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 - Božičević, Lucija A1 - Altmann, Korinna A1 - Hildebrandt, Jana A1 - Knigge, Xenia A1 - Vrček, Valerije A1 - Peranić, Nikolina A1 - Kalcec, Nikolina A1 - Vinkovic Vrcek, Ivana T1 - Estrogenic activity of plastic nanoparticles mixture under in vitro settings N2 - The plastic value chain, central part of modern living, caused environmental pollution and bioaccumulation of plastic nanoparticles (PNPs). Their ubiquitous presence in different environmental and biological compartments has become a serious threat to human health and ecosystems. Frequently used plastic materials such as polypropylene (PP), polystyrene (PS) and polyethylene (PE) have been detected in the form of PNPs in the food chain, soil, water and air, as well as in human feces and blood. In this study, we aimed to provide novel insights in endocrine disrupting properties of PNPs using in vitro estrogen receptor (ER) transactivation assay. The effects of PP-NPs, PE-NPs and PS-NPs and their mixture on T47D-KBluc cell line stably transfected with luciferase as reporter enzyme was evaluated by means of cytotoxicity, cellular uptake and ER activation. Tested dose range for PNPs was 0.001 – 10 mg/L. Both cellular uptake and cytotoxicity for all PNPs was found to be dose-dependent. Only the highest dose of PP-NPs and PE-NPs induced apoptosis and cell death, while PS-NPs were not cytotoxic in tested dose range. For tested concentrations, PP-NPs and PE-NPs showed significant agonistic activity on ER, while PS-NPs cannot be considered ER active. When, applied as mixture, PNP demonstrated additive toxicity effects compared to the effect of each individual PNPs. Additivity was also observed for ER agonistic effect of PNPs mixture according to the benchmark dose-addition modelling approach. This study provides missing science-based evidence on endocrine disrupting effects of PE-NPs, PP-NPs, PS-NPs and their mixtures and highlights the importance of considering unintentional, aggregate and combined exposure to different PNPs in risk management. KW - Risk assessment KW - Nanoplastics KW - Estrogenic activity of plastic nanoparticles PY - 2024 DO - https://doi.org/10.1039/D3EN00883E SN - 2051-8153 VL - 11 IS - 5 SP - 2112 EP - 2126 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59724 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 - Weber, Simone T1 - Influence of the pH Value to the Degradation of Ester-Based Thermoplastic Polyurethanes N2 - Microplastics are solid polymeric particles with a size of 1-1000 μm (ISO/TR21960:2020), which can be emitted from mismanaged waste into the environment, where microplastic is now ubiquitous. What happens to the microplastics after ending up in the environment, which risks entail and what effects it has are not sufficiently clarified up to now. The most certain issue is that the plastic particles in the environment are exposed to natural ageing, are fragmenting and degrading, such that the potential risk to ecosystems and humans is increasing due to the formation of smaller and smaller particles, potentially even including nanoplastics, if these are ingested before their further degradation. Therefore, and in view of a possible registration of polymers under REACH in the future, it is necessary to investigate the degradation of thermoplastic polyurethanes (TPU) regarding hydrolysis stability to evaluate possible risks and effects to the environment. In the present studies, one thermoplastic polyurethane – with and without hydrolysis stabilizer – is exposed to different pH buffers at 50°C for 14 days to investigate hydrolysis depending to different pH values (acid, alkali and neutral) based on OECD guideline TG111. The hydrolysis behavior of the TPUs is characterized by surface sensitive techniques and on bulk properties. First degradation effects can be detected by SEC. Hydrolysis, especially under acidic and basic conditions, leads to chain scissions to lower molecular masses. Furthermore, the degradation products which indicate the structure of the bulk material were detected by thermo-analytical methods like TGA-FTIR for the small degradation products and the thermo extraction/desorption-gaschromatography/mass spectrometry (TED-GC/MS) for bigger degradation products. Acidic and basic hydrolysis shows the same degradation behavior which is caused by a preferred scission of the ester and urethane functionalities. Surface-sensitive techniques such as XPS demonstrate less carboxylic acid formation at acidic than at alkaline pH value in the TPU without stabilator, where as the TPU with stabilator ages to the same extent in both pH ranges. Altogether, the hydrolysis of TPUs – independently of added stabilizer or not – in acid and alkali environment is accelerated compared to the neutral hydrolysis. T2 - SETAC CY - Dubin, Ireland DA - 30.04.2023 KW - Degradation KW - Thermoplastic Polyurethane KW - Microplastic KW - Polymer Hydrolysis KW - Polymer 3R KW - REACH PY - 2023 AN - OPUS4-58906 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 - CONF A1 - Moss, Caitlin T1 - Mechanochemistry as a Green Synthetic Route N2 - Mechanochemistry has emerged as a transformative approach in sustainable chemistry, offering a solvent-free and energy-efficient pathway for chemical synthesis. By utilizing mechanical force—typically through ball milling, grinding, or other shear-driven methods, reactions can proceed without the extensive use of harmful solvents, reducing waste and environmental impact. This poster explores the principles, methodologies, and applications of mechanochemistry in developing greener synthetic routes, with a focus on pharmaceutical and materials science applications. Key advantages, including reduced reaction times, enhanced selectivity, and improved atom economy, will be highlighted alongside challenges such as scalability. By presenting mechanochemistry as a frontier technology at the intersection of chemistry, materials science, and environmental stewardship, this work invites dialogue among students and academics about its future in sustainable innovation. T2 - Furture WINS 2024 CY - Berlin, Germany DA - 21.11.2024 KW - Mechanochemistry KW - Green chemistry PY - 2024 AN - OPUS4-62123 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - Synthesis of zirconiumfluorides using a sol-gel/postfluorination approach and their application in C-F bond activation N2 - ZrF4 species have shown to exhibit hard Lewis acidity in homogeneous systems. In order to study solid state Lewis acidic ZrF4 a sol-gel synthesis was adapted following previous approaches for AlF3 and a necessary post fluorination is being optimised to obtain a Lewis acidic heterogeneous catalyst for C-F bond activation. The influence of different Zr precursors was also studied while the local coordination sphere of a active species was found to be similar to β-ZrF4 using EXAFS of the Zr K-edge. T2 - RSC Twitter Poster Conference 2023 CY - Online meeting DA - 28.02.2023 KW - ZrF4 KW - Heterogeneous catalysis PY - 2023 AN - OPUS4-57227 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nag, Sayak A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Ghosh, Soumyajit T1 - Stress and Light-Induced Dual Mechanical Properties of Two 1,3-Dicyanostilbene Derivative Crystals N2 - Dynamic molecular crystals with multistimuli responses hold immense potential for applications as actuators and smart materials. Here, we report two new 1,3-dicyanostilbene derivative crystals (crystals 1 and 2), which exhibit dual mechanical responses. Both crystals 1 and 2 demonstrate stress-induced mechanical flexibility and light-induced photomechanical bending upon exposure to a 375 nm UV LED. These two distinct mechanical responses are associated with different underlying phenomena and are independent of each other. Mechanical flexibility is attributed to the absence of slip planes and a criss-cross packing arrangement in an isotropic structure, while photomechanical bending is ascribed to the formation of a heterogeneous phase distribution due to Z → E photoisomerization. However, they show thermal reversibility, pointing toward a reversible E → Z back isomerization. This study demonstrates that single molecular crystals combining mechanical flexibility and photomechanical bending can be designed and fabricated for developing multistimuli responsive actuators. KW - Photoisomerization KW - Crystal structure KW - Crystals KW - Flexibility KW - Molecules PY - 2025 DO - https://doi.org/10.1021/acs.cgd.5c00097 SN - 1528-7483 SP - 1 EP - 11 PB - American Chemical Society (ACS) AN - OPUS4-63267 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Cirkovic Velickovic, T. A1 - Altmann, Korinna A1 - Dailey, L T1 - CUSP Conference WG1 & WG3: MATERIALS AND METHODS N2 - This talk is a presentation about the main results of the CUSP cluster on micro- and nanoplastics human health that work from 2021 to 2025 in Horizon Europe programme according to the WG1 and 3. These groups combined the analytics and the materials with interlaboratory comparisons (ILC). The talk reflects the need of realistic test materials with defined properties for micro- and nanoplastic research. Some were developed are now available. The talk also highlights the need for harmonisation and the results of different ILCs that were performed. T2 - CUSP conference CY - Brussels, Belgium DA - 25.02.2025 KW - Microplastics KW - Reference materials KW - Interlaboratory comparison (ILC) PY - 2025 AN - OPUS4-62703 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Casali, Lucia T1 - Kinetics of the mechanically induced ibuprofen-nicotinamide co-crystal formation by in-situ X-ray diffraction N2 - Mechanochemistry offers sustainable synthesis for pharmaceuticals, though scaling remains challenging. By combining time-resolved in situ X-ray diffraction with kinetic modeling on the mechanosynthesis of the co-crystal ibuprofen-nicotinamide, we identified the reaction-driving factors. This deeper insight opens the way for a scale-up of mechanochemistry in the pharmaceutical industry. T2 - CGOM15 (15th International Workshop on Crystal Growth of Organic Materials) CY - Phuket, Thailand DA - 23.07.2024 KW - Mechanochemistry KW - Kinetics KW - In-situ monitoring PY - 2024 AN - OPUS4-61756 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Miliūtė, Aistė T1 - How experimental and computational methods allow us to design negative thermal expansion materials N2 - Combined experimental and computational methods allow comprehensive understanding, design, and tailoring of material properties. We focus on a well-known negative thermal expansion (NTE) material, zirconium vanadate (ZrV2O7), and address synthesis, characterisation and validation of results with computational simulations. Experimental and computational X-ray diffraction and Raman spectroscopy data highlighted differences between phase-pure and multiphase ceramics. These techniques allowed us to distinguish subtle differences in the structure of the material. Based on ab initio simulated phonon data, unaffected by impurities or instrumental errors, we could interpret the Raman spectra and visualise Raman active atom vibrations. These computational models allowed better insight and further experimental improvement while high-quality experimental data granted the validation and improvement of computational simulation strategy. T2 - Application of Neutrons and Synchrotron Radiation in Engineering Materials Science CY - Hamburg, Germany DA - 23.03.2025 KW - NTE KW - Sol-gel KW - Ab initio KW - Raman KW - XRD PY - 2025 AN - OPUS4-62832 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Casali, Lucia T1 - Kinetics of the mechanically induced ibuprofen-nicotinamide co-crystal formation by in-situ X-ray diffraction N2 - Mechanochemistry offers sustainable synthesis for pharmaceuticals, though scaling remains challenging. By combining time-resolved in situ X-ray diffraction with kinetic modeling on the mechanosynthesis of the co-crystal ibuprofen-nicotinamide, we identified the reaction-driving factors. This deeper insight opens the way for a scale-up of mechanochemistry in the pharmaceutical industry. T2 - BESSY User meeting CY - Berlin, Germany DA - 11.12.2024 KW - Mechanochemistry KW - Kinetics KW - In-situ monitoring PY - 2024 AN - OPUS4-62193 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - de Oliveira Guilherme Buzanich, Ana T1 - Time resolved in situ monitoring of mechanochemical transformations by X-ray spectroscopy (XAS) N2 - Mechanochemical reactions promise a new direction for environmentally benign preparation of materials, and has been dubbed by IUPAC as one of the 10 chemical innovations that will change our world. Despite this significant promise, very little is known about the mechanisms that drive mechanochemical transformations, posing significant barriers to realizing their full potential. To this end, there is growing need to follow mechanochemical reactions in situ and in real time. We here describe advances in the development and application of XAS methods to monitor material synthesis in real time under mechanochemical conditions. We demonstrate the generality of our approaches by describing mechanochemical syntheses of materials by both vibratory ball milling and by Resonant Acoustic Mixing (RAM), where a time resolution of 1 second is for a whole XAS spectrum was achieved. Moreover, we describe how spectroscopic methods can be coupled to diffraction-based approaches, thereby providing new dimensions in understanding mechanochemical synthesis. T2 - AfLS3 CY - Online meeting DA - 14.11.2021 KW - Dipsersive XAS KW - Mechanochemistry KW - Time-resolved KW - In situ PY - 2021 AN - OPUS4-56256 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Detektion von Mikroplastik N2 - In dem Vortrag geht es um die Möglichkeiten der Detektion von Mikroplastik im Allgemeinen. Es werden Beispiele für die Luft gezeigt. T2 - VDI-Workshop „Mikroplastik in der Außenluft – Was wir wissen und was wir (noch) nicht wissen CY - Online meeting DA - 15.11.2022 KW - Mikroplastik KW - Mikroplastik in Luft KW - Detektion von Mikroplastik PY - 2022 AN - OPUS4-56289 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Waniek, Tassilo T1 - MNP test and reference material production N2 - Reference materials are essential to analyze the impact of micro- and nanoplastics. The particle size D50 has been chosen as property of interest. They can be produced top-down by milling. For size separation down to a particle size D50 of 50 µm sieving is suitable while smaller particle sizes can be obtained by filtration. After production it is important to control the stability because microplastic in the size range below 10 µm tend to agglomerate. T2 - CUSP early-stage researchers meeting CY - Online meeting DA - 08.11.2022 KW - Particale size KW - Microplastic KW - Reference material KW - Cryo milling KW - Polymer PY - 2022 AN - OPUS4-56214 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ciornii, Dmitri T1 - Micro- and Nanoplastics: from physico-chemical properties to reference products N2 - In this presentation we demonstrate the importance of physico-chemical properties (pc) of micro- and nanoplastic particles (MNPs). These properties determine interaction between MNPs and cells or living organisms. To perform accurate experiments for acquiring pc information it is essential to develop well-characterized and understood plastic reference materials. Such reference materials can be used in interlaboratory comparisons (ILCs). BAM is organizing under VAMAS two ILCs, on micro- and nanoplastics to obtain reliable results and methodologies for pc characterization of MNPs. By gaining profound knowledge on pc properties it becomes possible to estimate the impact of MNPs on the humans and environment and therefore to translate the knowledge to the level of regulation. T2 - CUSP early-stage researchers meeting CY - Online meeting DA - 08.11.2022 KW - Micro- and nanoplastics KW - Plastic reference materials KW - Interlaboratory Comparisons PY - 2022 AN - OPUS4-56330 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Karafiludis, Stephanos T1 - Evolution of mesoporous frameworks from precipitated struvite-structured metal phosphate materialsls N2 - Mesoporous transition metal phosphates (TMPs) have attracted major interest due to their high (electro-)catalytic activity suitable for H2 generation, supercapacitors or batteries. Typically, mesoporous materials are synthesized via a template-based route. This way is in the case of TMP because the surfactants used are difficult to remove due to the sensitivity of the mesoporous framework. We present a template-free method including the formation of a precursor phase called M-struvite (NH4MPO4•6H2O, M = Mg2+, Ni2+, Co2+, Ni2+xCo2+1-x) to synthesize mesoporous and amorphous metal phosphates. This method relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneous mesoporous phase associated with the degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the coordination metal coordination environment was followed with diffraction and spectroscopy based in-situ and ex-situ methods. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions between the chemical systems. In a complex amorphous structure, thermal decomposed Mg-, Ni- and NixCo1-x-struvites exhibit high surface areas and pore volumes for phosphate materials with a spherical to channel-like pore geometry (240 m²g-1 and 0.32 cm-3 g-1 for Mg and 90 m²g-1 and 0.13 cm-3 g-1 for Ni). In addition to this low-cost, environmentally friendly and simple synthesis, M-struvites could grow as a recycling product from industrial and agricultural wastewaters. These waste products could be upcycled through a simple thermal treatment for further applications. T2 - SNI 2022 - German Conference for Research with Synchrotron Radiation, Neutrons and Ion Beams at Large Facilities CY - Berlin, Germany DA - 05.07.2022 KW - Struvite KW - Transition metal KW - Phosphate KW - Amorphous phases KW - Mesoporosity PY - 2022 AN - OPUS4-55911 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Braun, U. T1 - Thermoanalytical methods to measure mass in microplastics N2 - The talk adresses the use of thermoanalytical methods in microplastics analysis. T2 - EUROLAB webinar: MICROPLASTICS: regulations, standards and the role of laboratories CY - Online meeting DA - 15.02.2023 KW - TED-GC/MS KW - Thermoanalytical methods KW - Microplastic mass PY - 2023 AN - OPUS4-57009 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heilmann, Maria T1 - Size-Tunable Ni-Cu Core-Shell Nanoparticles: Structure, Composition, and Catalytic Activity N2 - Nanoparticles (NPs) have become important materials for a variety of chemical technologies, including catalysis. One of the main challenges is the reduction of green house gases, such as CO2. One opportunity besides the capturing is the conversion to synthesis gas via the reverse water-gas shift reaction. A facile and efficient method is described for the solvothermal synthesis of size-tunable, stable, and uniform NiCu core-shell NPs. The diameter of the NPs can be tuned in a range from 6 nm to 30 nm and the Ni:Cu ratio from 30:1 to 1:1. The NPs are structurally characterized with combination of transmission electron microscopy, anomalous small-angle X-ray scattering, X-ray photoelectron spectroscopy, and X-ray absorption fine structure. Using these analytical methods, a core-shell-shell structure their chemical composition is elucidated. A depletion from the core to the shell is observed, with the core consisting of NiCu alloy, surrounded by an inner Ni-rich shell and an outer NiO shell. The SiO2-supported NiCu core-shell NPs show pronounced selectivity of >99% for CO in the catalytic reduction of CO2 to CO using hydrogen as reactant (reverse water–gas shift reaction). T2 - Nanoalloys: recent developments and future perspectives Faraday Discussion CY - London, UK DA - 21.09.2022 KW - Nanoparticles KW - Core-shell KW - Catalysis PY - 2022 AN - OPUS4-56831 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Release of synthetic fibres during washing of typical household textiles: Findings from washing machine tests and resulting policy recommendations N2 - This talk summarizes the experimental setup and the results of one washing experiment under realistic conditions according to microplastic fiber release. T2 - Tackling microplastics in the environment CY - Brussels, Belgium DA - 09.03.2023 KW - Microplastics KW - Fibers of textile origin KW - Washing machine KW - Microplastic fibre release PY - 2023 AN - OPUS4-57204 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Linberg, Kevin T1 - Polymorphism in molecular cocrystals controlled by variable temperature ball milling N2 - Mechanochemistry offers a unique opportunity to modify or synthesize new crystal forms. Although the method is very promising, little is known about the mechanochemical means to control the synthesis of a solid form. Using an polymorphic organic cocrystal system, we show here that mechanochemistry can be used to obtain a polymorph transformation under the apparently conventional (thermal) transition point. T2 - Bessy User Meeting 2022 CY - Online meeting DA - 08.12.2022 KW - Mechanochemistry KW - Polymorphism KW - TRIS PY - 2022 AN - OPUS4-56473 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Karafiludis, Stephanos T1 - How do transition metal phosphates crystallise? N2 - Industrial and agricultural waste streams (waste waters, sludges, tailings etc.), which contain high concentrations of NH4+, PO43- and transition metals, are environmentally harmful due to their toxic pollutants. At the same time, phosphorus and selective transition metals such as Cobalt could be potentially depleted as a critical raw material due to the high demand and rapidly declining natural ore deposits. Therefore, due to simultaneous scarcity and abundance, the phosphorus and 3d metal recovery from agricultural, industrial, mining, or urban wastewaters have been an important factor in sustaining our global consumption and preservation of the natural environment. Typically, separate pathways have been considered to extract hazardous substances such as transition metals or phosphate, independently from each other. Here, we investigate the crystallization of transition metal phosphate (TMP) compounds (NH4MPO4∙6H2O, M3(PO4)2∙8H2O with M = Ni2+, Co2+, NixCo1-x2+ M-struvite and M-phosphate octahydrate) out of aqueous solutions, which allow for P, ammonia and metal co-precipitation. The precipitation of these compounds from industrial and agricultural waste waters has high potential as a P- and 3d metal recovery route. For this purpose, a detailed understanding of the crystallization process beginning from combination of solved ions and ending in a final crystalline product is required. Through adjusting the reaction conditions, the stability, crystallite size and morphology of the as-obtained TMPs could be controlled. Detailed investigations of the precipitation process in time using ex- and in-situ techniques provided new insights into their non-classical crystallization mechanism/crystal engineering of these materials. These TMPs involve transitional colloidal nanophases during the crystallization process. Over time, their complex amorphous framework changes significantly resulting simultaneously in an agglomeration and densification of the compound. After extended reaction times these colloidal nanophases condensed to a final crystal. However, the reaction kinetics of the formation of a final crystalline product and the lifetime of these intermediate phases vary significantly depending on the metal cation involved in the precipitation process. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P)-ratios, whereas Co tends to form Co-struvite and/or Co-phosphate octahydrate depending on the (M/P)-ratio. The mixed NixCo1-x system shows a significantly different crystallization behavior and reaction kinetics of the precipitation compared to the pure endmembers. The observed various degree of stability could be linked to the octahedral metal coordination environment in these compounds. The achieved level of control over the precipitates, is highly desirable for 3d- and P-recovery methods. Under this paradigm, the crystals can be potentially upcycled as precursor materials for (electro)catalytical applications. T2 - Granada Münster Discussion Meeting (GMDM) CY - Granada, Spain DA - 30.11.2022 KW - Struvite KW - Transition metal KW - Phosphates KW - Amorphous phases KW - Non-classical crystallization PY - 2022 AN - OPUS4-56478 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Karafiludis, Stephanos T1 - Crystallization study of transition metal phosphates: a new example for non-classical crystallization theory N2 - Industrial and agricultural waste streams (waste waters, sludges, tailings etc.), which contain high concentrations of NH4+, PO43- and transition metals, are environmentally harmful due to their toxic pollutants. At the same time, phosphorus and selective transition metals such as Cobalt could be potentially depleted as a critical raw material due to the high demand and rapidly declining natural ore deposits. Therefore, due to simultaneous scarcity and abundance, the phosphorus and 3d metal recovery from agricultural, industrial, mining, or urban wastewaters have been an important factor in sustaining our global consumption and preservation of the natural environment. Typically, separate pathways have been considered to extract hazardous substances such as transition metals or phosphate, independently from each other. Here, we report the synthesis routes for transition metal phosphate (TMP) compounds (M3(PO4)2∙8H2O, NH4MPO4∙6H2O, M = Ni2+, Co2+, NixCo1-x2+ M-struvite and M-phosphate octahydrate), which allow for P, ammonia and metal co-precipitation. The precipitation of these compounds from industrial and agricultural waste waters could be a promising P-recovery route. Through adjusting the reaction conditions, the stability, crystallite size and morphology of the as-obtained TMP could be controlled. Detailed investigations of the precipitation process using ex- and in-situ techniques provided new insights into their non-classical crystallization mechanism/crystal engineering of these materials. These TMPs involve transitional colloidal nanophases which subsequently aggregate and condense to final crystals after extended reaction times. However, the reaction kinetics of the formation of a final crystalline product vary significantly depending on the metal cation involved in the precipitation process. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P)-ratios, whereas Co tends to form Co-struvite and/or Co-phosphate octahydrate depending on the (M/P)-ratio. The mixed NixCo1-x system shows a significantly different crystallization behavior and reaction kinetics of the precipitation compared to the pure endmembers. The observed various degree of stability could be linked to the octahedral metal coordination environment in these compounds. The achieved level of control over the precipitates, is highly desirable for 3d- and P-recovery methods. Under this paradigm, the crystals can be potentially upcycled as precursor materials for (electro)catalytical applications. T2 - Adlershofer Forschungsforum 2022 CY - Berlin, Gemany DA - 11.11.2022 KW - Transition metal KW - Phosphates KW - Non-classical crystallization KW - In-situ SAXS/WAXS KW - Cryo-TEM PY - 2022 AN - OPUS4-56479 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - Exploring amorphous lewis-acidic zirconium chloro fluoride as a heterogeneous HF shuttle N2 - Owing to a growing shortage of fluorspar, a raw material used for producing fluorinated base chemicals, fluorspar has been named among the 30 critical raw materials in the EU. 1 However, the sustainable transfer of fluorine atoms from one molecule to another using heterogeneous catalysts has not yet been reported. Herein, we present the heterogeneous catalyst zirconium chloro fluoride (ZCF) that performs dehydrofluorination of a fluoroalkane and consecutive hydrofluorination of an alkyne at room temperature. T2 - InSynX Workshop 2023 CY - Sao Paulo, Brazil DA - 06.03.2023 KW - ZCF KW - Heterogeneous catalysis KW - C-F bond activation PY - 2023 AN - OPUS4-57228 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - Metal fluoride surfaces by protonation with surface immobilized HF N2 - Lewis-acidic zirconium or chromium fluoride surfaces on different aluminium oxide or fluoride substrates. T2 - CRC 1349 Symposium 2021 CY - Berlin, Germany DA - 25.11.2021 KW - HF KW - Heterogeneous catalysis PY - 2021 AN - OPUS4-57226 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Karafiludis, Stephanos T1 - Recycled transition metal phosphates as functional materials for electrochemistry N2 - In the last decade transition metal phosphates (TMPs) captured major interest due to their high electrochemical activity useful for electrode materials, supercapacitors or batteries. Importantly, TMPs are known to exhibit high proton conductivity of the order of >10-2 -10-5 S/cm from 25°C to temperatures as high as 400°C. The crucial milestone in the research on the applicational use of TMPs in all their varieties is an ability to obtain, explore and optimize different compositions and structures, both crystalline and amorphous. Thus, we elucidate the structures of amorphous and crystalline Ni- and Co phosphate phases, as they develop upon heating. This method relies on the thermal decomposition of a crystalline M-struvite precursor, i.e. NH4MPO4•6H2O (M = Mg, Ni, Co, NixCo1-x etc. Here, coincidently volatile components such as H2O or NH3 degas out of the compound resulting in a phase transformation to amorphous or crystalline metal phosphate phases depending on the reaction conditions. For this we used a suite of advanced methods such as FTIR, FT-RS and synchrotron-based XAS. Ni-struvite transforms to amorphous phases over a broad range of temperatures (90°C < T < 600°C) in which it remains in an octahedral coordination environment. On the other hand, Co-struvite treatment leads to multiple crystalline phases with only small amounts of short-lived amorphous phases. Importantly, the occurring amorphous phases exhibit uniform mesoporous frameworks (2–5 nm wide pore channels, specific surface area of 100 m2g−1 and a pore volume of 0.13 cm3g−1) at low temperatures (<200°C) while the crystalline compounds can be used as proton conductors demonstrating values of >10-4 S/cm at 25°C. Consequently, we investigated the amorphization/evolution of mesoporosity, the proton-conducting properties and the complex local structure with in- and ex-situ approaches during thermal treatment. Additionally, to this low cost, environmentally friendly and simple one pot synthesis, the precursor M-struvites could grow as a recovery product from industrial waste waters. In such a way, they would to a recycling economy of sought-after commodities like phosphorus or transition metals. T2 - E-MRS Spring Conference 2023 CY - Strasbourg, France DA - 29.05.2023 KW - Struvite KW - Transition metals KW - Phosphates KW - Functional materials KW - Mesoporosity KW - Proton conductivity PY - 2023 AN - OPUS4-57587 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Manoharan, D. A1 - Megha, S. N. A1 - Kiran, M. S. R. N. A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit A1 - Ghosh, S. T1 - Designing the Mechanical Plasticity of Benzylidene Indanones Based Molecular Crystals by Crystal Engineering N2 - Mechanically flexible molecular crystals have important implications in flexible optoelectronics, optical waveguides, etc. We report a series of 2-benzylidene 1-indanone based plastic crystals. Moreover, we have shown how plasticity can be fine-tuned through controlling intermolecular interactions. KW - Mechanical flexibility KW - Organic crystal KW - Mechanical property PY - 2023 DO - https://doi.org/10.1021/acs.cgd.2c01137 SN - 1528-7483 VL - 23 SP - 657 EP - 661 PB - ACS Publications AN - OPUS4-57773 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bernardes, C. E. S. A1 - Feliciano, I.O. A1 - Naese, Christoph A1 - Emmerling, Franziska A1 - Minas da Piedade, M. T1 - Energetics of dehydroepiandrosterone polymorphs I and II from solution and drop-sublimation Calvet microcalorimetry measurements N2 - The lattice enthalpies and monotropic relationship of two dehydroepiandrosterone (DEHA) polymorphs (forms I and II) were evaluated through a combination of differential scanning calorimetry (DSC), isothermal solution microcalorimetry, and drop-sublimation Calvet microcalorimetry experiments. The standard molar enthalpy of transition between both forms was determined as ΔtrsHom (II→I, 298.15 K) = - 0.90 ± 0.07 kJ mol-1 and ΔtrsHom (II→I, 417.8 K) = - 1.7 ± 1.0 kJ mol- 1, from measurements of standard molar enthalpies of solution in dimethyl sulfoxide and enthalpies of fusion, respectively. Drop-sublimation Calvet microcalorimetry experiments on form I led to ΔsubHom (cr I, 298.15 K) = 132.0±3.3 kJ mol - 1. This result, when combined with the more precise ΔtrsHom (II→I) value obtained by solution calorimetry, afforded ΔsubHom (cr II, 298.15 K) = 131.1±3.3 kJ mol - 1. The overall data indicate that on enthalpic grounds form I is more stable than form II from 298.15 K up to fusion. This conclusion, and the fact that DSC experiments indicated that form I has also a considerably higher temperature fusion, namely, Tfus(cr I)= 422.5±0.2 K and Tfus(cr II) = 413.1±0.2 K, suggest that the two polymorphs are monotropically related. KW - Calorimetry KW - Polymorphism KW - Enthalpy of solution KW - Enthalpy of sublimation KW - Thermochemistry KW - Lattice enthalpy PY - 2023 DO - https://doi.org/10.1016/j.jct.2023.107137 SN - 0021-9614 SN - 1096-3626 VL - 186 SP - 1 EP - 7 PB - Elsevier AN - OPUS4-58418 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Linberg, Kevin T1 - Controlled Polymorphism by Elevated Temperature Ball Milling N2 - Mechanochemistry provides polymorphs that are difficult to obtain by conventional solution-based methods. Based on the nicotinamide and pimelic acid cocrystal, we demonstrated that the ball size, frequency, and temperature are essential parameters. Our results indicate that fine-tuning the energy input during a mechanochemical reaction can provide control over polymorphism. T2 - Bessy User Meeting 2023 CY - Berlin, Germany DA - 22.06.2023 KW - Mechanochemistry KW - Temperature KW - Cocrystal KW - Energy input KW - Polymorph PY - 2023 AN - OPUS4-57985 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - Zirconium chloro fluoride as catalyst for C-F bond activation and HF transfer of fluoroalkanes N2 - In this work, we successfully synthesized amorphous zirconium chloro fluoride (ZCF), which exhibits medium lewis acidity. In addition to investigating the local coordination sphere around the Zr atoms and the material properties, we were able to establish a catalytic behavior of ZCF in C-F bond activation reactions. We present a heterogeneous catalyst that performs dehydrofluorination of a fluoroalkane and consecutive hydrofluorination of an alkyne at room temperature. T2 - MC 16 CY - Dublin, Ireland DA - 03.07.2023 KW - ZCF KW - Heterogeneous catalysis KW - C-F bond activation PY - 2023 AN - OPUS4-58052 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Miclea, P.-T. T1 - Real-life airborne micro- and nano-plastic particles and fibres on a porous membrane filter system from a textile factory suitable for both: vibrational and mass spectrometry N2 - The poster presents an application of Si wafer filter system on indoor air sampling. A textile factory producing PP fibres was sampled. T2 - SETAC Europe 2023 CY - Dublin, Ireland DA - 30.04.2023 KW - Microplastics KW - Polymer 3R KW - Textile fibres KW - Si wafer filter KW - Microplastics sampling PY - 2023 AN - OPUS4-57462 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Overview of CUSP and PlasticTrace N2 - The presentation summarises the work of CUSP and PlasticTrace EU joint research projects of the last year. T2 - Microplastics Scientific Workshop of PlasticsEurope CY - Amsterdam, The Netherlands DA - 08.05.2023 KW - Microplastics KW - Microplastics standardisation KW - Reference materials KW - Polymer 3R PY - 2023 AN - OPUS4-57460 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Material Selection Strategy N2 - This poster is a summary of the material used in the PlasticsFatE project. It indicates the strategies for testing of various polymer properties next to each other according to risk and hazard assessment. T2 - CUSP annual meeting and conference CY - Utrecht, Netherlands DA - 12.09.2023 KW - Microplastics KW - CUSP KW - Material selection PY - 2023 AN - OPUS4-58311 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Manoharan, Deepak A1 - Ahmad, Shamim A1 - Tothadi, Srinu A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit A1 - Ghosh, Soumyajit T1 - Linker size dependent mechanical properties of di-imine based molecular crystals N2 - We have demonstrated the ability to modify the mechanical flexibility of molecular crystals by modulating the length of intervening linker moieties while keeping the terminal shape synthons the same. KW - Mechanically flexible molecular crystals KW - Mechanical properties KW - Crystal Engineering PY - 2023 DO - https://doi.org/10.1039/D3CE00928A SN - 1466-8033 SP - 1 EP - 8 PB - RSC CY - London AN - OPUS4-58836 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Current projects in risk assessment and harmonisation N2 - The talk gives an overview about EU projects currently running for risk assessment and harmonisation in microplastic analysis. T2 - Micro- and Nanoplastics CY - Halle (Saale), Germany DA - 01.11.2023 KW - Microplastics KW - Harmonisation in microplastics KW - Polymer 3R PY - 2023 AN - OPUS4-58766 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Visileanu, E. T1 - Methods for the collection and characterization of airborne particles in the textile industry N2 - The presentation summarizes possibilities to sample airborne micro and nanoplastic particles. An example of a textil company is shown. T2 - 5th International Conference on Human Systems Engineering and Design: Future Trends and Applications (IHSED 2023 CY - Dubrovnik, Croatia DA - 27.09.2023 KW - Microplastics KW - Polymer 3R KW - Textile company PY - 2023 AN - OPUS4-58561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - A fluorolytic sol-gel route to access an amorphous Lewis-acidic Zr fluoride catalyst N2 - The Kemnitz et al. developed a fluorolytic route to access metal fluorides 1 such as AlF3 2 and MgF2 3 which possess a high surface area. In aluminium-based systems, the synthetic approach led to amorphous xerogels that can be further converted into Lewis superacids.2 Still, despite zirconium oxide being described as a stronger Lewis acid than other metal oxides4 zirconium fluoride-based materials have only recently been reported or investigated. In this work we extend the class of amorphous Lewis acidic heterogeneous catalysts to an amorphous ZrF4 that is active in C-F bond activation. T2 - CRC 1349 Summer School 2023 CY - Berlin, Germany DA - 28.08.2023 KW - ZrF4 KW - Heterogeneous catalysis KW - C-F bond activation KW - Postfluorination PY - 2023 AN - OPUS4-58638 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hein-Paar, Jakob T1 - Spectroscopic Insights into the Reactivity of Energetic Materials N2 - Energetic materials (explosives, propellants, pyrotechnics, and gas generators; EM) release large amounts of energy when initiated by mechanical loading and have many technological applications including in energy storage and propulsion. The accidental initiation of an EM – particularly in the wrong setting – has the potential to be catastrophic. Unfortunately, there is little understood about what determines the sensitivity of a given EM. This poses severe restrictions on our ability to design new and safer EMs. Aiming to better understand the initiation mechanisms of EMs, we here investigate the reactivity of simple, isomorphous azides (MN3 M=Li, Na). Both metal azides contain the same explosophoric azido anions, but differ significantly in their reactivity, presumably owing to different bonding interactions between the anion and the metal cation. This interaction offers a promising probe for X-ray spectroscopy and quantum chemical simulations. In noting that mechanical initiation results from mechanical impact – with high local pressures – we are particularly interested in identifying how this bonding interaction changes as a function of pressure. This interaction offers a promising probe for X-ray spectroscopy and quantum chemical simulations. In noting that mechanical initiation results from mechanical impact – with high local pressures – we are particularly interested in identifying how this bonding interaction changes as a function of pressure. Here we show results from DFT simulations that indicate a shift in electronic structure and changes in the metal-azide bond with increasing pressure, which is further investigated through experimental XAS spectra. Together, our results show promising insights into the behaviour of simple metal azide EMs. T2 - SXR2023 - Principles of Functionality From Soft X-Ray Spectroscopy CY - Berlin, Germany DA - 11.09.2023 KW - Energetic materials PY - 2023 AN - OPUS4-58824 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Purohit, Akash M A1 - Patel, Rishi I A1 - Bhatt, Vidhi A1 - Mosaffa, Elias A1 - Bhattacharya, Biswajit A1 - Manna, Arun K A1 - Iyer, Bragadish A1 - Emmerling, Franziska A1 - Banerjee, Atanu T1 - Solvent induced ligand transmuted substituted pyrazole housed copper complexes: Synthesis, characterization, DFT and anti-microbial performance N2 - Pyrazole-based ligand systems 3,5-dimethylpyrazole (L1) and 1-hydroxymethyl-3,5-dimethylpyrazole (L2OH) were synthesized and utilized to form copper complexes in various solvent environments. The ligand L2OH exhibits significant solvent-induced ligand transformation in polar protic solvent. The structural and electronic characteristics of the synthesized complexes were elucidated by X-ray single crystallography, Fourier Transform Infrared (FTIR) and electronic spectroscopy (UV-VIS). Whereas the ligand transformation has been evidenced from FTIR and Nuclear Magnetic Resonance (NMR) spectroscopic techniques. Furthermore, Density Functional Theory (DFT) highlights the pivotal role of solvent effects in modulating ligand transformations and complex formation, contributing to the rational design of metal-based bioactive compounds. Electronic transitions of the metal complexes have been analysed by time-dependent DFT (TD-DFT) calculations. The findings reinforce the significance of transition metal complexes in the development of antimicrobial agents and metallo-pharmaceuticals. The synthesized pyrazole compounds showed 100% inhibition against bacterial strains Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis and the yeast Candida albicans at a concentration ranging from 3.9 to 62.5 µg/ml depending upon the strain tested. KW - Pyrazole derivatives KW - Antibacterial and antifungal activity KW - Solvent induced ligand transformation Copper complexes KW - DFT study PY - 2025 DO - https://doi.org/10.1016/j.molstruc.2025.143001 SN - 0022-2860 VL - 1345 SP - 1 EP - 12 PB - Elsevier B.V. AN - OPUS4-63746 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Booth, A. T1 - Production of a 1-10 μm polypropylene reference material for development of analytical methods N2 - The poster is about the preparation of microplastics in the size range of 1-10 µm. These size range of particles can be inhalded and therefore be toxic for humans. The preparation is done by comminution of PP pellets and sieving. Characterisation occured for size with laser diffraction, for type with FTIR and for shape with SEM. T2 - SETAC Europe 2025 CY - Vienna, Austria DA - 11.05.2025 KW - Microplastics KW - Reference materials PY - 2025 AN - OPUS4-63367 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gugin, Nikita T1 - ZIF-8-Based Biocomposites via Reactive Extrusion: Towards Industrial-Scale Manufacturing N2 - Mechanochemistry offers a solvent-free, sustainable alternative to conventional synthesis of metal-organic framework (MOF) biocomposites, which hold great promise for applications in drug delivery, biocatalysis, and biosensing,[1] yet the field remains limited to batch-type, gram-scale processes that restrict industrial application. To overcome these limitations, we present a scalable solid-state method for producing MOF-based biocomposites via continuous reactive extrusion. The process begins with rapid model reactions using hand-mixing[2] to encapsulate a variety of biomolecules into zeolitic imidazolate framework-8 (ZIF-8), including proteins, carbohydrates, and enzymes, thereby enabling rapid screening and optimization of reaction conditions. The mild synthesis conditions preserve the catalytic activity of glucose oxidase, confirming the suitability of the method to sensitive biomaterials. Building on this, we translated the batch protocol to twin-screw extrusion,[3] enabling continuous and scalable synthesis of biocomposites such as bovine serum albumin (BSA)@ZIF-8 with tunable protein content. The extrusion process yielded highly crystalline, porous materials with protein loadings of up to 26 wt% and encapsulation efficiencies as high as 96%. The production rate reached 1.2 kg d⁻¹, significantly exceeding previously reported continuous methods.[4] To demonstrate the industrial viability of the method, we extended the approach to produce shaped ZIF-8 monoliths loaded with hyaluronic acid (HA) in a single-step extrusion. These monoliths retained their structural integrity during washing and released HA without measurable degradation, as confirmed by size-exclusion chromatography. Our study opens new avenues for the industrial implementation of MOF biocomposites and establishes reactive extrusion as a robust platform for their scalable synthesis and shaping, expanding the toolkit for drug delivery and biocatalytical applications. T2 - Tag der Chemie 2025 CY - Berlin, Germany DA - 03.07.2025 KW - Mechanochemistry PY - 2025 AN - OPUS4-63802 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meyer, Andreas A1 - Weidner, Steffen A1 - Kricheldorf, Hans R. T1 - Star-shaped poly(l-lactide)s based on pentaerythritol: About crystallization and polycondensation plus disproportionation and ring formation in the solid state N2 - Star-shaped poly( L-lactide)s (s-PLAs), were prepared by ring-opening polymerization of with pentaerythritol and catalyzed by tin(II) 2-ethylhyexanoate (SnOct out in bulk at either 120 ◦ C or 160 ◦ L-lactide (LA) initiated 2 ). Two small series of ROPs were carried C with variation of the LA/initiator ratio. Matrix-assisted laser desorption/ ionization time-of-flight (MALDI-TOF) mass spectra revealed traces of cycles in 120 ◦ C samples only at low initiator/catalyst ratios. In contrast, higher fractions of cycles were detected in samples prepared at 160 C, suggesting a "back-biting" origin. The influence of arm length and thermal history on crystallinity was investigated by differential scanning calorimetry (DSC) and wide-angle x-ray scattering (WAXS). It was shown that annealing increased the melting temperature (T ◦ ◦ m ) and crystallinity. However, annealing at 140 ◦ C for 14 d also caused significant solid-state transesterification. In addition, crystallites composed of s-PLAs with extended arms and, simultaneously, crystallites composed exclusively of extended rings were formed, identified by their typical "sawtooth" pattern in the MALDI mass spectra. Small angle x-ray scattering (SAXS) indicated that the crystal thickness was lower than that of linear PLAs annealed under identical conditions, but increased upon annealing at 140 C. KW - MALDI-TOF MS KW - Polylactide KW - Crystallisation KW - AStar-shaped polymers PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-636832 DO - https://doi.org/10.1016/j.polymer.2025.128709 SN - 0032-3861 VL - 334 SP - 1 EP - 11 PB - Elsevier Ltd. AN - OPUS4-63683 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, Hans R. A1 - Weidner, Steffen T1 - Ring-ring equilibration (RRE) of cyclic poly(L-lactide)s by means of cyclic tin catalysts N2 - With 2,2-dibutyl-2-stanna-1,3-dithiolane (DSTL) and 2-stanna-1,3-dioxa-4,5,6,7-dibenzoxepane (SnBiPh) as catalysts ring-expansion polymerizations (REP) were performed either in 2 M solution using three different solvents and two different temperatures or in bulk at 140 and 120 ◦C. A kinetically controlled rapid REP up to weight average molecular masses (Mẃs) above 300 000 was followed by a slower degradation of the molecular masses at 140 ◦C, but not at 120 ◦C Furthermore, a low molecular mass cyclic poly(L-lactide) (cPLA) with a Mn around 16 000 was prepared by polymerization in dilute solution and used as starting material for ring-ring equilibration at 140 ◦C in 2 M solutions. Again, a decrease of the molecular mass was detectable, suggesting that the equilibrium Mn is below 5 000. The degradation of the molecular masses via RRE was surprisingly more effective in solid cyclic PLA than in solution, and a specific transesterification mechanism involving loops on the surface of crystallites is proposed. This degradation favored the formation of extended-ring crystallites, which were detectable by a “saw-tooth pattern” in their MALDI mass spectra. KW - Organic Chemistry KW - Polymers and Plastics KW - MALDI-TOF MS KW - Materials Chemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593819 DO - https://doi.org/10.1016/j.eurpolymj.2024.112765 SN - 0014-3057 VL - 206 SP - 1 EP - 8 PB - Elsevier B.V. AN - OPUS4-59381 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Pauw, Brian Richard T1 - Holistic Experimentation in the HExX-Lab N2 - Through bottom-up, comprehensive digitalisation of all aspects of an experiment, the HEX-lab improves the trustworthiness (traceability, reproducibility, quality) of scientific findings. The five main parts that make up a materials science experiment, i.e. Sample preparation, Measurements, Processing, Analysis, and Interpretation, each have been addressed in thorough and unique ways in this lab, building up a foundation for a wide range of materials science collaborations. Improvements span the spectrum. Hardware developments include new sample environments and stages, such as grazing incidence motion towers, electrochemistry cells and flow-through holders, electronic components such as safety interlocks and multipurpose I/O controllers, and liquid handling systems such as coolant flow cross-over systems. Software developments include: 1) a new comprehensive control system operating on both the RoWaN as well as the MOUSE allowing for full Python control and sequencing of all experimentation, 2) Automated scripts for instrument optimization, sample alignments and measurements, 3) revamped data pipelines and analysis software, standalone or launched as part of operations sequencing dashboards on servers, and 4) meticulously structured archival datafiles, fully documenting sample preparation, measurements, processing and analyses. These allow for holistic databases and dashboards to be constructed to investigate the links between synthesis parameters and resulting morphology. This poster will highlight some of the tools and techniques developed and available in the HEX-lab over the years, from sample environments to overarching experiment and data organisation structures. T2 - Materials Science Core Facility Synergy Forum 2025 CY - Bremen, Germany DA - 26.02.2025 KW - Digitalization KW - Holistic experiments KW - Traceability KW - Data provenance PY - 2025 AN - OPUS4-62675 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ryll, Tom William T1 - In-situ analysis of nucleation processes – case study: calcium sulfate N2 - In this project we investigate nucleation pathways by utilizing synchrotron-XRD and running a case-study on calcium sulfate phases. To accomplish this, we developed a modular automation setup for reactions in solution to run synthesis and control reaction conditions. So far we successfully characterized the recycling process of gypsum and are now investigating the formation of anhydrite. T2 - BESSY@HZB User Meeting CY - Berlin, Germany DA - 02.12.2025 KW - Recycling KW - Gypsum KW - Synchrotron-X-ray-diffraction KW - Raman-spectroscopy KW - Automation PY - 2025 AN - OPUS4-65344 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hickel, Tilmann A1 - Waske, Anja A1 - Tehranchi, Ali A1 - Bhattacharya, Biswajit A1 - Stawski, Tomasz M. A1 - Fellinger, Tim-Patrick A1 - Mehmood, Asad A1 - Witt, Julia A1 - Ozcan, Ozlem A1 - Guilherme Buzanich, Ana A1 - Kumar, Sourabh A1 - Mishra, Rajesh Kumar A1 - Holzer, Marco A1 - Stucchi de Camargo, Andrea Simone A1 - Agudo Jácome, Leonardo A1 - Manzoni, Anna A1 - Fantin, Andrea A1 - John, Elisabeth A1 - Hodoroaba, Vasile-Dan A1 - Bührig, Sophia A1 - Murugan, Jegatheesan A1 - Marschall, Niklas A1 - George, Janine A1 - Darvishi Kamachali, Reza A1 - Maaß, Robert A1 - Emmerling, Franziska T1 - Chemically complex materials enable sustainable high-performance materials N2 - Chemically complex materials (CCMats) 􀀀 including high-entropy alloys, oxides, and related multi-principal element systems 􀀀 offer a paradigm shift in materials design by leveraging chemical diversity to simultaneously optimize functional, structural, and sustainability criteria. The vastness of the compositional and structural space in CCMats propels the field into an expanding exploratory state. To reconcile functional and structural performance across this immense parameter space remains an open challenge. This Perspective evaluates the opportunities and challenges associated with harnessing chemical complexity across a broad spectrum of applications, such as hydrogen storage, ionic conductors, catalysis, magnetics, dielectrics, semiconductors, optical materials, and multifunctional structural systems. It is delineated how three central design strategies: targeted substitution (SUB), defect engineering (DEF), and diversity management (DIV) enable the reconciliation of high functional performance with long-term structural stability and environmental responsibility. Advances in computational thermodynamics, microstructure simulations, machine learning, and multimodal characterization are accelerating the exploration and optimization of CCMats, while robust data infrastructures and automated synthesis workflows are emerging as essential tools for navigating their complex compositional space. By fostering cross-disciplinary knowledge transfer and embracing data-driven design, CCMats are poised to deliver next-generation materials solutions that address urgent technological, energy, and environmental demands. KW - Chemically complex materials KW - Structural stability KW - Functional performance KW - Design strategies KW - Sustainability PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-655598 UR - https://www.sciencedirect.com/science/article/pii/S1359028626000033?via%3Dihub DO - https://doi.org/10.1016/j.cossms.2026.101256 SN - 1359-0286 VL - 42 SP - 1 EP - 26 PB - Elsevier Ltd. CY - Amsterdam AN - OPUS4-65559 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Liu, Yuanbin A1 - Zhou, Yuxing A1 - Ademuwagun, Richard A1 - Walterbos, Luc A1 - George, Janine A1 - Elliott, Stephen R. A1 - Deringer, Volker L. T1 - Medium-Range Structural Order in Amorphous Arsenic N2 - Medium-range order (MRO) is a key structural feature of amorphous materials, but its origin and nature remain elusive. Here, we reveal the MRO in amorphous arsenic (a-As) using advanced atomistic simulations, based on machine-learned potentials derived using automated workflows. Our simulations accurately reproduce the experimental structure factor of a-As, especially the first sharp diffraction peak (FSDP), which is a signature of MRO. We compare and contrast the structure of a-As with that of its lighter homologue, red amorphous phosphorus (a-P): we find that a-As has a more uniform dihedral-angle distribution, and so we confirm that its structure can be thought of as a 3-fold coordinated continuous random network in first approximation, in contrast to the more molecular-cluster-like structure of a-P. The pressure-dependent structural behaviors of a-As and a-P differ as well, and the origin of the FSDP is closely correlated with the size and spatial distribution of voids in the amorphous networks. Our work provides fundamental insights into MRO in an amorphous elemental system, and more widely it illustrates the usefulness of automation for machine-learning-driven atomistic simulations. KW - Machine Learned Interatomic Potentials KW - Amorphous KW - Advanced Materials KW - Automation KW - Digitalisation KW - Structure-Property- Relationships PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-655952 DO - https://doi.org/10.1021/jacs.5c18688 SN - 0002-7863 SP - 1 EP - 13 PB - American Chemical Society (ACS) AN - OPUS4-65595 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Saeed, A. M. A1 - Saied, M. A. A1 - Szymoniak, Paulina A1 - Altmann, Korinna A1 - Schönhals, Andreas A1 - Fahmy, Alaa T1 - High performance novel polyelectrolyte membrane consisting of polyvinyl alcohol-phenylsilanol-polypyrrole N2 - The synthesis of composite membranes based on PVA, PPy, and sulfonated–hydrolyzed TMPS was investigated for application in proton–exchange membrane fuel cells. FT–IR confirmed the hydrolysis of TMPS through the appearance of Si–OH vibrations, disappearance of Si–O–CH3 bands, reduced CH3 stretching intensity (2840 cm− 1), and successful sulfonation of the phenyl ring (1030 cm− 1). XPS verified the introduction of sulfonic acid groups by identifying S2p peaks between 166–170 eV. Scanning electron microscopy (SEM) showed an incorporation of PPy and that the membrane morphology altered by silanol leading to an increased surface roughness and inducing phase separation in comparison to pure PVA. The PVA–PPy–Si membrane which did not undergo phase separation demonstrated improved mechanical stability (maximum stress 5.91 MPa), reduced methanol uptake (22%, lower than Nafion’s 30%), and enhanced thermal resistance compared to PVA–PPy and PVA–Si. It also exhibited a high ion–exchange capacity (1.5mmol g− 1, exceeding Nafion® at 0.9mmol g− 1 ) and a proton conductivity of 0.036 S/cm, twice that of Nafion 117. These combined properties identify the PVA–PPy–Si composite as a promising high–performance polyelectrolyte membrane for fuel cell applications. KW - Polyelectrolyte membrane PY - 2026 DO - https://doi.org/10.1016/j.apsusc.2026.166495 VL - 731 SP - 1 EP - 11 PB - Elsevier B.V. AN - OPUS4-65627 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Prinz, Carsten A1 - Zimathies, Annett A1 - Emmerling, Franziska T1 - Experimental raw data sets associated with certified reference material BAM-P115 (titanium dioxide) for comparison of nitrogen and argon sorption, available in the universal adsorption information format (AIF) N2 - These data sets serve as models for calculating the specific surface area (BET method) using gas sorption in accordance with ISO 9277. The present measurements were carried out with nitrogen at 77 Kelvin and argon at 87 Kelvin. It is recommended to use the following requirements for the molecular cross-sectional area: Nitrogen: 0.1620 nm² Argon: 0.1420 nm² Expected specific surface area for nitrogen (BET): 140 to 154 m²/g Expected specific surface area for argon (BET): 129 to 135 m²/g Titanium dioxides certified with nitrogen sorption and additionally measured with argon for research purposes were used as sample material. The resulting data sets are intended to serve as comparative data for own measurements and show the differences in sorption behaviour and evaluations between nitrogen and argon. These data are stored in the universal AIF format (adsorption information format), which allows flexible use of the data. KW - Physisorption KW - Specific surface area KW - AIF KW - Argon KW - Nitrogen PY - 2024 DO - https://doi.org/10.5281/zenodo.13269756 PB - Zenodo CY - Geneva AN - OPUS4-60783 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Monikh, F. A. A1 - Baun, A. A1 - Hartmann, N. B. A1 - Kortet, R. A1 - Akkanen, J. A1 - Lee, J.-S. A1 - Shi, H. A1 - Lahive, E. A1 - Uurasjärvi, E. A1 - Tufenkji, N. A1 - Altmann, Korinna A1 - Wiesner, Yosri A1 - Grossart, H.-P. A1 - Peijnenburg, W. A1 - Kukkonen, J. V. K. T1 - Exposure protocol for ecotoxicity testing of microplastics and nanoplastics N2 - Despite the increasing concern about the harmful effects of micro- and nanoplastics (MNPs), there are no harmonized guidelines or protocols yet available for MNP ecotoxicity testing. Current ecotoxicity studies often use commercial spherical particles as models for MNPs, but in nature, MNPs occur in variable shapes, sizes and chemical compositions. Moreover, protocols developed for chemicals that dissolve or form stable dispersions are currently used for assessing the ecotoxicity of MNPs. Plastic particles, however, do not dissolve and also show dynamic behavior in the exposure medium, depending on, for example, MNP physicochemical properties and the medium’s conditions such as pH and ionic strength. Here we describe an exposure protocol that considers the particle-specific properties of MNPs and their dynamic behavior in exposure systems. Procedure 1 describes the top-down production of more realistic MNPs as representative of MNPs in nature and particle characterization (e.g., using thermal extraction desorption-gas chromatography/mass spectrometry). Then, we describe exposure system development for short- and long-term toxicity tests for soil (Procedure 2) and aquatic (Procedure 3) organisms. Procedures 2 and 3 explain how to modify existing ecotoxicity guidelines for chemicals to target testing MNPs in selected exposure systems. We show some examples that were used to develop the protocol to test, for example, MNP toxicity in marine rotifers, freshwater mussels, daphnids and earthworms. The present protocol takes between 24 h and 2 months, depending on the test of interest and can be applied by students, academics, environmental risk assessors and industries. KW - Microplastics KW - TED-GC/MS KW - Cryo milling PY - 2023 DO - https://doi.org/10.1038/s41596-023-00886-9 SN - 1754-2189 SP - 1 EP - 38 PB - Nature Protocols AN - OPUS4-58557 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rautenberg, Max A1 - Bhattacharya, Biswajit A1 - Das, Chayanika A1 - Emmerling, Franziska T1 - Mechanochemical Synthesis of Phosphonate-Based Proton Conducting Metal-Organic Frameworks N2 - Water-stable metal−organic frameworks (MOFs) with proton-conducting behavior have attracted great attention as promising materials for proton-exchange membrane fuel cells. Herein, we report the mechanochemical gram-scale synthesis of three new mixed-ligand phosphonate-based MOFs, {Co(H2PhDPA)(4,4′-bipy)H2O)·2H2O}n (BAM-1), {Fe(H2PhDPA)(4,4′-bipy) (H2O)·2H2O}n (BAM-2), and {Cu(H2PhDPA)(dpe)2(H2O)2·2H2O}n (BAM-3) [where H2PhDPA = phenylene diphosphonate, 4,4′-bipy = 4,4′-bipyridine, and dpe = 1,2-di(4-pyridyl)ethylene]. Single-crystal X-ray diffraction measurements revealed that BAM-1 and BAM-2 are isostructural and possess a three-dimensional (3D) network structure comprising one-dimensional (1D) channels filled with guest water molecules. Instead, BAM-3 displays a 1D network structure extended into a 3D supramolecular structure through hydrogenbonding and π−π interactions. In all three structures, guest water molecules are interconnected with the uncoordinated acidic hydroxyl groups of the phosphonate moieties and coordinated water molecules by means of extended hydrogen-bonding interactions. BAM-1 and BAM-2 showed a gradual increase in proton conductivity with increasing temperature and reached 4.9 × 10−5 and 4.4 × 10−5 S cm−1 at 90 °C and 98% relative humidity (RH). The highest proton conductivity recorded for BAM-3 was 1.4 × 10−5 S cm−1 at 50 °C and 98% RH. Upon further heating, BAM-3 undergoes dehydration followed by a phase transition to another crystalline form which largely affects its performance. All compounds exhibited a proton hopping (Grotthuss model) mechanism, as suggested by their low activation energy. KW - Mechanochemistry KW - Metal-organic-frameworks KW - Proton conductivity PY - 2022 DO - https://doi.org/10.1021/acs.inorgchem.2c01023 VL - 61 SP - 10801 EP - 10809 PB - ACS Publications AN - OPUS4-55448 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Why shaken, not stirred, makes the difference: insights into mechanochemical reactions from in situ investigations N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Different analytical methods and their combinations have been developed for the time resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray adsorption spectroscopy, NMR, Raman spectroscopy, and thermography. Here we will discuss our recent results investigating the formation of (poly-morphic) cocrystals[1,3], metal-organic compounds, and salts, thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved. Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results. Our results indicate that time-resolved in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes. T2 - GdCh Vortrag Universität Potsdam CY - Potsdam, Germany DA - 05.06.2023 KW - Mechanochemistry KW - In Situ PY - 2023 AN - OPUS4-58982 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Mechanochemical formation of multicomponent crystal systems: Mechanism & Kinetics N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Different analytical methods and their combinations have been developed for the time resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray adsorption spectroscopy, NMR, Raman spectroscopy, and thermography. Here we will discuss our recent results investigating the formation of (poly-morphic) cocrystals, metal-organic compounds, and salts, thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved. Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results. Our results indicate that time-resolved in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes. T2 - 25th International Conference on the Chemistry of the Organic Solid State (ICCOSS XXV) CY - Ohrid, Macedonia DA - 03.07.2022 KW - Mechanochemistry KW - In situ real-time monitoring KW - Crystal Engineering PY - 2022 AN - OPUS4-55413 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Shaken not stirred: enhancing the flavor of mechanochemistry N2 - compounds and cocrystals. The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. Time-resolved in situ investigations of milling reactions (Figure 1) provide direct insights into the underlying mechanisms. We recently introduced different setups enabling in situ investigation of mechanochemical reactions using synchrotron XRD and XAS combined with Raman spectroscopy and thermography. The presented setup allows the detection of crystalline, amorphous, eutectic, and liquid intermediates. Furthermore, the chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key to future optimization of mechanochemical syntheses. In this contribution, we will discuss our recent results investigating the formation of (polymorphic) cocrystals and coordination polymers. Our results indicate that time-resolved in situ investigations of mechanochemical processes are key for tuning and optimizing mechanochemical syntheses allowing to unleash the potential of mechanochemistry for a green materials design. T2 - 2nd National Crystallographic Meeting Lisbon, Portugal CY - Lisbon, Portugal DA - 15.07.2022 KW - Mechanochemistry KW - In situ real-time monitoring KW - Crystal PY - 2022 AN - OPUS4-55415 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Mechanochemical formation of multicomponent crystals systems N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of mechanochemical reactivity and selectivity. Different analytical methods and their combinations have been developed for the time-resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography. Here we will discuss our recent results investigating the formation of (polymorphic) cocrystals, metal-organic compounds, and salts, thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. Our results indicate that time-resolved in situ investigations of milling reactions offer a new approach to tune and optimize mechanochemical processes. T2 - 5ECQUL Forging Bonds CY - Lisbon, Portugal DA - 12.07.2022 KW - Mechanochemistry KW - In situ real-time monitoring KW - N-Chlorination PY - 2022 AN - OPUS4-55414 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Mechanochemical formation of multicomponent crystal systems: Mechanism & Kinetics N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Different analytical methods and their combinations have been developed for the time resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray adsorption spectroscopy, NMR, Raman spectroscopy, and thermography.1 Here we will discuss our recent results investigating the formation of (polymorphic) cocrystals2–3 and metal-organic frameworks,4 thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved.6 Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results. Our results indicate that time-resolved in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes. T2 - 10th International conference on Mechanochemistry and Mechanical Alloying CY - Cagliari, Italy DA - 06.06.2022 KW - Mechanochemistry KW - In situ real-time monitoring KW - Cocrystal PY - 2022 AN - OPUS4-55421 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - ILC on Laser diffraction - preliminary results N2 - This presentation addresses an interlaboratory comparison on size of polymeric particles (microplastics) measured by laser diffraction. Two microplastic particles were measured separately and once as mixture. Evaluation was done with Fraunhofer and Mie. Here, the first results are presented. T2 - CUSP Annual Meeting CY - Utrecht, Netherlands DA - 12.09.2023 KW - Microplastics KW - Laser diffraction KW - Polymer 3R KW - Size distribution KW - Polymer size PY - 2023 AN - OPUS4-58318 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stawski, Tomasz T1 - Evolution of mesoporous frameworks from precipitated struvite-structured metal phosphate materials N2 - Mesoporous transition metal phosphates (TMPs) have attracted major interest due to their high (electro-)catalytic activity suitable for H2 generation, supercapacitors or batteries. Typically, mesoporous materials are synthesized via a template-based route. This way is in the case of TMP because the surfactants used are difficult to remove due to the sensitivity of the mesoporous framework. We present a template-free method including the formation of a precursor phase called M-struvite (NH4MPO4•6H2O, M = Mg2+, Ni2+, Co2+, Ni2+xCo2+1-x) to synthesize mesoporous and amorphous metal phosphates. This method relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneous mesoporous phase associated with the degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the coordination metal coordination environment was followed with diffraction and spectroscopy based in-situ and ex-situ methods. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions between the chemical systems. In a complex amorphous structure, thermal decomposed Mg-, Ni- and NixCo1-x-struvites exhibit high surface areas and pore volumes for phosphate materials with a spherical to channel-like pore geometry (240 m²g-1 and 0.32 cm-3 g-1 for Mg and 90 m²g-1 and 0.13 cm-3 g-1 for Ni). In addition to this low-cost, environmentally friendly and simple synthesis, M-struvites could grow as a recycling product from industrial and agricultural wastewaters. These waste products could be upcycled through a simple thermal treatment for further applications. T2 - ECCG7, European Conference on Crystal Growth CY - Paris, France DA - 25.07.2022 KW - Transition metals KW - Phosphates KW - Struvite KW - Amorphous phases KW - Mesoporosity PY - 2022 AN - OPUS4-55491 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Opitz, P. A1 - Asta, M. A1 - Fernandez-Martinez, A. A1 - Panthöfer, M. A1 - Kabelitz, Anke A1 - Emmerling, Franziska A1 - Mondeshki, M. A1 - Tremel, W. T1 - Monitoring a Mechanochemical Syntheses of Isostructural Luminescent Cocrystals of 9-Anthracenecarboxylic Acid with two Dipyridines Coformers N2 - Amorphous calcium carbonate (ACC) is an important precursor in the biomineralization of crystalline CaCO3. In nature, it serves as a storage material or as a permanent structural element, whose lifetime is regulated by an organic matrix. The relevance of ACC in materials science is primarily related to our understanding of CaCO3 crystallization pathways and CaCO3/(bio)polymer nanocomposites. ACC can be synthesized by liquid–liquid phase separation, and it is typically stabilized with macromolecules. We have prepared ACC by milling calcite in a planetary ball mill. Phosphate “impurities” were added in the form of monetite (CaHPO4) to substitute the carbonate anions, thereby stabilizing ACC by substitutional disorder. The phosphate anions do not simply replace the carbonate anions. They undergo shear-driven acid/base and condensation reactions, where stoichiometric (10%) phosphate contents are required for the amorphization to be complete. The phosphate anions generate a strained network that hinders ACC recrystallization kinetically. The amorphization reaction and the structure of BM-ACC were studied by quantitative Fourier transform infrared spectroscopy and solid state 31P, 13C, and 1H magic angle spinning nuclear magnetic resonance spectroscopy, which are highly sensitive to symmetry changes of the local environment. In the first—and fast—reaction step, the CO32– anions are protonated by the HPO42– groups. The formation of unprecedented hydrogen carbonate (HCO3–) and orthophosphate anions appears to be the driving force of the reaction, because the phosphate group has a higher Coulomb energy and the tetrahedral PO43– unit can fill space more efficiently. In a competing second—and slow—reaction step, pyrophosphate anions are formed in a condensation reaction. No pyrophosphates are formed at higher carbonate contents. High strain leads to such a large energy barrier that any reaction is suppressed. Our findings aid in the understanding of the mechanochemical amorphization of calcium carbonate and emphasize the effect of impurities for the stabilization of the amorphous phases in general. Our approach allowed the synthesis of new amorphous alkaline earth defect variants containing the unique HCO3– anion. Our approach outlines a general strategy to obtain new amorphous solids for a variety of carbonate/phosphate systems that offer promise as biomaterials for bone regeneration. KW - Crystallization KW - Mechanochemistry KW - PDF PY - 2020 DO - https://doi.org/10.1021/acs.cgd.0c00912 VL - 20 IS - 10 SP - 6831 EP - 6846 PB - American Chemical Society AN - OPUS4-51819 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ghazanfari, M. R. A1 - Vittadello, L. A1 - Al-Sabbagh, Dominik A1 - Santhosh, A. A1 - Frankcom, C. A1 - Fuß, F. A1 - von Randow, C. A. A1 - Siemensmeyer, K. A1 - Vrijmoed, J. C. A1 - Emmerling, Franziska A1 - Jerabek, P. A1 - Irmlau, M. A1 - Thiele, G. T1 - Remarkable Infrared Nonlinear Optical, Dielectric, and Strong Diamagnetic Characteristics of Semiconducting K3[BiS3] N2 - The ternary sulfido bismuthate K3[BiS3] is synthesized in quantitative yields. The material exhibits nonlinear optical properties with strong second harmonic generation properties at arbitrary wavelengths in the infrared spectral range and a notable laser-induced damage threshold of 5.22 GW cm−2 for pulsed laser radiation at a wavelength of 1040 nm, a pulse duration of 180 fs, and a repetition rate of 12.5 kHz. K3[BiS3] indicates semiconductivity with a direct optical band gap of 2.51 eV. Dielectric and impedance characterizations demonstrate κ values in the range of 6−13 at 1 kHz and a high electrical resistivity. A strong diamagnetic behavior with a susceptibility of −2.73 × 10−4 m3 kg−1 at room temperature is observed. These results suggest it is a promising nonlinear optical candidate for the infrared region. The synergic physical characteristics of K3[BiS3] provide insight into the correlation of optical, electrical, and magnetic properties. KW - Electrical properties KW - Insulators KW - Materials KW - Nonlinear optics KW - Quantum mechanics PY - 2022 DO - https://doi.org/10.1021/acs.jpclett.2c01689 VL - 13 IS - 30 SP - 6987 EP - 6993 PB - ACS Publications AN - OPUS4-55456 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chinnasamy, R. A1 - Ravi, J. A1 - Pradeep, V.V. A1 - Manoharan, D. A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit A1 - Ghosh, S. T1 - Adaptable Optical Microwaveguides From Mechanically Flexible Crystalline Materials N2 - Flexible organic crystals (elastic and plastic) are important materials for optical waveguides, tunable optoelectronic devices, and photonic integrated circuits. Here, we present highly elastic organic crystals of a Schiff base, 1-((E)-(2,5-dichlorophenylimino)methyl)naphthalen-2-ol (1), and an azine molecule, 2,4-dibromo-6-((E)-((E)-(2,6-dichlorobenzylidene)hydrazono)methyl)phenol (2). These microcrystals are highly flexible under external mechanical force, both in the macroscopic and the microscopic regimes. The mechanical flexibility of these crystals arises as a result of weak and dispersive C−H⋅⋅⋅Cl, Cl⋅⋅⋅Cl, Br⋅⋅⋅Br, and π⋅⋅⋅π stacking interactions. Singly and doubly-bent geometries were achieved from their straight shape by a micromechanical approach using the AFM cantilever tip. Crystals of molecules 1 and 2 display a bright-green and red fluorescence (FL), respectively, and selective reabsorption of a part of their FL band. Crystals 1 and 2 exhibit optical-path-dependent low loss emissions at the termini of crystal in their straight and even in extremely bent geometries. Interestingly, the excitation position-dependent optical modes appear in both linear and bent waveguides of crystals 1 and 2, confirming their light-trapping ability. KW - Crystal growth KW - Fluorescence KW - Mechanophotonics KW - Micromanipulation KW - Optical waveguides PY - 2022 DO - https://doi.org/10.1002/chem.202200905 SN - 0947-6539 SP - 1 EP - 8 PB - Wiley VHC-Verlag AN - OPUS4-55018 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - de Oliveira Guilherme Buzanich, Ana T1 - Time resolved in situ monitoring of mechanochemical transformations by X-ray spectroscopy (XAS) N2 - Mechanochemical reactions promise a new direction for environmentally benign preparation of materials, and has been dubbed by IUPAC as one of the 10 chemical innovations that will change our world. Despite this significant promise, very little is known about the mechanisms that drive mechanochemical transformations, posing significant barriers to realizing their full potential. To this end, there is growing need to follow mechanochemical reactions in situ and in real time. We here describe advances in the development and application of XAS methods to monitor material synthesis in real time under mechanochemical conditions. We demonstrate the generality of our approaches by describing mechanochemical syntheses of materials by both vibratory ball milling and by Resonant Acoustic Mixing (RAM), where a time resolution of 1 second is for a whole XAS spectrum was achieved. Moreover, we describe how spectroscopic methods can be coupled to diffraction-based approaches, thereby providing new dimensions in understanding mechanochemical synthesis. T2 - Denver X-ray Conference: DXC 2021 CY - Online meeting DA - 02.08.2021 KW - Dispersive XAS KW - Mechanochemistry KW - Time resolved KW - In situ PY - 2021 AN - OPUS4-56257 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Manoharan, Deepak A1 - Ranjan, Subham A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit A1 - Takamizawa, Satoshi A1 - Ghosh, Soumyajit T1 - Elasto-plastic behaviour with reversible thermosalient expansion in acrylonitrile-based organic crystals N2 - Crystalline materials that exhibit reversible mechanical responses upon exposure to external stimuli have garnered significant attention owing to their potential applications in various fields. Herein, we report a crystal of (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(4-bromophenyl)acrylonitrile) (DSBr), which displays simultaneous elasto-plastic behaviour and reversible thermosalient effects. While elasto-plastic behaviour is attributed to underlying packing features, reversible thermosalient expansion is attributed to uniaxial expansion mediated by heat. Exceptional length increase and contraction upon cooling is due to the restorative nature of weak interactions through a cooperative effect. The cooperative movement of molecules is reflected in the unidirectional expansion of the habit plane. Thermosalient reversible expansion–contraction in elasto-plastic crystals have not been discussed in the literature so far. Detailed analysis reported herein provides a comprehensive understanding of the underlying mechanism of flexibility and thermosalient responses. This crystal's unique blend of reversible thermal expansion with flexibility holds substantial promise for applications in flexible thermal actuators. KW - Materials Chemistry KW - General Chemistry PY - 2024 DO - https://doi.org/10.1039/D3TC04272C SN - 2050-7526 SP - 1 EP - 11 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59527 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Validation of microplastics detection methods and proficiency testing: Suitable microplastic reference materials for interlaboratory comparison N2 - The talk summarizes challenges in microplastic analysis. It shows the preparation of microplastic reference materials as well as the testing on homogeneity and stability. The reference material is used in an international laboratory comparison to compare different detection methods used for microplastic analysis. The methods used were µ-IR (FTIR+LDIR) for number-based methods and TED-GC/MS and Py-GC/MS for mass-based methods. The ILC was done under the umbrella of VAMAS TWA 45. Results of the participants are presented. T2 - BAM Akademie CY - Online meeting DA - 16.05.2024 KW - Microplastics KW - Reference materials KW - ILC KW - Microplastics detection KW - TED-GC/MS KW - Polymer 3R PY - 2024 AN - OPUS4-60085 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Giovannozzi, A T1 - Metrological traceability of measurement data from nano- to small microplastics for a greener environment and food safety N2 - This talk descibes the EMPIR project PlasticTrace. Reference materials for microplastics will be developed. The production process and characterisation is explained by SEM, Raman, IR, Py-GC/MS and TED-GC/MS. Homogeneity control was successful. Stability check show no changes over 6 month. T2 - SETAC Europe 2024 CY - Sevilla, Spain DA - 05.05.2024 KW - Microplastics KW - Reference materials KW - Polymer 3R KW - TED-GC/MS PY - 2024 AN - OPUS4-60033 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Radnik, Jörg T1 - Revealing surface functionalities of micro- and nanoplastic particles’ surface by means of XPS N2 - Over the last 20 years, many researchers, politicians, and citizens themselves have become increasingly aware of the growing plastic problem of our time. Inadequate recycling concepts, collection points, and careless dumping of plastic products in the environment lead to an accumulation of plastic. External weather influences can cause these to degrade and fractionate, so that today microplastics (1-1000 µm, ISO/TR 21960:2020) [1] of different polymer materials can be detected in all parts of the world. The precautionary principle applies to microplastics. The particles can break down further to form nanoplastics (<1 µm, ISO/TR 21960:2020) [1]. Whether microplastics or nanoplastics pose a toxicological hazard is being investigated in a variety of ways. Valid results are still pending, however, investigations into the frequency, transport, possible sinks and entry paths must be taken into account. This is why monitoring of microplastics is already required in the revision of the Drinking Water Framework Directive [2]. The same is still pending in the final version of the revision of the Waste Water Framework Directive this year, but is expected. Nanoplastics are particularly under discussion for having a toxic effect on humans and animals, as these particles are small enough to be absorbed by cells. For targeted toxicological studies, it is important to have test and reference materials that resemble the particles found in the environment. To mimic environmental samples, these materials should also have an irregular shape and show aging at the surface, which can be detected with XPS or SEM/EDS. BAM in collaboration with the EMPIR project "PlasticTrace" works on a reference material candidate of nano-sized polypropylene (nano-PP) [3]. The nano-PP vials were tested for homogeneity with PTA and further characterized with bulk and surface-sensitive techniques. An SEM image and a corresponding XPS spectrum are presented in Figure 1. Raman measurements as well as XPS indicate an aged surface. T2 - ECASIA 2024 CY - Gothenburg, Sweden DA - 09.06.2024 KW - Surface chemistry KW - Micro- and nanoplastics KW - X-ray Photoelectron Spectroscopy KW - MNP production technique PY - 2024 AN - OPUS4-60535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ciornii, Dmitri T1 - Interlaboratory comparisons for obtaining reliable data on microplastic detection methods N2 - Since microplastics (MPs) can be found everywhere and are becoming a problem of high concern, it is necessary to understand their occurrence and fate in the environment. However, to obtain data of high quality is very challenging, since measurement operating procedures differ from laboratory to laboratory. Currently, there are no standardized methods to analyze microplastics. One promissing possibility to adress standardization of the methodology and operating procedures are interlaboratory comparisons (ILCs). In this contribution we report the first results of an ILC on microplastic detection methods organized under the pre-stantdardisation plattform of VAMAS (www.vamas.org/twa45/) as Project 2 “Development of standardized methodologies for characterisation of microplastics with microscopy and spectroscopy methods”, within the Technical Working Area TWA 45 “Micro and Nano Plastics in the Environment”. The ILC has gathered 84 participants all over the world representing all continents. BAM, as the project leader, produced a set of reference microplastic materials, which have been distributed to all the participants together with the measurement protocols and reporting data templates. T2 - SETAC 34th Meeting CY - Seville, Spain DA - 05.05.2024 KW - ILC KW - Microplastic KW - Py-GC/MS KW - Polyethylene KW - µ-Raman KW - µ-FTIR KW - Polyethylene Terephtalate KW - TED-GC/MS PY - 2024 AN - OPUS4-60038 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Drago, C. T1 - Standardization Methods for the Analysis of Microplastics (10 100µm) in Food Matrix: Sample Preparation and Digestion of Milk Powder. N2 - Monitoring of microplastics in food matrices is crucial to determinate the human exposure. By direct ingestion microplastics could be released in the food during the production, through packaging and by consumer’s use. The absence of standard methods to quantify and detect different size range and type of microplastics has led to difficult and time consuming procedural steps, poor accuracy and lack of comparability. In this work, matrix characterization and laboratory experiments were used to investigate the efficiency of sample preparation in milk powder. This information is crucial to compile a standard procedure for sample preparation and digestion of common milk powder to detect different particle sizes and types of polymers. Charaterisation is done by TGA and TOC measurements. T2 - SETAC Europe 2024 CY - Sevilla, Spain DA - 05.05.2024 KW - Microplastics KW - Harmonisation in microplastics KW - Polymer 3R KW - Microplastics in milk PY - 2024 AN - OPUS4-60034 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - An Amorphous Lewis-acidic Zirconium Chlorofluoride as HF Shuttle: C-F Bond Activation and Formation N2 - In recent years, fluorine chemistry has gained increasing political attention. Owing to a growing shortage of fluorspar, a raw material used for producing fluorinated base chemicals, fluorospar has been named among the 30 critical raw materials in the EU.2 As such, it becomes increasingly important to recycle existing fluorinated compounds and make them available as sources of fluorine for reactions. Significant progress has been made in the field of C-F bond activation using heterogeneous catalysts such as aluminum chlorofluoride (ACF).3–5 However, the transfer of fluorine atoms from one molecule to another using heterogeneous catalysts has not yet been reported. In this study, we successfully synthesized amorphous zirconium chlorofluoride (ZCF), and we were able to establish a catalytic behavior of ZCF in C-F bond activation reactions. We present a heterogeneous catalyst that performs dehydrofluorination of a fluoroalkane and consecutive hydrofluorination of an alkyne at room temperature. T2 - 2nd South African Fluorine Symposium CY - Sun City, South Africa DA - 09.02.2024 KW - ZCF KW - Heterogeneous catalysis KW - C-F bond activation KW - HF-shuttle PY - 2024 AN - OPUS4-59618 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - A fluorolytic sol-gel route to access an amorphous Lewis-acidic Zr fluoride catalyst N2 - Kemnitz et al. developed a fluorolytic route to access metal fluorides 2 such as AlF3 3 and MgF2 4 which possess a high surface area. In aluminium-based systems, the synthetic approach led to amorphous xerogels that can be further converted into Lewis superacids.3 Still, despite zirconium oxide being described as a stronger Lewis acid than other metal oxides 4 zirconium fluoride-based materials have only recently been reported or investigated. 6 In this work we extend the class of amorphous Lewis acidic heterogeneous catalysts to an amorphous ZrF4 that is active in C-F bond activation. T2 - 2nd South African Fluorine Symposium CY - Sun City, South Africa DA - 11.02.2024 KW - ZrF4 KW - Heterogeneous catalysis KW - C-F bond activation PY - 2024 AN - OPUS4-59617 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - George, Janine T1 - Openness, Curiosity and Identity N2 - I am introducing early-career researchers to my view on the academic career. I highlighted openness with regard to people. I mentioned my interest in multiple fields of the natural sciences, driving my curiosity. I additionally highlight my core belief that science is a team sport. T2 - Open Minds – Exploring Science Careers CY - Berlin, Germany DA - 05.03.2026 KW - Materials Informatics PY - 2026 AN - OPUS4-65632 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mojsak, Mateusz A1 - Bodo, Filippo A1 - Erba, Alessandro A1 - Michalchuk, Adam A. L. A1 - Kraka, Elfi T1 - Local Vibrational Mode Analysis of Phonon Dispersion Relations in Crystals N2 - We present a general framework for performing local vibrational mode analysis of vibrations in crystalline materials at arbitrary wavevectors throughout the Brillouin zone. The approach enables phonon dispersion relations to be interpreted in terms of chemically meaningful interatomic interactions and structural motifs, providing direct insight into the microscopic origins of the phonon behavior in periodic systems. We demonstrate the methodology for representative one-, two-, and three-dimensional materials including polymeric chains, graphene, and prototypical rock-salt and perovskite crystals. Across these systems, the analysis reveals how specific bonding patterns and structural features govern phonon dispersion relations. This framework provides a quantitative tool for the chemically intuitive analysis of phonon spectra and offers a pathway toward the rational design of phonon-dependent properties in crystalline materials. KW - Phonons KW - Molecular Crystals PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-656430 DO - https://doi.org/10.1021/acs.jctc.6c00097 SN - 1549-9618 SP - 1 EP - 16 PB - American Chemical Society (ACS) AN - OPUS4-65643 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - George, Janine T1 - Robust data generation, heuristics and machine learning for materials design N2 - Machine learning (ML) offers new routes to overcome the limitations of density functional theory (DFT) for advanced materials. We present data-generation strategies and workflows for ML interatomic potentials, including large-scale quantum-chemical bonding analysis.[1,2,3] Incorporating bonding descriptors into ML models enables prediction of phononic properties and validation of correlations between bonding strength, force constants, and thermal conductivity.[3] We introduce autoplex, an automated framework for training ML potentials, supporting general-purpose and phonon-focused workflows.[4] These developments provide a basis for fine-tuning foundation models for thermal transport at reduced cost.[5] For properties such as magnetism or synthesizability, we discuss complementary approaches, comparing ab initio methods with chemical heuristics and experimental data-driven ML models.[6,7]Our work advances scalable, accurate simulations for materials discovery. T2 - DPG Dresden, Condensed Matter CY - Dresden, Germany DA - 10.03.2026 KW - Materials Design KW - Materials Acceleration Platforms KW - Advanced materials simulations KW - Automation KW - High-throughput KW - Thermal Conductivity KW - Chemical Bonding Analysis KW - Phonons KW - Amorphous Materials PY - 2026 AN - OPUS4-65648 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Mrkwitschka, Paul A1 - Hodoroaba, Vasile-Dan A1 - Radnik, Jörg T1 - XPS/HAXPES and EDS spectra with ROI N2 - XPS/HAXPES spectra as well as EDS spectra and SEM micrographs with regions of interest. Measurement scheme included as a powerpoint presentation. Investigated materials: Ionic liquid and commercial and lab-synthesized graphene oxide. KW - EDX KW - XPS KW - Graphene Oxide KW - Ionic Liquid PY - 2026 DO - https://doi.org/10.5281/zenodo.18231732 PB - Zenodo CY - Geneva AN - OPUS4-65624 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pütz, E. A1 - Smales, Glen Jacob A1 - Jegel, O. A1 - Emmerling, Franziska A1 - Tremel, W. T1 - Tuning ceria catalysts in aqueous media at the nanoscale: how do surface charge and surface defects determine peroxidase- and haloperoxidase-like reactivity N2 - Designing the shape and size of catalyst particles, and their interfacial charge, at the nanometer scale can radically change their performance. We demonstrate this with ceria nanoparticles. In aqueous media, nanoceria is a functional mimic of haloperoxidases, a group of enzymes that oxidize organic substrates, or of peroxidases that can degrade reactive oxygen species (ROS) such as H2O2 by oxidizing an organic substrate. We show that the chemical activity of CeO2−x nanoparticles in haloperoxidase- and peroxidaselike reactions scales with their active surface area, their surface charge, given by the ζ-potential, and their surface defects (via the Ce3+/Ce4+ ratio). Haloperoxidase-like reactions are controlled through the ζ-potential as they involve the adsorption of charged halide anions to the CeO2 surface, whereas peroxidase-like reactions without charged substrates are controlled through the specific surface area SBET. Mesoporous CeO2−x particles, with large surface areas, were prepared via template-free hydrothermal reactions and characterized by small-angle X-ray scattering. Surface area, ζ-potential and the Ce3+/Ce4+ ratio are controlled in a simple and predictable manner by the synthesis time of the hydrothermal reaction as demonstrated by X-ray photoelectron spectroscopy, sorption and ζ-potential measurements. The surface area increased with synthesis time, whilst the Ce3+/Ce4+ ratio scales inversely with decreasing ζ-potential. In this way the catalytic activity of mesoporous CeO2−x particles could be tailored selectively for haloperoxidase- and peroxidase-like reactions. The ease of tuning the surface properties of mesoporous CeO2x particles by varying the synthesis time makes the synthesis a powerful general tool for the preparation of nanocatalysts according to individual needs. KW - SAXS KW - Ceria KW - Zeta potential PY - 2022 DO - https://doi.org/10.1039/D2NR03172H SP - 1 EP - 12 PB - Royal Society of Chemistry AN - OPUS4-55649 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Altmann, Korinna T1 - Reference material candidates for microplastic analysis N2 - Every day, there are new headlines in the media about microplastics (1-1000 µm, ISO/TR 21960:2020) and nanoplastics (< 1 µm, ISO/TR 21960:2020) findings all over the planet with high variations in particle number and mass. The challenges in analytics are very complex, e.g. representative sampling, non-destructive sample preparation with concentrated particles and homogeneous distribution and true detection. All together lead to lacks in harmonization and results, which are hardly comparable. On the other hand, monitoring of microplastics is mandatory in the future strictly regulated by the EU commission in the Drinking water and Wastewater Framework Directive. One step to accurate and precise results will be the development of suitable reference materials mimicking particles in the environment. BAM developed test materials, which are produced by mixing a small portion of microplastic particles with a water-soluble matrix. After solid phase dilution and homogenisation small portions are pressed into tablets and bottled in glass vials (Figure 1). These tablets are well characterized with particle size distribution and SEM images. Additionally, they are tested as reference material candidate according to homogeneity and stability for particle number with µ-IR and µ-Raman as well as on particle mass with Py-GC/MS and TED-GC/MS after ISO Guide 35. Results are promising. The material passed the homogeneity control. No changes are observed within 6 months of storage. The same tested reference material is finally used in sample preparation experiments, where environmental suspended particular matter from surface water or baby milk powders are spiked with the tablets. T2 - ESOPS CY - Berlin, Germany DA - 09.09.2024 KW - Microplastics KW - TED-GC/MS KW - Reference materials KW - Polymer 3R KW - Tablets PY - 2024 AN - OPUS4-61017 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Miliūtė, Aistė T1 - Synthesis and phase purity of the negative thermal expansion material ZrV2O7 N2 - This repository contains computational and experimental data for the manuscript titled “Synthesis and phase purity of the negative thermal expansion material ZrV2O7”. KW - NTE KW - Sol-gel KW - Solid-state KW - Ab-initio KW - XRD KW - Raman PY - 2024 DO - https://doi.org/10.5281/zenodo.12688634 PB - Zenodo CY - Geneva AN - OPUS4-61360 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rautenberg, Max A1 - Bhattacharya, Biswajit A1 - Akhmetova, Irinia A1 - Emmerling, Franziska T1 - Mechanochemical and solution syntheses of two novel cocrystals of orcinol with two N,N0-Dipyridines: Structural diversity with varying ligand flexibility N2 - We studied the influence of coformers flexibility on the supramolecular assembly of 5-substituted resorcinol. Two cocrystals of orcinol (ORL) with two dipyridine molecules, i.e. 1,2-di(4-pyridyl)ethane (ORLeBPE) and 1,2-di(4-pyridyl)ethylene (ORLeBPY), were prepared by mechanochemical synthesis and slow evaporation of solvent. The new crystalline solids were thoroughly characterized by single crystal Xray diffraction (SCXRD), powder X-ray diffraction analysis (PXRD), Fourier-transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), and thermogravimetric analysis (TGA). Structural determination reveals that in both cocrystals, the phenolepyridine, i.e. OeH/N(py) heterosynthon takes the main role in the formation of cocrystals. In ORLeBPE, the components form infinite 1D zig-zag chains, which are extended to 2D layer structure by inter-chain CeH/O interactions between BPE hydrogen atoms and hydroxyl oxygen atoms of ORL. In ORLeBPY, the components form a 0D fourcomponent complex. Formation of the discrete assemblies is attributed to the comparative rigid nature of BPY, which restricts the formation of an extended network. KW - Cocrystal KW - Single crystal KW - X-ray diffraction KW - Mechanochemistry PY - 2020 DO - https://doi.org/10.1016/j.molstruc.2020.128303 SN - 0022-2860 VL - 1217 SP - 128303 PB - Elsevier B.V. AN - OPUS4-51023 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gugin, Nikita T1 - Advancing Industrial Mechanochemistry: Real-Time Insights for Sustainable, Solvent-Free Manufacturing N2 - Mechanochemistry is an environmentally friendly synthetic approach that enables the sustainable production of a wide range of chemicals while reducing or eliminating the need for solvents. Reactive extrusion aims to move mechanochemistry from its conventional gram-scale batch reactions, typically performed in laboratory ball mills, to a continuous, large-scale process. Meeting this challenge requires in situ monitoring techniques to gain insights into reactive extrusion and its underlying processes. While the effectiveness of in situ Raman spectroscopy in providing molecular-level information has been demonstrated, our study uses energy-dispersive X-ray diffraction to monitor reactive extrusion in real time at the crystalline level. Our results provide previously unavailable control over thereactiveextrusion process, promoting its perception as an industrially feasible green alternative to traditional solventbased syntheses. T2 - #RSCPoster 2025 CY - Online meeting DA - 04.03.2025 KW - Mechanochemistry PY - 2025 AN - OPUS4-63803 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Alić Stolar, Jasna T1 - Harnessing mechanochemistry to combat PFAS contamination N2 - For over 70 years, the uncontrolled production, use, and disposal of per- and polyfluoroalkyl substances (PFAS) have led to widespread global contamination, necessitating the rapid development of innovative and efficient remediation technologies. State-of-the-art strategies rely on energy-intensive incineration, which releases greenhouse gases and smaller, volatile PFAS derivatives. Here, we present a fast, simple, and sustainable method for the complete degradation of PFAS leveraging mechanochemistry to break down the persistent carbon-fluorine bonds. Our findings indicate that liquid-assisted grinding conditions accelerate the degradation of perfluorooctanoic acid compared to neat grinding conditions, resulting in a significant reduction in energy consumption. Moreover, the fluoride released during the process binds to inorganic additives, allowing fluorine recovery as crystalline salts and preventing the formation of secondary toxic waste. The method has strong potential for scaling up and offers a green and viable solution for real-world application in PFAS decontamination. T2 - The International Symposium on Mechanochemistry (Mech’cheM 2025) CY - Montpellier, France DA - 04.06.2025 KW - Mechanochemistry KW - PFAS PY - 2025 AN - OPUS4-63956 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Moss, Caitlin T1 - Framework Materials for the Electrocatalytic Reduction of Nitrate to Ammonia N2 - The electrocatalytic reduction of nitrate to ammonia offers a sustainable alternative to the energy-intensive Haber-Bosch process while simultaneously addressing the pressing issue of nitrate pollution in water sources. Developing efficient catalysts for this reaction is therefore vital for both environmental remediation and green ammonia production. Framework materials such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and coordination polymers present an emerging class of electrocatalytic materials due to their high surface area, tunable porosity, and structural modularity. Their ability to incorporate diverse metal centers and functional groups makes them promising candidates for selective and efficient nitrate reduction. In order to change and improve catalytic properties, different synthesis strategies can be pursued, such as metal alloying or calcination under different conditions. To fully understand and optimize these materials, advanced characterization techniques are essential to correlate structural features with catalytic performance, alongside in-situ methods for real-time mechanistic insights. T2 - Tag der Chemie 2025 CY - Berlin, Germany DA - 03.07.2025 KW - Electrocatalysis KW - Electrochemisty KW - Framework Materials KW - Ammonia Synthesis KW - Nitrate Reduction PY - 2025 AN - OPUS4-63815 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schmalz, Alina T1 - Framework Materials for the Electrocatalytic Reduction of Nitrate to Ammonia N2 - The electrocatalytic reduction of nitrate to ammonia offers a sustainable alternative to the energy-intensive Haber-Bosch process while simultaneously addressing the pressing issue of nitrate pollution in water sources. Developing efficient catalysts for this reaction is therefore vital for both environmental remediation and green ammonia production. Framework materials such as metal-organic frameworks (MOFs) or metalated covalent organic frameworks (COFs) present an emerging class of electrocatalytic materials due to their high surface area, tunable porosity, and structural modularity. Their ability to incorporate diverse metal centers and functional groups makes them promising candidates for selective and efficient nitrate reduction. In order to change and improve catalytic properties, different synthesis strategies can be pursued, such as metal alloying, doping or calcination. To fully understand and optimize these materials, advanced characterization techniques are essential to correlate structural features with catalytic performance, alongside in-situ methods for real-time mechanistic insights. T2 - 10th European Crystallography School CY - Ohrid, North Macedonia DA - 23.06.2025 KW - Electrocatalysis KW - Electrochemistry KW - Framework Materials KW - Ammonia Synthesis KW - Nitrate Reduction PY - 2025 AN - OPUS4-63846 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ryll, Tom William T1 - In-situ analysis of nucleation processes – case study: calciumsulfate N2 - In this project we investigate nucleation pathways by utilizing synchrotron-XRD and running a case-study on calcium sulfate and its polymorphs. To accomplish this, we developed a modular automation setup for reactions in solution to run synthesis and control reaction conditions. So far we successfully characterized the recycling process of gypsum (CaSO4*2H2O) and are now investigating the formation of anhydrite (CaSO4*0H2O) as well as possible applications for the automation setup and analysis. T2 - SALSA Make & Measure 2025 CY - Berlin, Germany DA - 10.09.2025 KW - Recycling KW - Gypsum KW - Synchrotron-X-ray-diffraction KW - Raman-spectroscopy KW - Automation PY - 2025 AN - OPUS4-64135 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stawski, Tomasz A1 - Smales, Glen Jacob A1 - Scoppola, E. A1 - Jha, D. A1 - Morales, L. F. G. A1 - Moya, A. A1 - Wirth, R. A1 - Pauw, Brian Richard A1 - Emmerling, Franziska A1 - Van Driessche, A. E. S. T1 - Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals N2 - In recent years, we have come to appreciate the astounding intricacies associated with the formation of minerals from ions in aqueous solutions. In this context, a number of studies have revealed that the nucleation of calcium sulfate systems occurs nonclassically, involving the aggregation and reorganization of nanosized prenucleation species. In recent work, we have shown that this particle-mediated nucleation pathway is actually imprinted in the resultant micrometer-sized CaSO4 crystals. This property of CaSO4 minerals provides us with the unique opportunity to search for evidence of nonclassical nucleation pathways in geological environments. In particular, we focused on large anhydrite Crystals extracted from the Naica Mine in Mexico. We were able to shed light on this mineral's growth history by mapping defects at different length scales. Based on this, we argue that the nanoscale misalignment of the structural subunits, observed in the initial calcium sulfate crystal seeds, propagates through different length scales both in morphological, as well as in strictly crystallographic aspects, eventually causing the formation of large mesostructured single crystals of anhydrite. Hence, the nonclassical nucleation mechanism introduces a “seed of imperfection,” which leads to a macroscopic “single” crystal whose fragments do not fit together at different length scales in a self-similar manner. Consequently, anisotropic voids of various sizes are formed with very welldefined walls/edges. However, at the same time, the material retains in part its single crystal nature. KW - Calcium sulfate KW - Anhydrite KW - Mesocrystal KW - Nucleation KW - Naica PY - 2021 DO - https://doi.org/10.1073/pnas.2111213118 SN - 0027-8424 VL - 118 IS - 48 SP - 1 EP - 11 PB - National Academy of Sciences (USA) CY - Washington AN - OPUS4-53820 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Altmann, Korinna A1 - Wimmer, Lukas A1 - Alcolea-Rodriguez, Victor A1 - Waniek, Tassilo A1 - Wachtendorf, Volker A1 - Matzdorf, Kay A1 - Ciornii, Dmitri A1 - Fengler, Petra A1 - Milczewski, Frank A1 - Otazo-Aseguinolaza, Itziar A1 - Ferrer, Manuel A1 - Bañares, Miguel A. A1 - Portela, Raquel A1 - Dailey, Lea Ann T1 - Quality-by-design and current good practices for the production of test and reference materials for micro- and nano-plastic research N2 - Understanding the environmental and human health impacts of micro- and nanoplastic pollutants is currently a high priority, stimulating intensive methodological research work in the areas of sampling, sample preparation and detection as well as intensive monitoring and testing. It is challenging to identify and quantify microplastics in complex organic matrices and concepts for nanoplastic detection are still in their infancy. All analytical techniques employed in studying micro- and nanoplastics require suitable reference materials for validation measurements, with requirements as diverse as the analytical tools used, ranging from different polymer types, size distributions and shapes of the material to the concentrations employed in different experimental set ups (ng to g amounts). The aim of this manuscript is to outline current good practices for small-scale laboratory production and characterization of suitable test and reference materials. The focus is placed on top-downfragmentation methods as well as bottom-up precipitation methods. Examples using polyethylene, polypropylene, polystyrene and polyethylene terephthalate with size distribution classes of mainly 10–1000, 1–10 and <1 μm particles will be provided. Experiences and suggestions on how to produce well-characterized micro- and nano-plastics for internal research needs will ensure that studies using the materials have robust and informative outcomes. KW - Mmicroplastics KW - Nanoplastics KW - Reference materials KW - Standard validation method PY - 2025 DO - https://doi.org/10.1016/j.jhazmat.2025.139595 SN - 0304-3894 VL - 497 SP - 1 EP - 20 PB - Elsevier B.V. AN - OPUS4-63958 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wiesner, Yosri T1 - Reference material candidates for Microplastic analysis N2 - Microplastic reference material is required for validation and harmonization purposes. This includes the analysis of the pure polymer particles and the validation of the respective measurement methods. In addition, there is the harmonization of different laboratories. On the other hand, sample preparation methods must be validated and harmonized with regard to their recovery and subsequent analysis in the respective matrices. For this purpose, we produce reference material candidates in the form of tablets with different mass fractions and particle numbers of polyethelene terephthalate. In the presentation first measurement results by µ-Raman, µ-FTIR, pyrolysis-GC-MS and TED-GC/MS will be presented. T2 - SETAC Europe 34th Annual Meeting CY - Seville, Spain DA - 05.05.2024 KW - Reference material KW - Microplastics KW - PlasticTrace PY - 2024 AN - OPUS4-60019 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stawski, Tomasz T1 - Solution-driven processing of calcium sulfate: the mechanism of the reversible transformation of gypsum to bassanite in brines N2 - Calcium sulfate hemihydrate (CaSO4ᐧ0.5H2O), also known as bassanite, has been used as a precursor to produce gypsum (dihydrate, CaSO4ᐧ2H2O) for various construction and decorative purposes since prehistoric times. The main route to obtain hemihydrate is a thermal treatment of gypsum at temperatures typically between 150 °C and 200 °C to remove some of the structural water. In this contribution, we introduce (Fig. 1) a more efficient and sustainable method (T < 100 °C) that enables the direct, rapid, and reversibly conversion of gypsum to bassanite using reusable high salinity aqueous solutions (brines with c[NaCl] > 4 M). The optimum conditions for the efficientproduction of bassanite in a short time (< 5 min) involve the use of brines with c(NaCl) > 4 M and maintaining a temperature, T > 80 °C. When the solution containing bassanite crystals is cooled down to around room temperature, eventually gypsum is formed. When the temperature is raised again to T > 80 °C, bassanite is rapidly re-precipitated. This contrasts with the typical behaviour of the bassanite phase in low salt environments. Traditionally, hemihydrate is obtained through a solid state thermal treatment because bassanite is considered to be metastable with respect to gypsum and anhydrite in aqueous solutions, and therefore gypsum-to-bassanite conversion should not occur in water. Its very occurrence actually contradicts numerical thermodynamic predictions regarding solubility of calcium sulfate phases. By following the evolution of crystalline phases with in situ and time-resolved X-ray diffraction/scattering and Raman spectroscopy, we demonstrated that the phase stability in brines at elevated temperatures is inaccurately represented in the thermodynamic databases. Most notably for c(NaCl) > 4 M, and T > 80 °C gypsum becomes readily more soluble than bassanite, which induces the direct precipitation of the latter from gypsum. The fact that these transformations are controlled by the solution provides extensive opportunities for precise manipulation of crystal formation. Our experiments confirmed that bassanite remained the sole crystalline structure for many hours before reverting into gypsum. This property is extremely advantageous for practical processing and efficient crystal extraction in industrial scenarios. T2 - Granada Münster Discussion Meeting GMDM 10 CY - Münster, Germany DA - 29.11.2023 KW - Gypsum KW - Bassanite KW - Calcium sulfate KW - Recycling KW - Scattering PY - 2024 AN - OPUS4-59162 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - May, Anastasia T1 - Pyrazinamide-Pimelic Acid Cocrystals: A Mechanochemical and Thermal Study N2 - Cocrystals represent a promising class of crystalline materials, offering a wide potential for physico-chemical property alteration of chemical compounds, such as their solubility, by cocrystallizing the targeted compound with another solid material. In the present study, we investigated the cocrystal system between the anti-tuberculosis drug pyrazinamide (PZA) and pimelic acid (PA) by thermal characterization and milling conditions of mechanochemical synthesis. Thermal treatment resulted in the formation of a eutectic between the compounds PZA and PA. Furthermore, irreversible separation of the cocrystal occurred upon melting. This finding indicated low stability of the cocrystal and the necessity of mechanochemical synthesis for cocrystal formation. The mechanochemical synthesis parameters were elucidated by investigating the temperature effect while milling and the role of pre-milling the coformer PA using in-situ monitoring techniques. The polymorphism of PA, influenced by temperature and pre-milling, exhibited a substantial impact on the kinetics of cocrystallization. This finding underscores the significance of coformer polymorphism as an additional factor in mechanochemical cocrystallization reactions. T2 - 11th International Conference on Mechanochemistry and Mechanical Alloying CY - Berlin, Germany DA - 14.09.2025 KW - Cocrystal PY - 2025 AN - OPUS4-65353 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martins, I. A1 - Carta, M. A1 - Haferkamp, Sebastian A1 - Feiler, Torvid A1 - Delogu, F. A1 - Colacino, E. A1 - Emmerling, Franziska T1 - Mechanochemical N‑Chlorination Reaction of Hydantoin: In Situ Real-Time Kinetic Study by Powder X‑ray Diffraction and Raman Spectroscopy N2 - Mechanochemistry has become a valuable tool for the synthesis of new molecules, especially in the field of organic chemistry. In the present work, we investigate the kinetic profile of the chlorination reaction of N-3-ethyl-5,5-dimethylhydantoin (EDMH) activated and driven by ball milling. The reaction has been carried out using 2 mm, 4 mm, 5 mm, 6 mm, and 8 mm ball sizes in a new small custom-made Perspex milling jar. The Crystal structure of the starting material EDMH and the 1-chloro-3-ethyl5,5′-dimethyl hydantoin (CEDMH) chlorination product was solved by single-crystal X-ray diffraction. The reaction was monitored, in situ and in real time, by both powder X-ray diffraction (PXRD) and Raman spectroscopy. Our kinetic data show that the reaction progress to equilibrium is similar at all milling ball sizes. The induction period is very short (between 10 and 40 s) when using 4 mm, 5 mm, 6 mm, and 8 mm balls. For the reaction performed with a 2 mm ball, a significantly longer induction period of 9 min was observed. This could indicate that an initial energy accumulation and higher mixing efficiency are necessary before the reaction starts. Using different kinetic models, we found that the amount of powder affected by critical loading conditions during individual impacts is significantly dependent on the ball size used. An almost linear correlation between the rate of the chemical transformations and the ball volume is observed. KW - Mechanochemistry KW - In situ real-time monitoring KW - N-Chlorination KW - Kinetics KW - Hydantoin KW - Powder X-ray diffraction KW - Raman spectroscopy PY - 2021 DO - https://doi.org/10.1021/acssuschemeng.1c03812 VL - 9 IS - 37 SP - 12591 EP - 12601 AN - OPUS4-53541 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Souza, B. A1 - Chauque, S. A1 - de Oliveira, P. A1 - Emmerling, Franziska A1 - Torresi, R. T1 - Mechanochemical optimization of ZIF-8/Carbon/S8 composites for lithium-sulfur batteries positive electrodes N2 - The application of lithium-sulfur (Li-S) batteries is still limited by their rapid capacity fading. The pulverization of the sulfur positive electrode after the lithiation and the consequence dissolution of long chain polysulfides in organic solvents lead to the shuttle effect. To address these issues, here we report the mechanochemical preparation of ZIF-8 (Zeolitic Imidazole Framework-8)-based composites as sulfur hosts for positive electrodes in Li-S batteries. We studied different methods for the incorporation of conductive carbon. Also, the replacement of Zn2+ metal centers by other bivalent metals (Cu2+, Co2+ and Ni2+), enabled the preparation of other ZIF-8-based materials. The positive electrode ZIF-8/C/S8 showed initial discharges of 772 mA h g−1 while the pristine one, ZIF-8/S8, displayed 502 mA h g−1. The enhanced performance of 54% for ZIF-8/C/S8 indicates that the direct mechanochemical synthesis of ZIF-8 with conductive carbon is beneficial at initials charge/discharge process in comparison to traditional slurry preparation (ZIF-8/S8). Also, the Li2S6 absorption tests shows 87% of discoloration with ZIF-8/C/S8, confirming the better polysulfides absorption. KW - Lithium-sulfur battery KW - Metal organic frameworks KW - ZIF-8 KW - Mechanochemistry PY - 2021 DO - https://doi.org/10.1016/j.jelechem.2021.115459 VL - 896 SP - 115459 PB - Elsevier B.V. AN - OPUS4-53542 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stawski, Tomasz T1 - Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals N2 - In recent years, we have come to appreciate the astounding intricacy of the formation process of minerals from ions in aqueous solutions. In this context, a number of studies have revealed that nucleation in the calcium sulfate system is non-classical, involving the aggregation and reorganization of nanosized prenucleation particles. In a recent work we have shown that this particle-mediated nucleation pathway is actually imprinted in the resultant single micron-sized CaSO4 crystals. This property of CaSO4 minerals provides us with an unique opportunity to search for evidence of non-classical nucleation pathways in geological environments. In particular, we focused on the quintessential single crystals of anhydrite extracted from the Naica mine in Mexico. We elucidated the growth history from this mineral sample by mapping growth defects at different length scales. Based on these data we argue that the nano-scale misalignment of the structural sub-units observed in the initial calcium sulfate crystal seed propagate through different length-scales both in morphological, as well as strictly crystallographic aspects, eventually causing the formation of large mesostructured single crystals of anhydrite. Hence, the nanoparticle mediated nucleation mechanism introduces a 'seed of imperfection', which leads to a macroscopic single crystal, in which its fragments do not fit together at different length-scales in a self-similar manner. Consequently, anisotropic voids of various sizes are formed with very well-defined walls/edges. But, at the same time the material retains its essential single crystal nature. These findings shed new light on the longstanding concept of crystal structure. T2 - S4SAS Conference 2021 CY - Online meeting DA - 01.09.2021 KW - SAXS KW - Calcium sulfate KW - Anhydrite KW - Mesocrystals PY - 2021 AN - OPUS4-53630 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - Fluorine Modified ZIF 8 for Electrochemical Catalysis: Where does the Fluorine go? N2 - Carbonization of fluorinated metal-organic frameworks (MOFs) should yield fluorinated nitrogen- and metal-doped carbons (F-NMCs), which are a combination of NMCs and fluorinated carbons, each promising electrocatalysts on their own. We synthesized two polymorphs of a fluorinated MOF by mechanical ball mill grinding, and carbonized them to yield potential electrocatalyt materials. The catalytical activity towards the oxygen reduction reaction (ORR) was examined, finding good activites. Simulations from a theoretic model helped assesing the stability of proposed catalytic sites and understanding the measured activites towards the ORR catalysis. T2 - Online symposium of the CRC 1349 "fluorine-specific interactions" CY - Online meeting DA - 29.06.2021 KW - PGM-free catalyst KW - Oxygen Reduction Reaction KW - Mechanochemistry KW - MOFs KW - Computational chemistry PY - 2021 AN - OPUS4-53538 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - Synthesis and characterization of fluorinated Co-Zn-Zeolitic imidazole frameworks for catalysis of the oxygen reduction reaction N2 - The oxygen reduction reaction (ORR) is a common process in a variety of electrochemical devices, like fuel cells and metal air batteries. The sluggish kinetics of the ORR require an electrocatalyst to pass this bottleneck.[1] Currently, the most used catalytical systems are platinum-based, with several drawbacks, such as the high cost, low availability, and deactivation by CO poisoning.[2] Efforts are made to develop efficient, durable and low cost catalysts to promote the commercialization of fuel cells. Non-precious metal catalysts are promising candidates for efficient ORR catalysis. It has been shown that pyrolyzing metal organic frameworks (MOFs) under inert conditions yields carbon-rich materials, with evenly distributed metal sites, which possess promising electrocatalytic activity.[3] One widely used type of MOF as ORR catalyst precursors is the zeolitic imidazole framework (ZIF) where metal cations are linked through imidazolebased ligands. Herein we report the mechanochemical synthesis, structural analysis and of Co-doped ZIF-8 (Zn), as well as its fluorinated counterpart Co-doped CF3 -ZIF-8 (Zn). The samples showed electrochemical performance comparable to platinum after carbonization for 1h at temperatures ranging between 850 – 1000°C. T2 - 15th International conference on materials chemistry (MC15) CY - Online meeting DA - 12.07.2021 KW - PGM-free catalyst KW - Oxygen Reduction Reaction KW - Mechanochemistry KW - MOFs PY - 2021 AN - OPUS4-53539 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - The Effect of Fluorine on Catalysts for the Oxygen Reduction Reaction obtained from Metal Organic Frameworks N2 - The oxygen reduction reaction (ORR) – an important reaction in electrochemical devices, such as fuel cells - is characterized by its sluggish kinetics and therefore requires catalysis. The industry currently relies on platinum as a catalyst, although it is scarce and expensive, hindering the commercial breakthrough of fuel cells in automotive applications. Platinum-free catalysts on basis of nitrogen- and metal doped carbons (NMCs) and fluorinated carbons are promising materials to replace platinum-based catalysts for the ORR. In this work we prepared six metal-organic frameworks (MOFs) by mechanical ball mill grinding and studied their formation by in-situ powder X-ray diffraction. Furthermore, the samples were carbonized under controlled conditions (900°C, 1h, N2-atmosphere) to yield carbon materials, that were employed in ORR-electrocatalysis. The effect of Co-doping and fluorination was systematically studied and outstanding ORR activity was found for the catalyst prepared from the Co-doped fluorinated ZIF-8. T2 - International Symposium on Fluorine-specific interactions CY - Berlin, Germany DA - 27.09.2021 KW - PGM-free catalyst KW - Oxygen Reduction Reaction KW - Mechanochemistry KW - MOFs PY - 2021 AN - OPUS4-53533 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - Fluorination and co-doping of ZIF-8 by ball mill grinding for efficient oxygen reduction electrocatalysis N2 - The oxygen reduction reaction (ORR) is a common process in a variety of electrochemical devices, like fuel cells and metal air batteries. The sluggish kinetics of the ORR require an electrocatalyst to pass this bottleneck.[1] Currently, the most used catalytical systems are platinum-based, with several drawbacks, such as the high cost, low availability, and deactivation by CO poisoning.[2] Efforts are made to develop efficient, durable and low cost catalysts to promote the commercialization of fuel cells. Non-precious metal catalysts are promising candidates for efficient ORR catalysis. It has been shown that pyrolyzing metal organic frameworks (MOFs) under inert conditions yields carbon-rich materials, with evenly distributed metal sites, which possess promising electrocatalytic activity.[3] One widely used type of MOF as ORR catalyst precursors is the zeolitic imidazole framework (ZIF) where metal cations are linked through imidazole-based ligands. Their porous nature is partially retained after carbonization, making MOFs very suitable precursor materials. Herein we report the mechanochemical synthesis and structural analysis of Co-doped ZIF-8 (Zn), as well as two polymorphs (dense and prorous) of fluorinated Co-doped CF3-ZIF-8 (Zn). The samples showed electrochemical performance comparable to platinum after carbonization for 1 h at temperatures ranging between 850 – 1000°C. T2 - XXV General Assembly and Congress of the International Union of Crystallography - IUCr 2021 CY - Prague, Czech Republic DA - 14.08.2021 KW - PGM-free catalyst KW - Oxygen Reduction Reaction KW - Mechanochemistry KW - MOFs PY - 2021 AN - OPUS4-53535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Linberg, Kevin T1 - Tipping the Energy Scales to Control Mechanochemical Polymorphism N2 - Control of ball milling conversions is required before the full potential of mechanochemical processing can be realized. It is well known that many parameters affect the outcome of mechanochemical polymorphism, but the energy of ball milling itself is often overlooked. We show here how this parameter alone can exert a significant influence on the polymorphic outcome of ball mill grinding by allowing the selective isolation of two polymorphic forms in their pure form under the same grinding conditions. Furthermore, we show how apparent mechanochemical equilibria can be deceptive. Our results clearly demonstrate the need for careful design and interpretation of ball milling experiments beyond current thinking. T2 - SALSA make and measure CY - Online meeting DA - 16.09.2021 KW - Mechanochemistry KW - Energy KW - Polymorph KW - Cocrystal PY - 2021 AN - OPUS4-53293 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Altmann, Korinna A1 - Abusafia, A A1 - Bannick, C-G A1 - Braun, U A1 - Crasselt, Claudia A1 - Dittmar, S A1 - Fuchs, M A1 - Gehde, M A1 - Hagendorf, C A1 - Heller, C A1 - Herper, D A1 - Heymann, S A1 - Kerndorff, A A1 - Knefel, M A1 - Jekel, M A1 - Lelonek, M A1 - Lunkenbein, T A1 - Obermaier, N A1 - Manhart, M A1 - Meurer, Maren A1 - Miclea, P-T A1 - Paul, A A1 - Richter, S A1 - Ricking, M A1 - Rohner, C A1 - Ruhl, A A1 - Sakai, Y A1 - Saravia Arzabe, C A1 - Scheid, C A1 - Schmitt, M A1 - Schnarr, M A1 - Schwertfirm, F A1 - Steinmetz, H A1 - Wander, Lukas A1 - Wiesner, Yosri A1 - Zechmeister, L T1 - RUSEKU - Repräsentative Untersuchungsstrategien für ein integratives Systemverständnis von spezifischen Einträgen von Kunststoffen in die Umwelt : Abschlussbericht N2 - Im Verbundprojekt RUSEKU wurde die Probenahme von Wasserproben entscheidend weiterentwickelt. Wichtig ist hierbei zu gewährleisten, dass genügend Merkmalsträger in jeder Probe untersucht werden. Es muss daher eine für den Probenahmeort repräsentative Beprobung hinsichtlich des Wasservolumens in Abhängigkeit der Partikelanzahl gewährleistet sein. Das Hauptaugenmerk lag im vorliegenden Projekt auf einer praxisnahen Beprobungsstrategie. Es wurden verschiedene Konzepte ausprobiert. • Grundsätzlich hat sich gezeigt, dass eine Stichprobe eine Momentaufnahme des MP-Massengehaltes zeigt. Es wird eine hohe Statistik, also eine Vielzahl an Messungen am gleichen Probenahmeort, benötigt, um eine valide Aussage über den MP-Gehalt zu machen. • Es zeigt sich, dass eine integrale Probenahme über mehrere Wochen mit dem SK routinemäßig möglich ist. Die erfassten MP-Massen sind reproduzierbar und robust. • Die DFZ ist für Stichproben geeignet. Partikel < 50 µm werden eventuell unterschätzt • Die fraktionierte Filtration kann für Stich- und Mischproben direkt im Feld genutzt werden. Fraktionen von 10 und 5 µm werden später im Labor Vakuum filtriert. Es erfolgt eine Fraktionierung der Probe mit Siebmaschenweiten von 1000, 500, 100, 50, 10 und 5 µm. • Die fraktionierte Filtration kann auch anschließend an die Beprobung mit dem SK zur Anwendung kommen. Wird die mit dem SK gewonnene Wasserprobe fraktioniert filtriert, kann neben einem MP-Gesamtgehalt auch eine Einschätzung über die Partikelgrößen gewonnen werden. • Für Wässer mit geringen Partikelzahlen wurde ein Messfiltertiegel entwickelt. Dieser hat eine Maschenweite von 6 µm. Seine Anwendung kann mögliche Verluste beim Transferieren vom Probenahmetool zum Messgefäß und mögliche Kontaminationen reduzieren. Die Optimierung der Probenahmestrategie wurde durch Modellversuche und Simulationen unterstützt. Modellversuche zum Sinkverhalten und Simulationen von MP in realen Gewässern verdeutlichten das komplexe Verhalten der Partikel. Es konnte gezeigt werden, dass Partikel ab einer bestimmten Größe (und kleiner) bei genügend starker Turbulenz sich in der Wassersäule unabhängig von ihrer Dichte verhalten und so auch MP mit kleiner Dichte (z.B. PE) in der gesamten Wassersäule zu finden sind. Es konnte mit dem TEM die Existenz von NP gezeigt werden. Ein wesentlicher Aspekt des RUSEKU Projektes war die Beprobung realer Kompartimente. Beprobt wurde neben Oberflächengewässern, das urbane Abwassersystem der Stadt Kaiserslautern, Waschmaschinenabwasser und Flaschenwasser. • In Oberflächengewässern wurde hauptsächlich PE gefunden. Je nach Probe und Gewässer konnten auch PP, PS, PET, PA, SBR und Acrylate nachgewiesen werden. • Im urbanen Abwassersystem der Stadt Kaiserslautern konnte an allen Probenahmestandorten MP nachgewiesen werden. Es wurde hauptsächlich PE, neben geringeren Mengen an PP, PS und SBR gefunden. Nach einem Regenereignis war der SBR Anteil deutlich erhöht. • Die Beprobung eines realen Wäschepostens, bestehend aus T-Shirts und Hemden mit PA/CO oder PES/CO Mischgewebe, zeigte einen PA- und PES-Austrag im Waschwasser. Der überwiegende Teil der detektierten Fasern ist aber auf Baumwolle zurückzuführen. Reine gravimetrische Messungen zur Detektion von MP führen zu einer starken Überschätzung. • In Flaschenwasser (PET-Flaschen) konnte MP detektiert werden. PET wurde nur im stillen Mineralwasser, nicht in Mineralwasser mit Kohlensäure gefunden werden. Teilweise wurde auch das MP-Material des Verschlusses im Wasser detektiert. • Für Luftproben konnte ein Aufbau zur größenselektiven Beprobung getestet werden. Neben der Probenahme hat das Projekt auch gezeigt, dass die TED-GC/MS geeignet für die MP-Detektion im Routinebetrieb ist. Die TED-GC/MS konnte weiter optimiert werden. Es wurden MP-Massen bestimmt. Im Projekt wurden erste realitätsnahe Referenzmaterialien für die MP Detektion hergestellt. Die Herstellung von realitätsnahen Polymeren in ausreichender Homogenität und Menge hat sich als große Herausforderung herausgestellt. KW - Mikroplastik KW - Probennahme KW - TED-GC/MS KW - Fraktionierte Filtration KW - Mikroplastikreferenzmaterial PY - 2022 SP - 1 EP - 201 AN - OPUS4-57800 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Pauw, Brian Richard T1 - Laboratory x-ray scattering instruments as agile test-beds towards holistic experimentation N2 - Laboratory sources offer a unique advantage compared to synchrotron sources, largely in terms of freedom of operation. This freedom from user obligations, technology and software stacks and legacy decisions make the laboratory a very flexible place to develop and explore new ideas. The unparalleled availability furthermore allows for iterative improvement of instrumentation, sample environments and measurement methodologies to maximise the quality of the data obtained. This talk will highlight the use of the laboratory as an agile test-bed and development space, by giving examples of some complete and incomplete investigations undertaken in our laboratory over the last years. Furthermore, it will introduce the concept of holistic experimentation, where the laboratory provides broad-ranging support for materials science investigations. This means that we assist in the experimental preparation, perform the measurements, correction and analysis, and follow-up with assistance in interpretation of our analyses in light of the results from other techniques applied to the investigation. T2 - Invited talk at Diamond Light Source CY - Didcot, UK DA - 22.05.2024 KW - X-ray scattering KW - Methodology development KW - Laboratory management KW - Holistic experimentation KW - Laboratory automation KW - Nanostructural analysis PY - 2024 AN - OPUS4-60582 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Pauw, Brian Richard T1 - Glimpses of the Future : Oh my god it’s full of metadata! N2 - In this talk, the importance of metadata is underscored by real-world examples. Metadata is essential to alleviating the reproducibility crises in science. This imples that a wide range of metadata must be collected, with a heavy emphasis on the automated collection of such metadata. This must subsequently be organized in an intelligible, archival structure, when possible with units and uncertainties. Such metadata can aid in improving the usage efficiency of instrumentation, as is demonstrated on the MOUSE instrument. This metadata can now be used to connect the various aspects of the holistic experimental procedure to gain better insights on the materials structure. A second example shows the extraction and organization of such metadata from an automated materials development platform, collected during the synthesis of 1200 samples. These metadata from the synthesis can then be linked to the results from the analysis of these samples, to find direct correlations between the synthesis parameters and the final structure of the materials. T2 - Helmholtz Incubator Summer Academy - Next Level Data Science CY - Online meeting DA - 18.09.2023 KW - Metadata KW - Lab automation KW - Data provenance KW - High-throughput KW - Correlative analysis KW - MOUSE KW - X-ray scattering KW - Robotics PY - 2023 AN - OPUS4-58463 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -