TY - CONF A1 - Falkenhagen, Jana T1 - Challenges of SEC and the necessity of round robin tests N2 - Size exclusion chromatography (SEC) is still the method of choice for determining the molar mass and molar mass distribution of macromolecules. It is a liquid chromatographic technique that separates molecules based on their size, respectively their hydrodynamic volume using a porous stationary phase that allows smaller molecules to pass through the pores while excluding larger molecules. The chromatogram from the size separation can be calibrated using polymers of known molar mass resulting in a relative molar mass distribution curve. From this distribution curve molar mass averages and the oligomer content (percentage of peak area smaller than 1000 g/mol and 500 g/mol) of polymers can be derived. The determination of oligomer content is important, because it is often used in regulatory contexts as a measure of small, mobile and potentially more toxic parts of the polymer. Polymer regulations are of increasing political and societal importance. Regulations often strive for narrow limits. But SEC has rather large error margins of 10-20% for the molar mass determination performed in different laboratories or on different instruments. These variances are well known to all experts and users and have been investigated in several round robin tests in the past. These resulted in DIN and ISO standards which, in our opinion, no longer meet today's requirements. Gaps have been identified that require further harmonization. Different polymer types or classes require different methods. On the other hand, as far as we know, the margins of error in determining oligomer content have not yet been investigated. It is expected that the variation will be rather high. This is because it depends on many factors related to the experimental conditions (column sets used, solvent, temperatures, sample preparation) on the one hand, and the data evaluation mechanisms (choice of baseline and peak limits) on the other. In order to actually measure the error margins and to support this with actual data a round robin test has been performed from June to November 2024 with approx. 40 participating laboratories. Three different solvents were selected, namely THF, DMAc or DMF and water. The samples were selected taking into account a wide range of practical aspects far from narrowly distributed standards: e.g higher distribution range, reduced solubility, included side components, copolymers and dispersions with gel content. In this contribution we will present the detailed concept of this round robin test and first impressions. T2 - 11th International Symposium on the Separation and Characterization of Natural and Synthetic Macromolecules CY - Amsterdam, Netherlands DA - 21.01.2025 KW - Size exclusion chromatography KW - Round robin tests PY - 2025 AN - OPUS4-62533 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chandna, Sanjam A1 - Povolotsky, Tatyana L. A1 - Nie, Chuanxiong A1 - Schwartz, Sophia A1 - Wedepohl, Stefanie A1 - Quaas, Elisa A1 - Ludwig, Kai A1 - Boyakova, Yulia A1 - Bhatia, Sumati A1 - Meyer, Klas A1 - Falkenhagen, Jana A1 - Haag, Rainer A1 - Block, Stephan T1 - Lignin-Based Mucus-Mimicking Antiviral Hydrogels with Enzyme Stability and Tunable Porosity N2 - Mucus is a complex hydrogel that acts as a defensive and protective barrier in various parts of the human body. Therise in the level of viral infections has underscored the importance of advancing research into mucus-mimicking hydrogels for theefficient design of antiviral agents. Herein, we demonstrate the gram-scale synthesis of biocompatible, lignin-based virus-bindinginhibitors that reduce waste and ensure long-term availability. The lignin-based inhibitors are equipped with sulfate moieties, whichare known binding partners for many viruses, including SARS-CoV-2 and herpes viruses. In addition, cross-linking the synthesizedinhibitors yielded hydrogels that mimicked native mucus concerning surface functionality and rheology. The degree of sulfationexhibits a very strong impact on the mesh size distribution of the hydrogels, which provides a new means to fine-tune the steric andelectrostatic contributions of the virus−hydrogel interaction. This feature strongly impacts the sequestration capability of the lignin-based hydrogels, which is demonstrated by infection inhibition assays involving human herpes simplex virus 1, influenza A viruses,and the bacterium Escherichia coli (E. coli). These measurements showed a reduction in plaque-forming units (HSV-1) and colony-forming units (E. coli) by more than 4 orders of magnitude, indicating the potent inhibition by the lignin-based hydrogels KW - Lignin functionalization KW - Mucus-mimicking hydrogels PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-625301 DO - https://doi.org/10.1021/acsami.4c18519 SP - 1 EP - 14 PB - American Chemical Society (ACS) CY - USA AN - OPUS4-62530 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Fink, Friedrich A1 - Falkenhagen, Jana T1 - From bench to mini – Classification of technical lignins with NIR N2 - Lignin, a by-product of the pulp and paper industry, is the second most abundant biopolymer but remains underutilized due to its complex structure and variability in biomass origin. Classification based on biomass source is crucial for quality assurance and application predictability. This study employs near-infrared (NIR) spectroscopy to classify technical lignins from softwoods, hardwoods, straw, and grasses. Machine learning models (ML), including Support Vector Machines (SVM), Gaussian Process Classification (GPC), Gaussian Naive Bayes (GNB), and Decision Tree Classification (DTC), were developed using spectral preprocessing and principle component analysis (PCA). The models were compared with spectra from handheld and compact spectrometers. Results highlight the potential of NIR spectroscopy and machine learning to enable rapid, reliable lignin classification, paving the way for improved industrial utilization of this abundant resource. T2 - 11th International Symposium on the Separation and Characterization of Natural and Synthetic Macromolecules CY - Amsterdam, The Netherlands DA - 21.01.2025 KW - Lignin KW - Classification KW - Near infrared spectroscopy PY - 2025 AN - OPUS4-62531 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dolai, Malay A1 - Saha, Urmila A1 - Goswami, Juli Nanda A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Ifseisi, Ahmad A. A1 - Biswas, Surajit ED - Bhattacharya, Biswajit T1 - Nickel(II)-mediated in situ complex formation with unexpected ligand transformations: crystal structures, DFT calculations, and catalytic activity in CO2 fixation reactions N2 - Two transformed ligands, namely 1,3,5-triazapentadienato(imidoylamidinato) and N-(methoxy(pyrimidin-2-yl)(pyrimidine-2-carboxamido)methyl)pyrimidine-2-carboxamide, are reported here as the first products derived from 2-cyano pyridine/pyrimidine, respectively, under nickel metal mediation in the presence of hydroxylamine hydrochloride in situ. Two different nickel-coordinated complexes (1 and 2) were formed. Single crystal X-ray diffraction revealed that complex 1 is a mononuclear complex with tetra-coordinated square planar geometry, whereas complex 2 is a dinuclear complex with hexa-coordinated distorted octahedral geometry. The synthetic pathways of both transformed ligands are explained with the support of energy calculations of different states via density functional theory (DFT) calculations. The catalytic addition reactions of epoxides and carbon dioxide efficiently produce organic cyclic carbonates in the presence of complexes 1–2, attributed to the presence of Lewis acidic nickel and Lewis basic centers, such as free amine, imine, methoxy, or nitrogen in complexes 1 and 2. Under mild reaction conditions (1 atm CO2 pressure and 60 °C temperature), different types of epoxides (exocyclic, endocyclic, and aromatic epoxides) yield high levels of respective cyclic carbonates in the presence of both complexes 1–2 as catalysts, with tert-butylammonium bromide (TBAB) acting as a co-catalyst. The high turnover number (TON) and turnover frequency (TOF) of these catalytic reactions clearly indicate the efficacy of the two catalysts. KW - Catalytic activity in CO2 fixation reactions DFT calculations KW - Nickel(II)-complex KW - In situ complex formation KW - Crystal Structure PY - 2025 DO - https://doi.org/10.1039/d4nj01801j SN - 1369-9261 VL - 49 IS - 11 SP - 4451 EP - 4463 PB - Royal Society of Chemistry (RSC) AN - OPUS4-62782 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Reigl, Selina A1 - Van Driessche, Alexander A1 - Stawski, Tomasz A1 - Koltzenburg, Sebastian A1 - Kunz, Werner A1 - Kellermeier, Matthias T1 - Sustainable Pathways for the Synthesis of Calcium Sulfate Hemihydrate N2 - Calcium sulfate, and especially its hemihydrate form (bassanite), is crucial in the construction industry, primarily used as a hydraulic binder in cements, mortars, and wallboards. Because of the rapid transformation of bassanite into thermodynamically stable gypsum (calcium sulfate dihydrate) upon contact with water, natural deposits are scarce, rendering it one of the most extensively produced inorganic materials worldwide. Currently, bassanite is derived from mined or waste gypsum through a thermal dehydration process, which is energy-intensive and costly. As sustainability has become a key target for industrial processes and products, a series of studies aiming to increase the energy efficiency and reduce the carbon footprint of bassanite production was published recently. Two primary approaches are pursued: conversion of gypsum and direct precipitation of bassanite from solution. In both cases, organic solvents, (specific) additives and/or elevated temperatures have been used to control the activity/availability of water in the reaction medium and thus direct phase selection towards bassanite. This review offers a comprehensive overview of alternative bassanite production methods, critically examining their benefits, potential downsides, and overall impact on the sustainability of industrial-scale use. KW - Calcium sulfate KW - Gypsum KW - Bassanite KW - Recycling PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630657 DO - https://doi.org/10.1002/anie.202415161 SN - 1521-3773 SP - 1 EP - 20 PB - Wiley VHC-Verlag AN - OPUS4-63065 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stawski, Tomasz M. A1 - Salvalaglio, Matteo A1 - Wallace, Adam F. A1 - De Yoreo, James J. T1 - The Birth of Minerals: From Single Step to Multiple Step Mechanisms N2 - Mineral formation from ions in aqueous solutions begins with complex initial stages, where amorphous and liquid-like precursors play pivotal roles before crystalline growth occurs. Both classical and non-classical nucleation and growth theories, introduced in previous chapters, offer explanations, each with their own strengths and limitations, for the complex intermediate phases observed in experimental research. Analytical techniques play a critical role in detecting and characterizing precursor phases, offering valuable insights into nucleation and growth mechanisms across various temporal and spatial scales. Molecular dynamics and modelling provide in-depth perspectives on these phases, allowing for a closer examination of their nucleation and growth mechanisms at the molecular level, and revealing the intricate processes that govern their behaviour. KW - Crystallisation KW - Nucleation KW - Synchrotron KW - Thermodynamics KW - Minerals PY - 2025 DO - https://doi.org/10.2138/gselements.21.1.25 SN - 1811-5217 VL - 21 IS - 1 SP - 25 EP - 32 PB - Mineralogical Society of America AN - OPUS4-62841 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mishmastnehi, Moslem A1 - Stawski, Tomasz M. A1 - Eftekhari, Negar A1 - Schneider, Kathrin P. A1 - Vaccaro, Carmela A1 - Aghajani, Iman A1 - Grbanovic, Ana Marija A1 - Korn, Lorenz T1 - Unveiling the craftsmanship and knowledge behind iranian stuccoes (11th–14th centuries): New insights from an archaeometric perspective N2 - Gypsum-based stucco decorations of 47 monuments in Iran, from the Seljuq to the Ilkhanid period (11th-14th centuries), were studied by multimodal analytical methods, including X-ray diffraction, X-ray fluorescence, scanning electron microscopy and image analysis to evaluate their composition properties. The assessment of results shows that stucco masters in those periods exerted control over the setting process of the gypsum-paste and its microstructure by adjusting water-to-plaster ratio, fine-clay addition, and by means of mechanical processing. Furthermore, the presence of anhydrite in the composition of stucco decorations located in the hot-desert climate of Iran provides evidence for the probability of gypsum-anhydrite transition, which has technical and preservation consequences for this less-investigated type of cultural materials. KW - Gypsum KW - Diffraction KW - Anhydrite KW - Calcium sulfate PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-628406 DO - https://doi.org/10.1016/j.jas.2025.106199 SN - 1095-9238 VL - 177 SP - 1 EP - 13 PB - Elsevier B.V. AN - OPUS4-62840 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nag, Sayak A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska L. 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 - Falkenhagen, Jana T1 - Challenges of sec and the necessity of round robin tests N2 - Size exclusion chromatography (SEC) is still the method of choice for determining the molar mass and molar mass distribution of macromolecules. From the distribution curve molar mass averages and the oligomer content (percentage of peak area smaller than 1000 g/mol and 500 g/mol) of polymers can be derived. The determination of oligomer content is important, because it is often used in regulatory contexts as a measure of small, mobile and potentially more toxic parts of the polymer. Polymer regulations are of increasing political and societal importance. Regulations often strive for narrow limits. But SEC has rather large error margins of 10-20% for the molar mass determination performed in different laboratories or on different instruments. These variances are well known to all experts and users and have been investigated in several round robin tests in the past. These resulted in DIN and ISO standards which, in our opinion, no longer meet today's requirements. Gaps have been identified that require further harmonization. Different polymer types or classes require different methods. On the other hand, as far as we know, the margins of error in determining oligomer content have not yet been investigated. It is expected that the variation will be rather high. This is because it depends on many factors related to the experimental conditions (column sets used, solvent, temperatures, sample preparation) on the one hand, and the data evaluation mechanisms (choice of baseline and peak limits) on the other. In order to actually measure the error margins and to support this with actual data a round robin test has been performed from June to November 2024 with approx. 40 participating laboratories. Three different solvents were selected, namely THF, DMAc or DMF and water. The samples were selected taking into account a wide range of practical aspects far from narrowly distributed standards: e.g higher distribution range, reduced solubility, included side components, copolymers and dispersions with gel content. In this contribution we will present the detailed concept of this round robin test and impressions T2 - 2025 Polymer Separations GNT meeting, Dow CY - Online meeting DA - 25.02.2025 KW - Polymers KW - Size exclusion chromatography KW - REACH PY - 2025 AN - OPUS4-63314 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana T1 - 70 years size exclusion chromatography - An ongoing challenge N2 - The reason for our current activities is that polymers may also be subject to REACh regulations in the future. In this context, the determination of oligomer content is important. SEC is still the method of choice for determining molar mass distribution. The regulations aim for narrow limits and SEC has rather large error margins, which are well known to all experts. Different polymers need different methods. What to do when samples with a wide range of practical aspects, samples with higher distribution range, reduced solubility, including side components, gel content etc. need be analyzed? A concept for round robin tests and first impressions will be presented. T2 - Analytical Solutions 2025 CY - Ede, Netherlands DA - 04.06.2025 KW - Polymers KW - Size exclusion chromatography KW - REACH KW - Round Robin Tests PY - 2025 AN - OPUS4-63310 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 - JOUR A1 - Feiler, Torvid A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit T1 - Sustainable mechanochemical approach for the selective synthesis of multicomponent organic solids: real-time in situ insights N2 - Crystalline multicomponent organic solids (MOSs) such as cocrystals and ionic cocrystals hold immense potential in diverse functional applications, ranging from pharmaceuticals to optoelectronics. However, conventional solution-based crystallization methods often result in polymorphic mixtures and lack precise control over product composition. Herein, we report a comparative investigation of solution crystallization versus mechanochemical synthesis for constructing MOSs from 9-anthracenecarboxylic acid (ACA) and 4,4 '-bipyridine (BPY). Solution-based approaches consistently yielded concomitant formation of neutral cocrystal (CC) and ionic cocrystal (ICC) forms, regardless of the solvent used. The resulting multicomponent solids were comprehensively characterized using a combination of single crystal X-ray diffraction, powder X-ray diffraction, Fourier-transform infrared spectroscopy, differential thermal analysis, and thermogravimetric analysis. In contrast, mechanochemical methods, including neat grinding (without solvent) and liquid-assisted grinding (with minimum solvent), enabled selective formation of either a phase pure CC or ICC form. Less polar and nonpolar organic solvents favor the kinetic CC, while polar water promotes formation of the thermodynamically stable ICC. Time-resolved in situ powder X-ray diffraction (TRIS-PXRD) captures the dynamic evolution of solid-state phases and reveals the complete transformation of the CC into ICC under neat grinding or water-assisted conditions. This study highlights the powerful role of mechanochemistry and in situ monitoring in steering solid-state reactivity and offers a sustainable pathway for the targeted and scalable synthesis of pure multicomponent organic materials. KW - Cocrystal KW - Synchrotron X-ray powder diffraction KW - Time-resolved in situ investigation PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641409 DO - https://doi.org/10.1039/D5CE00663E SN - 1466-8033 SP - 1 EP - 9 PB - Royal Society of Chemistry (RSC) CY - Cambridge AN - OPUS4-64140 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ryll, Tom William T1 - Applied and Technical Mineralogy:� high-throughput automated platform for in-situ monitoring of CaSO4 formation 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 - Geo4Göttingen 2025 CY - Göttingen, Germany DA - 14.09.2025 KW - Recycling KW - Gypsum KW - Synchrotron-X-ray-diffraction KW - Raman-spectroscopy KW - Automation PY - 2025 AN - OPUS4-64139 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 - OPUS4-64138 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 - CONF A1 - Falkenhagen, Jana T1 - Error margins in the Determination of Molar Mass and Oligomer Content of Polymers N2 - Size exclusion chromatography (SEC) is still the method of choice for determining the molar mass and molar mass distribution of macromolecules. It is a liquid chromatographic technique that separates molecules based on their size, respectively their hydrodynamic volume using a porous stationary phase that allows smaller molecules to pass through the pores while excluding larger molecules. The chromatogram from the size separation can be calibrated using polymers of known molar mass resulting in a relative molar mass distribution curve. From this distribution curve molar mass averages and the oligomer content (percentage of peak area smaller than 1000 g/mol and 500 g/mol) of polymers can be derived. The determination of oligomer content is important, because it is often used in regulatory contexts as a measure of small, mobile and potentially more toxic parts of the polymer. Polymer regulations are of increasing political and social importance. Regulations often set very narrow limits. SEC has rather large error margins of 10-20% for the molar mass determination performed in different laboratories or on different instruments. These variances are well known to all experts and users and have been investigated in several round robin tests in the past. These resulted in DIN and ISO standards which, in our opinion, no longer meet today's requirements. As far as we know, the margins of error in determining oligomer content have not yet been investigated. It is expected that the variation will be rather high. This is because it depends on many factors related to the experimental conditions (column sets used, solvent, temperatures, sample preparation) on the one hand, and the data evaluation mechanisms (choice of baseline and peak limits) on the other. In order to actually measure the error margins and to support this with actual data a round robin test has been performed from June to November 2024 with approx. 40 participating laboratories. Three different solvents were selected, namely THF, DMAc or DMF and water. The samples were selected together with all the experts, taking into account a wide range of practical aspects far from narrowly distributed standards: e.g higher distribution range, reduced solubility, included side components, copolymers and dispersions with gel content. In this contribution we will present the detailed concept of this round robin test and first results. T2 - SETAC Europe 35th Annual Meeting CY - Vienna, Austria DA - 11.05.2025 KW - Size exclusion chromatography KW - REACH KW - Polymers KW - Round Robin Tests PY - 2025 AN - OPUS4-63307 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana T1 - Limitations of SEC: Strategies for Improved Regulatory Polymer Analysis N2 - Polymers, composed of repeating units called monomers, exhibit a diverse range of properties, with molecular weight distribution (MWD) being particularly important for regulatory risk assessments. Size exclusion chromatography (SEC), or gel permeation chromatography (GPC), is the primary technique for MWD characterization, as detailed in OECD guidelines 118 and 119, along with DIN and ISO standards. However, SEC faces significant shortcomings that complicate the accurate determination of MWD and oligomer content. These limitations include the insolubility of certain polymers, crosslinking, and ultra-high molecular weight characteristics, which can exceed SEC's separation capabilities. The presence of salts or modifiers can further interfere with oligomer content determination, and the availability of appropriate SEC columns and calibration standards limits comparability across laboratories. To enhance SEC's reliability and applicability within regulatory frameworks, innovative methods and strategies are essential. Proposed solutions involve new sample preparation techniques, advanced data interpretation methods, and the establishment of standardized methodologies to promote harmonization. This is especially crucial in light of the expected Polymer REACh (PREACh) legislation, which aims to regulate polymer registration and risk assessment within the European market. Given the anticipated complexity of the registration process, which requires extensive data generation, proactive strategies are needed to address SEC's challenges. Currently, there are no viable alternatives for oligomer content determination, and the unique properties of polymers often necessitate tailored analytical approaches. Without new methodologies and guidelines, the polymer registration process could become burdensome and costly, jeopardizing important products and markets in the EU. Key areas for improvement include extending existing norms to cover a broader range of solvents, addressing high error margins in oligomer content determination, establishing harmonized approaches for dealing with side components, and providing clarity on measuring partially soluble polymers. In conclusion, addressing SEC's limitations through the development of comprehensive guidelines and harmonization is critical for ensuring accurate and efficient polymer analysis, ultimately facilitating smoother registration processes. T2 - SETAC Europe 35th Annual Meeting CY - Vienna, Austria DA - 11.05.2025 KW - Size exclusion chromatography KW - Polymers KW - REACH PY - 2025 AN - OPUS4-63309 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fink, Friedrich A1 - Stawski, Tomasz M. A1 - Emmerling, Franziska A1 - Falkenhagen, Jana T1 - A novel machine-learning approach to unlock technical lignin classification by NIR spectroscopy - bench to handheld N2 - In this research, the utilization of near-infrared (NIR) spectroscopy in conjunction with advanced machine learning methods is investigated for categorizing technical lignins obtained from different biomass sources and industrial procedures. Technical lignins, such as kraft, organosolv and lignosulfonates, have different chemical compositions, which continue to make uniform characterization and application in sustainable sectors extremely difficult. Fast, universally accessible analytics combined with data analysis is still an open question. For the first time three distinct NIR spectrometers—a high-performance benchtop system, a mid-priced compact device, and an economical handheld unit—were utilized to record NIR spectra of 31 unique lignin samples. The spectra underwent pre-processing through standard normal variate (SNV) transformation and Savitzky-Golay derivatives to amplify spectral features and decrease noise. Principal component analysis (PCA) was employed to reduce data complexity and extract crucial characteristics for classification purposes. Subsequently, four machine learning algorithms—Support Vector Machines (SVM), Gaussian Naive Bayes (GNB), Gaussian Process Classification (GPC), and Decision Tree Classification (DTC)—were implemented for the classification of the lignin samples. The DTC model exhibited the highest accuracy among them across different spectrometers. Although the benchtop spectrometer produced the most precise outcomes, the compact NeoSpectra system also displayed potential as a cost-efficient option. Nonetheless, the restricted spectral coverage of the handheld NIRONE spectrometer resulted in reduced classification accuracy. Our discoveries highlight the capability of NIR spectroscopy, combined with robust data analysis techniques, for the swift and non-destructive classification of technical lignins, facilitating their improved utilization in sustainable fields. KW - Technical lignins KW - NIR spectroscopy KW - Classification KW - Machine-learning KW - PCA PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634518 DO - https://doi.org/10.1016/j.chemolab.2025.105467 SN - 0169-7439 VL - 264 SP - 1 EP - 10 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-63451 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Parthasarathy, Thiyagaraj A1 - Mishra, Manish Kumar A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Ghosh, Soumyajit T1 - Simultaneously Mechanically Flexible, Photobending, and Acidochromic Cyanostilbene Molecular Crystals N2 - Molecular crystals that respond to multiple stimuli are gaining significant attention for their potential in smart materials like actuators and sensors. However, imparting multiple stimuli-responsive properties to a single crystal remains a major challenge. Herein, we report two cyanostilbene derivative-based crystals 1 and 2, with various responses to stimuli such as mechanical stress, light, acid vapors, etc. Both crystals 1 and 2 demonstrated mechanical flexibility and reversible acidochromism. Additionally, crystal 1 also exhibited light-induced photobending, which is ascribed to Z to E photoisomerization. Detailed structure–property correlation was established to unravel distinct mechanical responses. The development of these multitasking crystals may find applications in multitasking actuators, anticounterfeiting materials, and more. KW - Absorption KW - Crystals KW - Mechanical flexiblity KW - Photoisomerization PY - 2025 DO - https://doi.org/10.1021/acs.cgd.4c01341 VL - 25 IS - 2 SP - 309 EP - 318 PB - American Chemical Society (ACS) AN - OPUS4-62568 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ryll, Tom William T1 - Researching automation of gypsum recycling N2 - This poster illustrates the recent work on a setup for automated in-situ analysis of gypsum recycling processes. Analysis in synchrotron X-rays, Raman- and UV-vis spectroscopy are made possible with this compact and mobile setup. First results from Raman spectroscopy on the conversion of gypsum to bassanite in hypersaline solutions are presented and future plans on optimization are formulated. T2 - ANAKON 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Recycling KW - Automation KW - Synchrotron-X-ray-diffraction KW - Raman-spectroscopy KW - Gypsum PY - 2025 AN - OPUS4-62706 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Speight, Isaiah R. A1 - Ardila-Fierro, Karen J. A1 - Hernández, José G. A1 - Emmerling, Franziska A1 - Michalchuk, Adam A. L. A1 - García, Felipe A1 - Colacino, Evelina A1 - Mack, James T1 - Ball milling for mechanochemical reactions N2 - Mechanochemistry is an emerging field with the potential to pave the way for sustainable chemistry. Although the use of mechanical force to initiate chemical reactions has been recognized for millennia, it has often taken a backseat to thermal and photonic methods. Over the past 30 years, mechanochemistry has seen a resurgence of interest, attracting researchers across the globe. Despite its proven ability to address numerous challenges within the chemical community, mechanochemistry remains on the periphery. This Primer serves as a valuable guide for conducting mechanochemical reactions by ball milling, offering an overview of the processes, methods, tools and terminology necessary to embark on research in this field. It also highlights persistent hurdles such as equipment standardization, understanding the impact of new discoveries and the lack of predictability of reaction outcomes. The Primer’s focus is on how mechanochemical ball milling is used in various chemical transformations, distinguishing it from other forms of mechanochemistry discussed in the literature. With a promising future, this Primer serves as a gateway for those aspiring to contribute to the field’s advancement. KW - Mechanochemistry KW - Ball milling KW - Upscaling PY - 2025 DO - https://doi.org/10.1038/s43586-025-00401-2 SN - 2662-8449 VL - 5 IS - 1 SP - 1 EP - 18 PB - Springer Science and Business Media LLC AN - OPUS4-63447 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhuang, Yiling A1 - Haderlein, Stefan B. A1 - Lutze, Holger V. A1 - Sun, Chen A1 - Fink, Friedrich A1 - Paul, Andrea A1 - Spahr, Stephanie T1 - Persulfate activation by biochar for trace organic contaminant removal from urban stormwater N2 - Persistent and mobile trace organic contaminants (TrOCs) in urban stormwater are difficult to remove through sedimentation- or sorption-based treatment and pose a risk to aquatic ecosystems and drinking water supplies. We demonstrate that the chemical oxidant peroxydisulfate (PDS) can be activated by shrimp shell biochar at pH 7 to form reactive species that selectively react with widespread stormwater contaminants. Of 11 TrOCs tested, oxidative transformation was observed for 1,3-diphenylguanidine, 2-hydroxybenzothiazole, 1H-benzotriazole, 5-methyl-benzotriazole, and diuron during water treatment with biochar and PDS. Laboratory batch experiments conducted with street runoff and a synthetic water showed that the water matrix, containing up to 7.5 mg L-1 dissolved organic carbon and 100 mM chloride, had a minor effect on the formation of reactive species and contaminant transformation. Using a set of scavengers and probe compounds, we provide evidence for singlet oxygen (1O2) as the predominant reactive species in the biochar/PDS system, which is in agreement with the selectivity of the process to oxidize electron-rich organic contaminants. The results of our study inform new strategies for stormwater treatment using heterogeneous oxidation processes for the abatement of persistent and mobile organic contaminants. KW - Stormwater treatment KW - Oxidation processes KW - Pyrogenic carbon PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-637952 DO - https://doi.org/10.1016/j.watres.2025.123921 SN - 0043-1354 VL - 284 SP - 1 EP - 8 PB - Elsevier Ltd. AN - OPUS4-63795 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Go, Eun Sul A1 - Hong, Eun Ji A1 - Lee, Ji Yeong A1 - Stolar, Tomislav A1 - Peterson, Gregory I. A1 - Emmerling, Franziska L. A1 - Kim, Kyoungsoo A1 - Kim, Jeung Gon T1 - Insights into Mechanochemical Solid-State Ball-Milling Reaction: Monitoring Transition from Heterogeneous to Homogeneous Conditions N2 - As mechanochemical synthesis has advanced significantly, there has been intense interest in understanding the underlying mechanisms of these reactions. Given that many mechanochemical processes are conducted in the solid-state without solvation yet sometimes yield faster reactions than those in solution, we sought to address the following question: Are mechanochemical reactions homo- or heterogeneous? To investigate, we employed a model system involving the mixing and copolymerization of l-lactide (LLA) and d-lactide (DLA), monitored through powder X-ray diffraction (PXRD), nuclear magnetic resonance, and differential scanning calorimetry. In situ and ex situ PXRD analyses of the mixture of LLA and DLA showed that vibratory ball milling rapidly transformed the initially heterogeneous lactide mixture into a homogeneous phase within one min due to collisions between the balls and the jar. By varying the milling conditions, we were able to regulate the level of mixing, which subsequently influenced the copolymerization outcomes. In the solid-state ball-milling copolymerization of LLA and DLA in the presence of a catalyst and initiator, multiblock copolymers of poly(l-lactic acid) and poly(d-lactic acid) were formed within one min during the early stage of the reaction, when incomplete mixing of the monomers led to a process governed by phase heterogeneity. In contrast, prolonged polymerization promoted conditions approaching homogeneity, ultimately yielding atactic poly(lactic acid). This transition from heterogeneous to homogeneous reactions is a distinctive feature compared to conventional homogeneous reactions, potentially leading to mechano-exclusive reaction designs. KW - Mechanochemistry KW - Ball-milling KW - Homogeneous reaction KW - Heterogeneous reaction PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-638008 DO - https://doi.org/10.1021/jacsau.5c00322 SN - 2691-3704 VL - 5 IS - 6 SP - 2720 EP - 2727 PB - American Chemical Society (ACS) AN - OPUS4-63800 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - May, Anastasia T1 - Thermomechanochemical Synthesis of Pimelic Acid Cocrystals N2 - Milling temperature is a critical factor in mechanochemistry, affecting the kinetics and outcomes of reactions. In the context of cocrystallization, the influence of milling temperature on the process has been investigated for cocrystal systems pyrazinamide:pimelic acid (PZA:PA) and 4,4'-bipyridine:pimelic acid (BPY:PA). By means of temperature-controlled milling, stabilization of metastable polymorph of PZA:PA was achieved, thereby decelerating the aging process of the polymorph. This was accomplished through controlled heated milling of PZA and PA. Furthermore, we have successfully synthesized all three BPY:PA polymorphs by mechanochemistry involving controlled cooled and heated milling. In previous studies, only the most stable polymorph was obtained by mechanochemistry. T2 - 10th European Crystallography School CY - Ohrid, North Macedonia DA - 23.06.2025 KW - Mechanochemistry KW - Cocrystal PY - 2025 AN - OPUS4-63797 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Paul, Sagar A1 - Dolai, Malay A1 - Nanda Goswami, Juli A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Drew, Michael G. B. A1 - Chattopadhyay, Shouvik A1 - Sarkar, Rabi Sankar A1 - Sunil, Appu A1 - Novitchi, Ghenadie A1 - Moreno-Pineda, Eufemio A1 - Wernsdorfer, Wolfgang T1 - From strong to weak interaction: Reconciling SQUID and μSQUID-EPR data in anomalous Co(ii) dimers N2 - Magnetic molecules have been proposed as scaffolds for novel quantum technologies, ranging from quantum sensing and quantum memory to multilevel quantum bits (qudits) and fault-tolerant quantum computation. Integration of magnetic molecules into cutting-edge applications hinges on a deep understanding and tunability of their spin states. To date, the strategic manipulation of the local environment of the ion and careful selection of the magnetic core have enabled the desired tunability and scalability of the spin states. For such goals, however, extracting the anisotropic parameters that dictate the characteristics of the Spin Hamiltonian is challenging, especially for molecules consisting of multiple magnetic cores. We address these challenges by studying two cobalt(II) dinuclear systems, complicated by inherent spin–orbit coupling. We explore the magnetic properties of these systems in two temperature regimes: (i) at sub-Kelvin temperatures employing single crystals at 30 mK using a unique μSQUID-EPR technique that examines the microwave absorption peaks in the magnetisation data and their variation with field angle and frequency; and (ii) in bulk employing convectional SQUID magnetometry above 2 K i.e., χMT(T) and M(H). Unexpectedly, sub-Kelvin temperature investigations reveal a negligible interaction, whereas the SQUID data reveal a much stronger interaction between the Co(II) ions. An understanding of these data is developed based on a strong coupling model and the coupling of two moieties with a spin-effective ground state. KW - cOBALT(II)-complex KW - In situ complex formation KW - Magnetic property KW - Crystal structure PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641421 DO - https://doi.org/10.1039/D5QI01387A SN - 2052-1553 SP - 1 EP - 13 PB - Royal Society of Chemistry (RSC) CY - Cambridge AN - OPUS4-64142 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 - 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 - Alić Stolar, Jasna T1 - Harnessing mechanochemistry to tackle PFAS pollution N2 - We are currently facing one of the most serious environmental crises in human history – the widespread pollution caused by PFAS. PFAS stands for per- and polyfluoroalkyl substances, which are toxic, persistent, highly mobile, and bioaccumulative compounds, often referred to as 'forever chemicals'. For over 70 years, they have been used to make products resistant to water, heat, and stains, but the cost of damaging ecosystems and harming human health was revealed far too late. As of 2023, there were more than 23,000 confirmed PFAS contamination sites in Europe alone, with at least an equal number of presumptive contamination sites due to historical and current industrial activities.1 Public concern has pushed regulatory bodies to restrict the production of the most common PFAS, but with over 10,000 PFAS compounds and existing contamination, the problem remains largely unresolved. State-of-the-art remediation strategies rely on energy-intensive incineration, which releases greenhouse gases and smaller, volatile PFAS derivatives.2 Here, we present a fast, simple, and sustainable method for the complete degradation of PFAS, leveraging mechanochemistry3 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 - Tag der Chemie CY - Berlin, Germany DA - 03.07.2025 KW - Mechanochemistry KW - Forever chemicals KW - Sustainability PY - 2025 AN - OPUS4-63972 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 - International Conference on Sustainable Chemistry for Net Zero (ICSC-NZ) CY - St. Andrews, Scotland DA - 10.06.2025 KW - Mechanochemistry KW - PFAS KW - Remediation PY - 2025 AN - OPUS4-63970 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 - International Conference on Sustainable Chemistry for Net Zero (ICSC-NZ) CY - St. Andrews, Scotland DA - 10.06.2025 KW - Mechanochemistry KW - PFAS KW - Remediation PY - 2025 AN - OPUS4-63971 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Das, Prasenjit A1 - Chakraborty, Gouri A1 - Yang, Jin A1 - Roeser, Jérôme A1 - Küçükkeçeci, Hüseyin A1 - Nguyen, Anh Dung A1 - Schwarze, Michael A1 - Gabriel, Jose A1 - Penschke, Christopher A1 - Du, Shengjun A1 - Weigelt, Vincent A1 - Khalil, Islam E. A1 - Schmidt, Johannes A1 - Saalfrank, Peter A1 - Oschatz, Martin A1 - Rabeah, Jabor A1 - Schomäcker, Reinhard A1 - Emmerling, Franziska A1 - Thomas, Arne T1 - The Effect of Pore Functionality in Multicomponent Covalent Organic Frameworks on Stable Long‐Term Photocatalytic H2 Production N2 - AbstractIn nature, organic molecules play a vital role in light harvesting and photosynthesis. However, regarding artificial water splitting, the research focus is primarily on inorganic semiconductors. Although organic photocatalysts have high structural variability, they tend to exhibit lower quantum efficiencies for water splitting than their inorganic counterparts. Multicomponent reactions (MCRs) offer an attractive route to introduce different functional units into covalent organic frameworks (COFs) and enable semiconducting properties and high chemical stability, creating promising materials for long‐term photocatalytic applications, such as H2 production. Herein, five highly crystalline donor‐acceptor based, 4‐substituted quinoline‐linked MCR‐COFs are presented that are prepared via the three‐component Povarov reaction. The pore functionality is varied by applying different vinyl derivatives (e.g., styrene, 2‐vinyl pyridine, 4‐vinylpyridine, 4‐vinyl imidazole, 2,3,4,5,6‐pentafluorostyrene), which has a strong influence on the obtained photocatalytic activity. Especially an imidazole‐functionalized COF displays promising photocatalytic performance due to its high surface area, crystallinity, and wettability. These properties enable it to maintain its photocatalytic activity even in a membrane support. Furthermore, such MCR‐COFs display dramatically enhanced (photo)chemical stability even after long‐term solar light irradiation and exhibit a high and steady H2 evolution for at least 15 days. KW - Sstability KW - Covalent organic frameworks KW - Pore functionality KW - Long-term H2 production KW - Multicomponent reactions PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639787 DO - https://doi.org/10.1002/aenm.202501193 SN - 1614-6832 SP - 1 EP - 10 PB - Wiley VHC-Verlag AN - OPUS4-63978 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wagner, Jan A1 - Dudziak, Mateusz A1 - Falkenhagen, Jana A1 - Rockel, Daniel A1 - Reimann, H.-A A1 - Schartel, Bernhard T1 - This is the way: An evidence based route to phytic-acid–based flame retardant poly(lactide acid) N2 - A systematic sequence of materials was investigated to develop phytic-acid (Phyt)–based flame retarded poly (lactide acid) (PLA), while factoring in molecular weight (MW), crystallinity and mechanical properties. Synergistic approaches were developed based on combinations with lignin and expandable graphite (EG), as well as by applying different Phyt salts of melamine (Mel), piperazine (Pip), and arginine (Arg). Compounds were twin screw extruded, injection molded, hot pressed and investigated with thermal analysis, size exclusion chromatography, infrared spectroscopy, tensile testing, limited oxygen index (LOI), UL 94, cone calorimeter, and scanning electron microscope. 16.7 wt.% flame retardant (FR) slightly enhances crystallization while MW remains unchanged in PLA Phyt Arg and PLA Phyt Mel. LOI was improved to 43.7 vol.% for PLA Phyt Arg, UL 94 V0 achieved for PLA Phyt Pip. Cone calorimeter results show total heat evolved reduced by 14 %, maximum average rate of heat emission 43 % lower, and peak heat release rate reduced by 50 % for PLA Phyt Mel. Phyt Mel combined with EG increased the char yield of PLA to 20 wt.% and 15.5 wt.% at 600 and 900 ◦C, respectively. Phyt is exploited to enhance char yield, stabilize the intumescent char, and lower the apparent effective heat of combustion. The combination of Phyt Mel and EG was proposed as an efficient FR for PLA via an evidence based developing route. KW - Polylactide acid KW - Intumescent flame retardant KW - Phosphorous flame retardant KW - Phytic acid KW - Expandable graphite KW - Melamine PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626395 DO - https://doi.org/10.1016/j.polymdegradstab.2025.111242 SN - 1873-2321 SN - 0141-3910 VL - 234 SP - 1 EP - 14 PB - Elsevier Ltd. AN - OPUS4-62639 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wagner, Jan T1 - This is the Way: An Evidence Based Route to Phytic-acid-based Flame Retardant Poly(lactide acid) N2 - Main message: This study provides an evidence-based route to flame retard poly (lactide acid) (PLA) with phytic acid (Phyt)-based flame retardants (FR). Phyt was prepared with lignin (Lig) and expandable graphite (EG). Three amine salts (arginine (Arg), piperazine (Pip), melamine (Mel)) were also synthesized with Phyt. Findings include UL 94 V0 classification, limited oxygen index (LOI) = 43.7 vol% and reduced total heat released (THR), while molecular weight (MW) was not affected. Combinations lead to the most effective FR. Introduction: As demand for biobased polymers increases, biobased FRs remain scarce in the market. With 28 wt.% P, Phyt is promising to be a biobased FR, but Phyt efficiency as a FR needs to be improved. [1] Furthermore, as a strong acid, it esterifies and hydrolysis PLAs backbone. With the combinations proposed in this study, processability and MW in PLA compounds were untouched, while FR performance of Phyt was enhanced. Experimental: Compounds analyzed in this study were: PLA, PLA Lig, PLA EG, PLA PhytLig, PLA PhytEG, PLA Mel, PLA PhytArg, PLA PhytPip, PLA PhytMel, PLA PhytMel Lig and PLA PhytMel EG. Addition of Phyt based FR was 16.7 wt.%, Lig and EG 10wt.%. Compounds were processed with twin screw extrusion, injection molding and hot press. Analysis was done with size exclusion tomography, differential scanning calorimetry (DSC), tensile strength, cone calorimeter, UL 94, LOI and thermogravimetry analysis (TGA) combined with Fourier transformation infrared spectroscopy (FTIR). Residues were analyzed with scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). Results and Discussion: To synthesize the FR, Lig and Phyt (solved in water) were mixed and dried. A solid material formed, which was grinded and then compounded with PLA. The same was done with EG. Phyt + Arg/Pip/Mel FR materials were each titrated to a pH of ~4.5, since this pH is known to be least harmful for the PLA backbone. For PhytMel a salt precipitated. PhytPip and PhytArg were dried and a resin-like structure was obtained, which was grinded to a powder. The molar mass distribution of PLA PhytArg (10,000 g/mol – 600,000 g/mol) is similar to PLAs ranging from 15,000 g/mol – 600,000 g/mol. MW distribution from highest to lowest was PLA > PLA PhytArg > PLA PhytMel > PLA PhytMel EG > PLA PhytMel Lig > PLA PhytEG > PLA PhytLig > PLA PhytPip. The reaction between Phyt and Arg/Mel prevents MW decomposition of PLA through a reaction of P acid and NH2 groups. Tensile strength declined to 35.9 MPA for PLA PhytMel and 32.1 MPA for PLA PhytArg, compared to 51.4 MPA for PLA. DSC analysis revealed TG was not affected for the FR compounds: Phyt Lig/EG/Arg/Mel, compared to PLA. PLA PhytMel crystallinity 𝐾∆𝐻𝑐𝑐𝑐𝑐 was 30%, PLA PhytArg crystallinity was 50%, compared to PLA 𝐾∆𝐻𝑐𝑐 was 46%. Melting peaks were not affected in PLA Phyt Arg/Mel. Flammability investigations lead to results of LOI 25.8 vol%/ UL 94 V2 classification in PLA, PLA PhytArg LOI 43.7 vol%/ UL 94 V2, due to strong dripping as a cooling mode of action. [2] PLA PhytMel burned with intumescent char and LOI 38.2 vol%/ UL 94 V2 was measured. Due to strong melt dripping, PLA PhytPip reached UL 94 V0. TGA revealed increased residue for all FR compounds. When materials were combined in PLA PhytMel EG residue was maximized to 19.9 wt.% (600°C, 𝑁𝑁2 atmosphere). FTIR analysis revealed PO and PH stretching vibrations, indicating radical scavenging. Cone calorimeter investigations of PLA, PLA PhytPip and PLA PhytArg lead to a steep incline in HRR to peak heat release rate (pHRR). Values are provided in Table 1. PLA PhytMel containing compounds exhibited prolonged burning and protective layer. PLA PhytLig, PLA PhytEG, PLA Mel (pHRR >1000) were investigated but proved inferior to PLA PhytMel, PLA PhytMel Lig and PLA PhytMel EG. THR was reduced in all Phyt compounds. Intumescence was observed in all compounds except for PLA Lig, PLA PhytLig and PLA PhytMel Lig. PLA PhytMel EG proved as the most effective compound in fire testing with a firm, coherent and intumescent char structure. This study provides an understanding of Phyt as a FR. It systematically improves Phyts effectiveness and processability in PLA. This evidence T2 - 20th European Meeting on Fire Retardant Polymeric Materials (FRPM2025) CY - Madrid, Spain DA - 03.06.2025 KW - Polylactide acid KW - Intumescence KW - Phosphorous flame retardant KW - Phytic acid PY - 2025 AN - OPUS4-63395 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Mechanochemical conversion of polyethylene terephthalate into valuable metal-organic frameworks N2 - Single-use plastics are causing plastic pollution, and less than 10% of plastic waste is recycled globally. Here, we present a sustainable mechanochemical1 protocol for converting post-consumer polyethylene terephthalate (PET) textile and bottles into the porous metal-organic framework (MOF) UiO-66. We used time-resolved in situ synchrotron powder X-ray diffraction and Raman spectroscopy to monitor the depolymerization of PET during ball milling with sodium and potassium hydroxide and water as a liquid additive (Figure 1). For synthesizing UiO-66, we focused on the better performing sodium hydroxide and optimized two distinct synthetic routes to produce high-quality UiO-66. Our results demonstrate the potential of mechanochemistry to enable more circular MOF synthesis using post-consumer PET waste. T2 - The International Symposium on Mechanochemistry (Mech’cheM) 2025: New forces in Mechanochemistry CY - Montpellier, France DA - 04.06.2025 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2025 AN - OPUS4-63943 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Mechanochemical Conversion Of Polyethylene Terephthalate Into Valuable Metal-organic Frameworks N2 - Single-use plastics are causing plastic pollution, and less than 10% of plastic waste is recycled globally. Here, we present a sustainable mechanochemical protocol for converting post-consumer polyethylene terephthalate (PET) textile and bottles into the porous metal-organic framework (MOF) UiO-66. We used time-resolved in situ synchrotron powder X-ray diffraction and Raman spectroscopy to monitor the depolymerization of PET during ball milling with sodium and potassium hydroxide and water as a liquid additive. For synthesizing UiO-66, we focused on the better performing sodium hydroxide and optimized two distinct synthetic routes to produce high-quality UiO-66. Our results demonstrate the potential of mechanochemistry to enable more circular MOF synthesis using post-consumer PET waste. T2 - International Conference on Sustainable Chemistry for Net Zero CY - St. Andrews, United Kingdom DA - 10.06.2025 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2025 AN - OPUS4-63944 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 - Gugin, Nikita T1 - Advancing Industrial Mechanochemistry: Real-Time Insights for Sustainable, Solvent-Free Manufacturing N2 - Reactive extrusion has emerged as a continuous approach for conducting mechanochemical reactions on a large scale. However, the use of this method under industrial conditions is hindered by limited understanding. In this study, we unveil the black box of reactive extrusion by employing energy-dispersive X-ray diffraction (EDXRD) to collect time- and spatially resolved in situ data. Our findings demonstrate the EDXRD method’s applicability to a range of chemical transformations and conditions associated with reactive extrusion. T2 - Chemie-Kolloquium & IfC Science Day CY - Berlin, Germany DA - 22.01.2025 KW - Mechanochemistry PY - 2025 AN - OPUS4-63801 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska A1 - Michalchuk, Adam A1 - Bhattacharya, Biswajit A1 - Rodríguez Sánchez, Noelia A1 - Gugin, Nikita T1 - Mechanochemical innovations for sustainable synthesis of framework materials and industrial scaleup N2 - Mechanochemistry has emerged as a powerful approach for sustainable materials synthesis and processing, with significant potential to meet the UN Sustainable Development Goals. This presentation will highlight our recent advancements in understanding, monitoring, and scaling-up mechanochemical synthesis of framework materials, focusing on the balance between fundamental understanding of reaction mechanisms and its practical applications in energy storage and energy transfer materials. A central focus of our work has been the development and application of time-resolved in situ monitoring techniques for mechanochemical processes. Our research on real-time synchrotron X-ray diffraction has enabled unprecedented insights into reaction pathways and kinetics. Recently, we have successfully applied energy-dispersive X-ray diffraction for time-resolved in situ monitoring of reactive extrusion, marking a significant step towards ‘lighting up’ industrial-scale mechanochemistry. Bridging fundamental understanding with practical applications, we have explored the mechanochemical synthesis of functional materials for energy storage and transfer, making process in the mechanochemical synthesis of highly proton-conductive metal phosphonates, demonstrating the potential of mechanochemistry to manufacture advanced materials for energy applications. T2 - 17. international-conference für Materialchemie CY - Edinburgh, United Kingdom DA - 07.07.2025 KW - MOF KW - Synchrotron KW - ZIF PY - 2025 AN - OPUS4-64841 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batteas, James A1 - Blank, Kerstin G. A1 - Colacino, Evelina A1 - Emmerling, Franziska A1 - Friščić, Tomislav A1 - Mack, James A1 - Moore, Jeffrey A1 - Rivas, Maria Elena A1 - Tysoe, Wilfred T1 - Moving mechanochemistry forward N2 - Arguably mechanochemistry is one of the oldest, and at the same time one of the newest, areas of chemistry. One of the oldest, because it has been theorized that early hominids were able to develop rapidly due to their ability to heat and mechanically process their food to make it easier to digest. Old, because the ancient Greeks knew that mechanically activating stones (consisting of cinnabar) with vinegar in a copper pestle and mortar caused them to convert into mercury. We might be forgiven for thinking that this could have led our alchemical forbears to wonder if there were other stones that might also be persuaded to convert into gold. Early chemical luminaries such as Michael Faraday and Wilhelm Röntgen dabbled in mechanochemistry. However, in the late 19th and early 20th centuries, the field developed separately in many areas. Perhaps most significantly, synthetic chemists realized that reactions could be carried out with surprisingly high yields and selectivities by shaking them in a ball mill, and that they could even make novel compounds that their colleagues just using heat were not able to. Physicists were mechanically rearranging atoms into new configurations (i.e., doing chemistry) using exotic means such as atomic force microscope tips and optical tweezers. Scientists and engineers studying the formation of lubricious and anti-wear films realized that they were mechanochemically formed. Biochemists found molecular motor proteins, such as myosin and kinesin, that were able to convert chemical energy into motion or, vice versa, mechanical energy into the biochemical energy storage molecule adenosine triphosphate. In 2023, this confluence of advances convinced the Royal Society of Chemistry that the time was ripe to establish a new journal dedicated to the field of mechanochemistry. It is rare that a journal has the privilege of helping to create a new sub-branch of chemistry but, having done so, it has the obligation of helping to define the field and, optimistically, suggesting how the field might develop. This editorial has two major goals. The first is to bring to the attention of the scientific community the challenges faced by the field to set people thinking about how they might contribute and, second, to form the basis for more thorough discussions in the future. The sub-topics below outline current thoughts brought forward from members of our editorial board. We lay out areas and topics here with the intent of establishing a new editorial series, which we invite the community to contribute to, and outline topics and hopefully lay out challenges, which will enable us as a community to come together to move mechanochemistry forward. KW - Mechanochemistry PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646086 DO - https://doi.org/10.1039/d4mr90021a SN - 2976-8683 VL - 2 IS - 1 SP - 10 EP - 19 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64608 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lopes, Chrystal A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Leyssens, Tom A1 - Dupray, Valérie A1 - Brandel, Clement A1 - Cartigny, Yohann T1 - Efficient racemization of the pharmaceutical compound Levetiracetam using solvent-free mechanochemistry N2 - We present the racemization of an active pharmaceutical ingredient Levetiracetam using a novel approach. We demonstrate the design of a 100% solvent-free process that proceeds by high energy milling inside a regular mixer mill. The kinetics of the racemization process is drastically improved compared to the solution-based approach and illustrates the tremendous potential of mechanochemistry. In this study, we highlight the importance of mixing efficiency regarding data reproducibility, and we show, in particular, that water contamination has a negative impact on the reaction rate. Moreover, in situ X-ray diffraction gives us first insights into the mechanisms involved in the solid state during the mechanochemical racemization process. KW - Mechanochemistry PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646108 DO - https://doi.org/10.1039/d4mr00103f SN - 2976-8683 VL - 2 IS - 1 SP - 83 EP - 90 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64610 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stawski, Tomasz T1 - Towards sustainable solution-driven recycling of gypsum 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 (brineswith c[NaCl] > 4 M). The optimum conditions for the efficient production 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 - RAL-SAS - UK Small angle scattering meeting 2025 CY - Oxford, United Kongdom DA - 16.06.2025 KW - Scattering KW - SAXS KW - Calcium sulfate KW - Gypsum PY - 2025 AN - OPUS4-64682 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Stawski, Tomasz A1 - Miliute, Aiste T1 - Structural Refinement of ZrV₂O₇ with Negative Thermal Expansion Using Pair Distribution Function Analysis N2 - This repository contains Python scripts specifically developed for structural refinement of Zirconium Vanadate (ZrV₂O₇), a material known for its negative thermal expansion (NTE). The scripts implement Pair Distribution Function (PDF) analysis to refine crystal structures directly from experimental X-ray diffraction (XRD) data. The refinement workflow is built around the DiffPy-CMI library, enhanced with custom functionalities tailored for ZrV₂O₇ and similar oxide materials. KW - Zirconium vandate KW - Total scattering KW - Pair distribution function KW - Structure refinement PY - 2025 DO - https://doi.org/10.5281/zenodo.15395752 PB - Zenodo CY - Geneva AN - OPUS4-64750 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mishra, Rajesh K. A1 - Minussi, F.B. A1 - Kumari, Priyanka A1 - Shahi, Rohit R. A1 - Yadav, R.P. A1 - Emmerling, Franziska A1 - Araújo, E.B. T1 - Effect of sintering temperature on structural, microstructural, and dielectric properties of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 multi-cations high entropy oxides N2 - The study reports the effect of sintering temperature on structural, microstructural, and dielectric properties of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 spinel high-entropy oxides (HEOs) synthesized through the solid-state mechanochemistry method. The sintering of the ceramic powders was accomplished at three different temperatures (1000 ◦C, 1100 ◦C, and 1250 ◦C), followed by air quenching. XRD analysis along with Le-Bail refinement confirms that 1100 ◦C and 1250 ◦C sintered oxides comprised of a single cubic spinel phase (Fd3m), while 1000 ◦C sintered oxide contains constituent oxides and a spinel phase. The phase formation of oxides sintered at 1100 ◦C and 1250 ◦C has also been confirmed by Raman spectroscopic analysis. Microstructural analysis revealed that the aggregated particle size increases with the rise in sintering temperature. With the change in sintering temperature, the dielectric behavior of the ceramic changed extensively. The 1100 ◦C sintered ceramic exhibits high frequency-dependent behavior, whereas the 1250 ◦C sintered ceramic yields low frequency-dependent behavior. The 1250 ◦C sintered HEO exhibits low-loss tangent (tan δ = 0.01) with higher dielectric permittivity (εʹ = 44) at high frequency (1 MHz) compared to the 1100 ◦C sintered ceramic and many other conventional dielectrics. Fractal concept and impedance analysis have been employed to correlate the microstructure-dielectric property relation of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 spinel HEOs. The found Hurst exponent values for both different temperature-sintered HEOs are less than 0.5, indicating the anti-persistent behavior. This signifies that the height variations at neighboring pixels are negatively correlated. The present work is of fundamental importance in employing fractal analysis for the first time on spinel HEOs and correlating their properties. It also shows that processing conditions can effectively tailor the dielectric properties of the materials. KW - Multi-cations high entropy oxide KW - Mechanochemistry KW - Spinel structure KW - Fractal and impedance spectroscopic analysis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647584 DO - https://doi.org/10.1016/j.ceramint.2025.09.256 SN - 0272-8842 VL - 51 IS - 27 SP - 55341 EP - 55354 PB - Elsevier Ltd. AN - OPUS4-64758 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska A1 - Michalchuk, Adam A1 - Stolar, Jasna A1 - Falkenhagen, Jana A1 - Bhattacharya, Biswajit A1 - Gugin, Nikita A1 - Casali, Lucia T1 - Mechanochemical pathways to sustainability: from molecular insights to applications N2 - Mechanochemical Innovations for Sustainable Synthesis of Framework Materials and Industrial ScaleUp Mechanochemistry has emerged as a powerful approach for sustainable materials synthesis and processing, with significant potential to meet the UN Sustainable Development Goals. This presentation will highlight our recent advancements in understanding, monitoring, and scaling-up mechanochemical synthesis of framework materials, focusing on the balance between fundamental understanding of reaction mechanisms and its practical applications in energy storage and energy transfer materials. A central focus of our work has been the development and application of time-resolved in situ monitoring techniques for mechanochemical processes. Our research on real-time synchrotron X-ray diffraction has enabled unprecedented insights into reaction pathways and kinetics. Recently, we have successfully applied energy-dispersive X-ray diffraction for time-resolved in situ monitoring of reactive extrusion, marking a significant step towards ‘lighting up’ industrial-scale mechanochemistry. Bridging fundamental understanding with practical applications, we have explored the mechanochemical synthesis of functional materials for energy storage and transfer, making process in the mechanochemical synthesis of highly proton-conductive metal phosphonates, demonstrating the potential of mechanochemistry to manufacture advanced materials for energy applications. T2 - GDCh Universität Marburg CY - Marburg, Germany DA - 10.02.2025 KW - Situ investigation KW - Nanoparticles KW - Metal phosphonates PY - 2025 AN - OPUS4-64844 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska A1 - Michalchuk, Adam A1 - Casali, Lucia A1 - May, Anastasia T1 - Real-Time Monitoring and Temperature Control for Optimized Polymorph Engineering N2 - Integrating real-time monitoring with precise temperature control and mechanochemical processing represents a transformative approach to the controlled engineering of polymorphic forms in molecu-lar solids. Combining these methodologies overcomes the limitations of traditional solution-based or purely thermal approaches, enabling access to metastable or otherwise elusive polymorphs under milder and more sustainable conditions. Recent studies have shown that mechanochemical trans-formations proceed through distinct kinetic stages, including prolonged induction periods that can be tuned by adjusting the mechanical energy input[1]. These induction periods are associated with pro-cesses of mechanical activation, such as the accumulation of defects and increased surface energy, which lower the effective energy barriers for polymorphic transitions. Crucially, it is the total accumu-lated mechanical energy, rather than the duration or intensity of milling alone, that dictates the onset of polymorphic conversion, offering a new dimension of kinetic control[2-5]. Variable temperature ball milling reveals that the temperature required to induce polymorphic trans-formations can be significantly lower than under conventional thermal methods. For instance, tran-sitions that typically require high temperatures under equilibrium conditions can be achieved at sub-stantially lower temperatures in the presence of mechanical activation. This has been demonstrated in cocrystal systems such as nicotinamide-pimelic acid and isonicotinamide-glutaric acid, where the transition temperature was lowered by up to 25°C[2,3]. Real-time, in situ powder X-ray diffraction and temperature monitoring are essential for capturing transient phases and elucidating the interplay between thermal and mechanical effects. This confirms that combining mechanical energy with con-trolled temperature not only accelerates transformation kinetics, but also expands the accessible polymorphic landscape [2,3]. Collectively, these advances underscore the potential of real-time monitored, temperature-controlled mechanochemistry as a robust platform for the selective design and manufacturing of polymorphs. This approach provides unprecedented control over solid-state reactivity and opens new avenues for the sustainable and targeted engineering of functional materials and pharmaceuticals. T2 - 13th Bologna´s convention on Crystal Forms - CF@Bo n.13 University of Bologna CY - Bologna, Italy DA - 07.09.2025 KW - Plymorhism KW - Pre-activation PY - 2025 AN - OPUS4-64839 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska A1 - Michalchuk, Adam A1 - Bhattacharya, Biswajit A1 - Rodríguez Sánchez, Noelia A1 - Gugin, Nikita T1 - Advancing sustainable synthesis through in situ monitoring and industrial scale-up of mechanochemical processes N2 - Mechanochemistry has emerged as a powerful approach for sustainable materials synthesis and processing, with significant potential to meet the UN Sustainable Development Goals. This presentation will highlight our recent advancements in understanding, monitoring, and scaling-up mechanochemical transformations, focusing on the balance between fundamental understanding of reaction mechanisms and its practical applications in energy storage and energy transfer materials. Our research has made significant strides in elucidating the fundamental mechanisms of mechanochemical reactions. We have investigated delayed polymorphism under mechanochemical conditions, revealing new insights into the interplay between mechanical impact, thermal effects, and structural transformations in molecular crystals. By employing variable temperature ball milling, we have demonstrated unprecedented control over polymorphic forms in organic cocrystals, opening new avenues for tailoring material properties. A central focus of our work has been the development and application of time-resolved in situ monitoring techniques for mechanochemical processes. Our research on real-time synchrotron X-ray diffraction has enabled unprecedented insights into reaction pathways and kinetics. Recently, we have successfully applied energy-dispersive X-ray diffraction for time-resolved in situ monitoring of reactive extrusion, marking a significant step towards ‘lighting up’ industrial-scale mechanochemistry. Bridging fundamental understanding with practical applications, we have explored the mechanochemical synthesis of functional materials for energy storage and transfer, making process in the mechanochemical synthesis of highly proton-conductive metal phosphonates, demonstrating the potential of mechanochemistry to manufacture advanced materials for energy applications. Addressing the challenges of industrial scale-up, we have investigated the role of solvent polarity in mechanochemical reactions, providing valuable guidance for optimizing organic syntheses such as the Knoevenagel condensation. This work contributes to our broader efforts to develop more efficient and sustainable chemical manufacturing processes. Looking to the future, we will discuss emerging directions in mechanochemistry, including the development of continuous flow processes and the integration of machine learning approaches for reaction prediction and optimization. As we anticipate the next decade of research, we envision mechanochemistry playing an increasingly crucial role in sustainable chemical manufacturing and materials processing, with far-reaching implications for addressing global energy and environmental challenges. T2 - Mech’cheM 2025: New forces in Mechanochemistry Conference CY - Montpellier, France DA - 04.06.2025 KW - Phosphonates KW - Biocomposites PY - 2025 AN - OPUS4-64845 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 - CONF A1 - Stawski, Tomasz T1 - Towards sustainable solution-driven recycling of gypsum N2 - Gypsum (CaSO₄·2H₂O) is a crucial mineral across sectors such as construction, agriculture, and biomedicine. Despite its potentially full recyclability, a shortage looms due to limited mining in Europe and decreasing production of flue gas desulfurization (FGD) gypsum, a byproduct of coal power plants. With current EU consumption at 24 MT/a (17 MT mined, 7 MT FGD), a deficit of 10-35 MT/a is projected by the 2030s as CaSO₄ becomes a critical raw material [1]. Meanwhile, substantial CaSO₄ waste is produced in various industries (e.g., phosphogypsum, red gypsum), but its recycling remains limited (10% in Germany, 5% in the EU) due to contamination and separation challenges. This contribution introduces a sustainable, efficient wet-chemical method for converting gypsum to bassanite (CaSO₄·0.5H₂O), and thus recycling gypsum, under mild conditions (T < 100 °C) using reusable high-salinity aqueous solutions (brines with c[NaCl] > 4 M) [2]. The optimal conversion conditions (T > 80°C, c[NaCl] > 4 M) enable rapid (<5 min) and reversible transformation (Fig. 1). Upon cooling, gypsum re-forms, offering a temperature-dependent control over phase transition. Unlike conventional thermal dehydration (150-200 °C), this approach promotes the dissolution of gypsum, allowing contaminants to be separated via selective precipitation or adsorption. Additionally, the wet-chemical process facilitates the physical removal of impurities from gypsum matrices, making it advantageous for recycling gypsum waste from sources such as demolition or urban mining, where it is often mixed with other materials. Our approach presents a sustainable pathway for recovering high-purity bassanite from contaminated gypsum waste, aligning with EU goals for resource conservation and waste reduction. T2 - MaterialsWeek 2025 CY - Frankfurt am Main, Germany DA - 02.04.2025 KW - Gypsum KW - Calcium sulfate KW - Recycling PY - 2025 AN - OPUS4-64677 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stawski, Tomasz T1 - Towards circular economy of gypsum N2 - Gypsum (CaSO₄·2H₂O) is a crucial mineral across sectors such as construction, agriculture, and biomedicine. Despite its potentially full recyclability, a shortage looms due to limited mining in Europe and decreasing production of flue gas desulfurization (FGD) gypsum, a byproduct of coal power plants. With current EU consumption at 24 MT/a (17 MT mined, 7 MT FGD), a deficit of 10-35 MT/a is projected by the 2030s as CaSO₄ becomes a critical raw material [1]. Meanwhile, substantial CaSO₄ waste is produced in various industries (e.g., phosphogypsum, red gypsum), but its recycling remains limited (10% in Germany, 5% in the EU) due to contamination and separation challenges. This talk introduces a sustainable, efficient wet-chemical method for converting gypsum to bassanite (CaSO₄·0.5H₂O), and thus recycling gypsum, under mild conditions (T < 100 °C) using reusable high-salinity aqueous solutions (brines with c[NaCl] > 4 M) [2]. The wet-chemical process facilitates the physical removal of impurities from gypsum matrices, making it advantageous for recycling gypsum waste from sources such as demolition or urban mining, where it is often mixed with other materials. The approach presents a sustainable pathway for recovering high-purity bassanite from contaminated gypsum waste, aligning with EU goals for resource conservation and waste reduction. T2 - GFZ Interface Geochemistry Seminars Spring 2025 CY - Potsdam, Germany DA - 06.05.2025 KW - Calcium sulfate KW - Circular economy KW - Gypsum PY - 2025 AN - OPUS4-64681 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stawski, Tomasz T1 - Historical Plaster Formulations and Their Influence on Crystallographic Microstructure N2 - Historical plaster formulations offer valuable insights into advanced engineering in pre-modern cultures. This study examines two such gypsum-based recipes: Gach-e Koshteh from 14th-century Iran and Gesso Sottile from 15th-century Italy, both of which have unique characteristics and were essential for artistic and architectural decoration. By replicating these recipes in a laboratory setting, we demonstrate how traditional masters manipulated gypsum microstructure without additives to optimize the surface and mechanical properties of plaster for specific functional and artistic purposes. The Koshteh recipe involves intensive kneading during plaster hydration, which retards setting and produces a platelet-like crystal morphology with alignment of the {010} faces, resulting in a hydrophilic surface ideal for water-based wall paintings. Sottile, in contrast, relies on slow recrystallization in excess water, generating loosely packed, needle-like crystals with reduced wettability—suitable for oil-based painting and gilding. Using wide-angle X-ray scattering (WAXS), atomic force microscopy (AFM), and scanning electron microscopy (SEM), we reveal that the Koshteh recipe yields a denser, better-packed plaster with enhanced wettability, while the Sottile recipe forms larger, more loosely arranged crystals and a more hydrophobic surface. These findings underscore the ingenuity of historical materials engineering and offer valuable insights for modern conservation and sustainable restoration practices. T2 - Geo4Göttingen 2025 CY - Göttingen, Germany DA - 14.09.2025 KW - Plaster KW - Gypsum KW - Stucco KW - Cultural heritage PY - 2025 DO - https://doi.org/10.48380/4e5z-av91 AN - OPUS4-64685 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stawski, Tomasz T1 - Towards solution-driven recycling of gypsum N2 - Gypsum (CaSO₄·2H₂O) is a crucial mineral across sectors such as construction, agriculture, and biomedicine. Despite its potentially full recyclability, a shortage looms due to limited mining in Europe and decreasing production of flue gas desulfurization (FGD) gypsum, a byproduct of coal power plants. With current EU consumption at 24 MT/a (17 MT mined, 7 MT FGD), a deficit of 10-35 MT/a is projected by the 2030s as CaSO₄ becomes a critical raw material [1]. Meanwhile, substantial CaSO₄ waste is produced in various industries (e.g., phosphogypsum, red gypsum), but its recycling remains limited (10% in Germany, 5% in the EU) due to contamination and separation challenges. This contribution introduces a sustainable, efficient wet-chemical method for converting gypsum to bassanite (CaSO₄·0.5H₂O), and thus recycling gypsum, under mild conditions (T < 100 °C) using reusable high-salinity aqueous solutions (brines with c[NaCl] > 4 M) [2]. The optimal conversion conditions (T > 80°C, c[NaCl] > 4 M) enable rapid (<5 min) and reversible transformation. Upon cooling, gypsum re-forms, offering a temperature-dependent control over phase transition. Unlike conventional thermal dehydration (150-200 °C), this approach promotes the dissolution of gypsum, allowing contaminants to be separated via selective precipitation or adsorption. Additionally, the wet-chemical process facilitates the physical removal of impurities from gypsum matrices, making it advantageous for recycling gypsum waste from sources such as demolition or urban mining, where it is often mixed with other materials. T2 - Geo4Göttingen 2025 CY - Göttingen, Germany DA - 14.09.2025 KW - Calcium sulfate KW - Gypsum PY - 2025 DO - https://doi.org/10.48380/fhck-bv98 AN - OPUS4-64684 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -