghaus, Thomas T1 - Sputtering derived artefacts in austenitic steel during Time-of-Flight Secondary Ion Mass Spectrometry analyses N2 - Among the very few techniques to localize hydrogen (H) at the microscale in steels, Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a reliable tool. The necessity to detect hydrogen stems from its deleterious effects in metals, that are often used as structural components and to obtain better understanding of the underlying metallurgical mechanisms of hydrogen embrittlement (HE) which are still unclear. Austenitic stainless steels are nowadays commonly used in a wide variety of application, from hydrogen transport and storage facilities to petrochemical and offshore applications where they are exposed to aggressive environments and therefore prone to HE. One of the greater risks in the austenitic class is the embrittlement of the material due to the instability of the γ austenite and its transformation into a brittle α martensitic phase. This transformation takes place due to the local stresses that are induced by the uptake of hydrogen during service. Nonetheless, it was shown that this transformation can occur as an artefact during SIMS analysis itself where Cs-sputtering is necessary not only to remove surface contaminations but mainly to enhance H/D secondary ion yield. In the following contribution we show the influence of different sputtering conditions on AISI 304L austenitic stainless steel in order to distinguish the artefact from the hydrogen induced transformation. The material was charged electrochemically in a deuterium based electrolyte. Deuterium (D) must be in these experiments as a replacement for hydrogen which cannot be used because adsorbed hydrogen superimposes hydrogen originating from charging the sample in the SIMS images. ToF-SIMS analyses were conducted by ToF SIMS IV (IONTOF GmbH, Münster, Germany). The experiments were carried out on deuterium charged and non-charged samples. The structural characterization was carried out by SEM and EBSD examinations before and after charging, both with a Leo Gemeni 1530VP field-emission scanning electron microscope and a Zeiss Supra 40 instrument (Carl Zeiss Microscopy GmbH, Oberkochen, Germany). The results showed that the use of 1keV Cs+ beam induces stacking faults while higher sputter beam energies results in γ→α transformation. T2 - SIMS Europe 2018 CY - Münster, Germany DA - 16.09.2018 KW - Austenitic steel KW - Hydrogen KW - ToF-SIMS KW - Artefact PY - 2018 AN - OPUS4-46701 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kricheldorf, H. T1 - Transesterification in alcohol-initiated ROPs of l- and meso-lactide catalyzed by Sn(II) and Sn(IV) compounds at low temperatures N2 - The purpose of this study is to shed more light on the transesterification processes in alcohol-initiated and tin(II) 2-ethylhexanoate (SnOct2)-catalyzed polymerizations of lactides at low or moderate temperatures. Ethanol-initiated polymerizations are conducted in concentrated solutions at 80 °C and a strong dependence of even/odd equilibration on the alcohol/Sn ratio. Around or above 120 °C cyclization of poly(l-lactide) via “backbiting” occurs as a third mechanism. However, poly(m-lactide) shows a higher cyclization tendency and yields cyclics even at 100 °C. Combinations of ethanol and certain cyclic dibutyltin(IV) catalysts also yield cyclic oligomers of l-lactide at 80 °C. Reaction conditions allowing for a total suppression of all transesterification reactions are not found, but even-numbered poly(m-lactide)s with a purity >95% are obtained at 70 or 60 °C. KW - Cyclization KW - MALDI-TOF MS KW - Polyester KW - Polylactide KW - Transesterification PY - 2018 DO - https://doi.org/10.1002/macp.201800445 SN - 1022-1352 SN - 1521-3935 VL - 219 IS - 24 SP - 1800445, 1 EP - 10 PB - Wiley-VCH CY - Weinheim AN - OPUS4-46705 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Thin polymer films as model systems for polymer nanocomposites N2 - Polymers at interfaces play a major role in a broad variety of applications ranging from engineering purposes (for instance polymer based nanocomposites) to high tech implications (for instance light emitting diodes). Here, thin films with thicknesses down to few nanometers are prepared on different substrates as model systems for polymer composites. The thin films are investigated by a combination of surface analytical and volume sensitive methods. As surface analytical methods atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and contact angle measurements (CAM) are employed. As volume sensitive broadband dielectric spectroscopy (BDS), specific heat spectroscopy (SHS), and ellipsometry are used. Especially attention is paid to understand the glass transition behavior of thin films because the glass transition is the key phenomenon determines the application of polymers also in thin films. To understand the glass transition behavior of thin films, which is controversially discussed in literature, a three layer model is discussed. Firstly, a mobile surface layer is assumed at polymer air interface of the film due to missing of segment/segment interactions. Secondly, in the middle of the film a bulk-like layer should be expected. Thirdly, for polymers having non-repulsive interactions with the substrate an irreversibly adsorbed layer is expected to be formed. Due the adsorption the molecular mobility of the segments in this layer is slowed down. What is measured for the glass transition of thin films is a complicated average of all of these effects. The different layers are hardly to address separately. Therefore, in the presentation especially model systems are selected and investigated to verify the layer model. T2 - Kolloquiumsvortrag and der Universität des Saarlandes CY - Saarbrücken, Gemany DA - 20.11.2018 KW - Thin polymer films PY - 2018 AN - OPUS4-46692 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Schönhals, Andreas A1 - Zorn, R. T1 - Quasi-elastic scattering of high free volume polymers by neutron time-of-flight spectroscopy N2 - Experimental report to proposal 13562 Quasi-elastic scattering of the polymer with intrinsic microporoasity PIM-1 is measured by neutron time-of-flight spectroscopy and discussed. KW - Neutron scattering KW - PIM-1 PY - 2018 SP - 1 EP - 2 CY - Garching AN - OPUS4-46693 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Müller, Anja A1 - Radnik, Jörg A1 - Lippitz, Andreas A1 - Unger, Wolfgang T1 - Progress Talk 3 / Non-destructive depth profiling of core-shell nanoparticles by ER-XPS N2 - This presentation deals with the progress between month twenty and twenty-nine of my PhD thesis. I prepared it, in order to update my supervisor Prof. Kemnitz and my colleagues from the department of chemistry at the Humboldt-Universität zu Berlin (HU). T2 - Working Group Meeting of Prof. Erhard Kemnitz CY - Humboldt-Universität zu Berlin (HU), Germany DA - 20.11.2018 KW - ER-XPS KW - Synchrotron KW - Core-shell nanoparticles KW - Depth-profiling PY - 2018 AN - OPUS4-46676 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Goedecke, Caroline A1 - Altmann, Korinna A1 - Eisentraut, Paul A1 - Bannick, C. G. A1 - Braun, Ulrike T1 - Mikroplastik - Suchen und Finden N2 - Der Vortrag stellt spektroskopische und neue thermoanalytische Verfahren zum Nachweis von Mikroplastik in Umweltproben vor. Ein spezieller Fokus liegt auf dem neu entwickelten Verfahren der TED-GC-MS. Zusätzlich wird gezeigt, wie die TED-GC-MS eingesetzt werden kann, um Reifen in der Umwelt zu bestimmen. T2 - Fachforum Ressourcen - Kunststoffe und Nachhaltigkeit CY - Leverkusen, Germany DA - 06.11.2018 KW - Mikroplastik KW - TED-GC-MS KW - Thermoanalytische Verfahren KW - Spektroskopische Verfahren PY - 2018 AN - OPUS4-46652 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brandl, F. A1 - Thünemann, Andreas A1 - Beuermann, S. T1 - Poly(meth)acrylate-PVDF core–shell particles from emulsion polymerization: preferential formation of the PVDF β crystal phase N2 - A facile and convenient approach for the synthesis of core–shell particles via emulsion polymerization is presented. The shell consists of poly(vinylidene fluoride) (PVDF) and the core of poly(methyl methacrylate) (PMMA), poly(glycidyl methacrylate) (PGMA) or poly(methyl acrylate) (PMA). In a first step, a non-fluorinated (meth)acrylate monomer is polymerized in the emulsion to produce poly(meth)acrylate core particles. Secondly, vinylidene fluoride (VDF) is directly added to the reactor and polymerized for shell formation. Small-angle X-ray scattering (SAXS) was employed to characterize the structure of the core–shell particles. Interestingly, the particles’ core contains fluorinated and non-fluorinated polymers, whereas the shell of the particles consists only of PVDF. The resulting particles with a diameter of around 40 nm show a significantly higher PVDF β phase content than the PVDF homopolymer obtained by emulsion polymerization KW - Small-angle x-ray scattering KW - SAXS KW - Nanopatricle KW - Polymer PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-465910 DO - https://doi.org/10.1039/C8PY01236A SN - 1759-9954 SN - 1759-9962 VL - 9 IS - 44 SP - 5359 EP - 5369 PB - The Royal Society of Chemistry AN - OPUS4-46591 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schütter, Jan T1 - Tailored Micro- and Nanostructured Surfaces for Bacterial Attachment Studies N2 - To investigate the attachment behavior of bacteria, tailored surfaces are needed. Differences in the chemical charge of the substrate are varied by -COO-, -CH3, -OH, -NH3 terminated functional groups. Regular patterns of them on the surfaces enable bacteria to choose their preferred attachment sides. Tools to tailor the samples are µ-contact printing, self-assembled monolayers and physical vapor deposition. The same concept of preferred sides in patterned surfaces is transferred to the nano- and microroughness which is accomplished by using zinc oxide nanorods synthesis. T2 - PhD Retreat CY - Warnemünde, Germany DA - 28.09.2018 KW - ZnO nanorods KW - µ-contact printing KW - Surface modification KW - Microbial induced corrosion PY - 2018 AN - OPUS4-46577 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hodoroaba, Vasile-Dan T1 - Nanoanalytik-Aktivitäten @ BAM N2 - In dieser Präsentation werden Aktivitäten im Bereich der 'nano'-Charakterisierung bei der BAM vorgestellt. Beispiele von F&E-Projekten und -Kooperationen im nano-Analytik-Bereich bei der BAM werden genannt. Thematische Kooperations-Möglichkeiten zwischen BAM und dem Netzwerk NanoAnalytik und -Messtechnik in der Produktion werden diskutiert. T2 - Treffen des Netzwerkes NanoAnalytik und -Messtechnik CY - Berlin, Germany DA - 06.11.2018 KW - Nanoanalytik KW - Nano-Projekte KW - Nano-Kompetenzzentrum KW - Nano-Charakterisierung PY - 2018 UR - https://www.nanoinitiative-bayern.de/nanoanalytik/ AN - OPUS4-46563 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Müller, Anja A1 - Unger, Wolfgang A1 - Wirth, Thomas A1 - Kjaervik, Marit A1 - Cant, D. A1 - Shard, A. A1 - Clifford, C. T1 - Measurement of the thickness and nature of nanoparticle coatings - ISO/PWI TR 23173 N2 - This presentation explains the outline and scientific content of the ISO technical report 23173 "Measurement of the thickness and nature of nanoparticle coatings using electron spectroscopies". This technical report deals with those electron spectroscopy methods that are able to determine the coating thickness of nanoparticles. This specifically includes X-ray photoelectron spectroscopy (XPS), energy-resolved X-Ray photoelectron spectroscopy (ERXPS) using synchrotron radiation, near abient pressure photoelectron spectroscopy (NAPXPS) and Auger electron spectroscopy (AES). T2 - 18. Sitzung des DIN-Normenausschusses 062-08-16 AA CY - Berlin, Germany DA - 08.11.2018 KW - Core-shell nanoparticles KW - Electron spectroscopy KW - XPS KW - Synchrotron radiation KW - AES PY - 2018 AN - OPUS4-46550 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kjaervik, Marit A1 - Unger, Wolfgang T1 - New work item proposal for a technical report for ISO/TC 201 WG4 “Surface characterization of biomaterials”: Surface chemical analysis – Surface chemical analysis of cells and biofilms N2 - The proposed ISO Technical Report provides a description of a variety of physical methods of analytical chemistry by which bacteria and biofilms can be analysed. The state of the art, sample requirements and strengths associated with each method are identified. Presented at the DIN-meeting for NA 062-08-16 AA „Chemische Oberflächenanalyse und Rastersondenmikroskopie“ T2 - 18. Sitzung des DIN-meeting NA 062-08-16 AA "Chemische Oberflächenanalyse und Rastersondenmikroskopie“ CY - Berlin, Germany DA - 08.11.2018 KW - 3D nano SIMS KW - Fourier transform infrared spectroscopy KW - Raman-spectroscopy KW - Biofilms KW - XPS PY - 2018 AN - OPUS4-46548 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -