TY - JOUR A1 - Emamverdi, Farnaz A1 - Huang, J. A1 - Szymoniak, Paulina A1 - Bojdys, M. J. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Structure and molecular mobility of phosphinine-based covalent organic frameworks – glass transition of amorphous COFs N2 - Two-dimensional covalent organic frameworks (COFs) based on phosphinine and thiophene building blocks have been synthesized with two different side groups. The materials are denoted as CPSF-MeO and CPSF-EtO where CxxF correspond to the covalent framework, whereas P and S are related to heteroatoms phosphorous and sulfur. MeO and EtO indicate the substituents, i.e. methoxy and ethoxy. Their morphologies were studied by scanning electron microcopy and X-ray scattering. The absence of crystalline reflexes in the X-ray pattern reveal that both materials are amorphous and can be considered as glasses. Furthermore, N2 adsorption measurements indicate substantial Brunauer–Emmett–Teller (BET) surface area values pointing to the formation of three-dimensional pores by stacking of the aromatic 2D layer. An analysis of the porosity of both COFs showed a mean radius of the pores to be of ca. 4 nm, consistent with their chemical structure. The COFs form nanoparticles with a radius of around 100 nm. The thermal behavior of the COFs was further investigated by fast scanning calorimetry. These investigations showed that both COFs undergo a glass transition. The glass transition temperature of CPSF-EtO is found to be ca. 100 K higher than that for CPSF-MeO. This large difference in the glass transition is discussed to be due to a change in the interaction of the COF sheets induced by the longer ethoxy group. It might be assumed that for CPSF-EtO more individual COF sheets assemble to larger stacks than for CPSF-MeO. This agrees with the much larger surface area value found for CPSF-EtO compared to CPSF-MeO. To corroborate the results obtained be fast scanning calorimetry dielectric measurements were conducted which confirm the occurrence of a dynamic glass transition. The estimated temperature dependence of the relaxation rates of the dielectric relaxation and their absolute values agrees well with the data obtained by fast scanning calorimetry. Considering the fragility approach to the glass transition, it was further found that CPSF-MeO is a fragile glass former whereas CPSF-EtO behaves as a strong glass forming material. This difference in the fragility points also to distinct differences in the interaction between the 2D COF molecules in both materials. KW - Covalent Organic frameworks PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596770 DO - https://doi.org/10.1039/d3ma01123b SP - 1 EP - 10 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59677 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen A1 - Meyer, A. T1 - Syntheses of Polyglycolide via Polycondensation: A Reinvestigation N2 - The Na salt of chloroacetic acid is condensed in suspension. Furthermore,glycolic acid is condensed in bulk or in concentrated solution by means of SnCl2 or 4-toluene sulfonic acid (TSA) as catalysts. The temperatures are varied from 160 to 200°C and the time from 1 to 5 days. Low molar mass cyclic poly(glycolic acid) (PGA) is detected by means of matrix-assisted laser desorption ionization time-of-flight (MALDI TOF) mass spectrometry in most PGAs. A predominance of certain cycles having an even number of repeat units is observed suggesting a thermodynamically favored formation of extended-ring crystals. Extremely high melting temperatures (up to 237.5°C)and high melting enthalpies are found for polycondensations with TSA in 1,2-dichlorobenzene. KW - MALDI TOF MS KW - Polycondensation KW - Polyglycolide KW - Cyclization PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596856 DO - https://doi.org/10.1002/macp.202300397 IS - 2300397 SP - 1 EP - 7 PB - Wiley VHC-Verlag AN - OPUS4-59685 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Kricheldorf, H. T1 - Cyclic polyglycolides via ring-expansion polymerization with cyclic tin catalysts N2 - Glycolide was polymerized in bulk with two cyclic catalysts − 2,2-dibutyl-2-stanna-1,3-dithiolane (DSTL) and 2-stanna-1,3-dioxa-4,5,6,7-dibenzepane (SnBiph). The monomer/initiator ratio, temperature (140 – 180 °C) and time (1–––4 days) were varied. The MALDI TOF mass spectra exclusively displayed peaks of cyclic polyglycolide (PGA) and revealed an unusual “saw-tooth pattern” in the mass range below m/z 2 500 suggesting formation of extended ring crystallites. The DSC measurements indicated increasing crystallinity with higher temperature and longer time, and after annealing for 4 d at 160 °C a hitherto unknown and unexpected glass transition was found in the temperature range of 170–185 °C. Linear PGAs prepared by means of metal alkoxides under identical conditions did not show the afore-mentioned features of the cyclic PGAs, neither in the mass spectra nor in the DSC measurements. All PGAs were also characterized by SAXS measurements, which revealed relatively small L-values suggesting formation of thin crystallites in all cases with little influence of the reaction conditions. KW - Polyglycolide KW - MALDI-TOF MS KW - Ring-expansion polymerization KW - Crystals PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595541 DO - https://doi.org/10.1016/j.eurpolymj.2024.112811 SN - 0014-3057 VL - 207 SP - 1 EP - 9 PB - Elsevier Ltd. AN - OPUS4-59554 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tukhmetova, Dariya A1 - Lisec, Jan A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Development of an Online Isotope Dilution CE/ICP–MS Method for the Quantification of Sulfur in Biological Compounds N2 - We report an analytical methodology for the quantification of sulfur in biological molecules via a speciesunspecific postcolumn isotope dilution (online ID) approach using capillary electrophoresis (CE) coupled online with inductively coupled plasma−mass spectrometry (online ID CE/ICP−MS). The method was optimized using a mixture of standard compounds including sulfate, methionine, cysteine, cystine, and albumin, yielding compound recoveries between 98 and 105%. The quantity of sulfur is further converted to the quantity of the compounds owing to the prior knowledge of the sulfur content in the molecules. The limit of detection and limit of quantification of sulfur in the compounds were 1.3−2.6 and 4.1−8.4 mg L−1, respectively, with a correlation coefficient of 0.99 within the concentration range of sulfur of 5−100 mg L−1. The capability of the method was extended to quantify albumin in its native matrix (i.e., in serum) using experimentally prepared serum spiked with a pure albumin standard for validation. The relative expanded uncertainty of the method for the quantification of albumin was 6.7% (k = 2). Finally, we tested the applicability of the method on real samples by the analysis of albumin in bovine and human sera. For automated data assessment, a software application (IsoCor) which was developed by us in a previous work was developed further for handling of online ID data. The method has several improvements compared to previously published setups: (i) reduced adsorption of proteins onto the capillary wall owing to a special capillary-coating procedure, (ii) baseline separation of the compounds in less than 30 min via CE, (iii) quantification of several sulfur species within one run by means of the online setup, (iv) SI traceability of the quantification results through online ID, and (v) facilitated data processing of the transient signals using the IsoCor application. Our method can be used as an accurate approach for quantification of proteins and other biological molecules via sulfur analysis in complex matrices for various fields, such as environmental, biological, and pharmaceutical studies as well as clinical diagnosis. Sulfur is an essential element in living organisms, where it plays important roles in various biological processes, such as protein synthesis, enzyme activity, and antioxidant defense. However, the biological effects of different sulfur species can vary widely, and imbalances in sulfur speciation have been observed in a range of diseases, including cancer, Alzheimer’s disease, and diabetes.1−3 The accurate quantification of sulfur and its species in biological samples requires sensitive and selective analytical techniques. In recent years, separation techniques coupled online with inductively coupled plasma−mass spectrometry (ICP−MS) have emerged as powerful online analytical tools complementary to molecular spectrometric methods for speciation analysis of biological compounds. External calibration4−9 and isotope dilution (ID)10−15 are common calibration approaches applied for online quantification of sulfur species in complex samples. The ID analysis is advantageous over. KW - Analytical Chemistry KW - CE/MC-ICP-MS KW - species-specific isotope information PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594736 DO - https://doi.org/10.1021/acs.analchem.3c03553 SN - 0003-2700 SP - 1 EP - 8 PB - American Chemical Society (ACS) AN - OPUS4-59473 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Prabhakara, Prathik A1 - Lay, Vera A1 - Mielentz, Frank A1 - Niederleithinger, Ernst A1 - Behrens, Matthias T1 - Enhancing the Performance of a Large Aperture Ultrasound System (LAUS): A Combined Approach of Simulation and Measurement for Transmitter–Receiver Optimization N2 - The Large Aperture Ultrasound System (LAUS) developed at BAM is known for its ability to penetrate thick objects, especially concrete structures commonly used in nuclear waste storage and other applications in civil engineering. Although the current system effectively penetrates up to ~9 m, further optimization is imperative to enhance the safety and integrity of disposal structures for radioactive or toxic waste. This study focuses on enhancing the system’s efficiency by optimizing the transducer spacing, ensuring that resolution is not compromised. An array of twelve horizontal shear wave transducers was used to find a balance between penetration depth and resolution. Systematic adjustments of the spacing between transmitter and receiver units were undertaken based on target depth ranges of known reflectors at depth ranges from 5 m to 10 m. The trade-offs between resolution and artifact generation were meticulously assessed. This comprehensive study employs a dual approach using both simulations and measurements to investigate the performance of transducer units spaced at 10 cm, 20 cm, 30 cm, and 40 cm. We found that for depths up to 5 m, a spacing of 10 cm for LAUS transducer units provided the best resolution as confirmed by both simulations and measurements. This optimal distance is particularly effective in achieving clear reflections and a satisfactory signal-to-noise ratio (SNR) in imaging scenarios with materials such as thick concrete structures. However, when targeting depths greater than 10 m, we recommend increasing the distance between the transducers to 20 cm. This increased spacing improves the SNR in comparison to other spacings, as seen in the simulation of a 10 m deep backwall. Our results emphasize the critical role of transducer spacing in achieving the desired SNR and resolution, especially in the context of depth imaging requirements for LAUS applications. In addition to the transducer spacing, different distances between individual sets of measurement positions were tested. Overall, keeping the minimal possible distance between measurement position offsets provides the best imaging results at greater depths. The proposed optimizations for the LAUS in this study are primarily relevant to applications on massive nuclear structures for nuclear waste management. This research highlights the need for better LAUS efficiency in applications such as sealing structures, laying the foundation for future technological advances in this field. KW - Engineered barrier system KW - Phased array technique KW - Ultrasonic testing KW - Non-destructive testing in civil engineering KW - Seismic migration PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-592426 DO - https://doi.org/10.3390/s24010100 VL - 24 IS - 1 SP - 1 EP - 23 PB - MDPI CY - Basel, Switzerland AN - OPUS4-59242 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Thiele, Isabel A1 - Santolin, Lara A1 - Meyer, Klas A1 - Machatschek, Rainhard A1 - Bölz, Uwe A1 - Tarazona, Natalia A. A1 - Riedel, Sebastian L. T1 - Microbially synthesized poly(hydroxybutyrate-co-hydroxyhexanoate) with low to moderate hydroxyhexanoate content: Properties and applications N2 - Plastic pollution is the biggest environmental concern of our time. Breakdown products like micro- and nanoplastics inevitably enter the food chain and pose unprecedented health risks. In this scenario, bio-based and biodegradable plastic alternatives have been given a momentum aiming to bridge a transition towards a more sustainable future. Polyhydroxyalkanoates (PHAs) are one of the few thermoplastic polymers synthesized 100 % via biotechnological routes which fully biodegrade in common natural environments. Poly(hydroxybutyrate-cohydroxyhexanoate) [P(HB-co-HHx)] is a PHA copolymer with great potential for the commodity polymers industry, as its mechanical properties can be tailored through fine-tuning of its molar HHx content. We have recently developed a strategy that enables for reliable tailoring of the monomer content of P(HB-co-HHx). Nevertheless, there is often a lack of comprehensive investigation of the material properties of PHAs to evaluate whether they actually mimic the functionalities of conventional plastics. We present a detailed study of P(HB-co-HHx) copolymers with low to moderate hydroxyhexanoate content to understand how the HHx monomer content influences the thermal and mechanical properties and to link those to their abiotic degradation. By increasing the HHx fractions in the range of 2 – 14 mol%, we impart an extension of the processing window and application range as the melting temperature (Tm) and glass temperature (Tg) of the copolymers decrease from Tm 165 ◦C to 126 ◦C, Tg 4 ◦C to − 5.9 ◦C, accompanied by reduced crystallinity from 54 % to 20 %. Elongation at break was increased from 5.7 % up to 703 % at 14 mol% HHx content, confirming that the range examined was sufficiently large to obtain ductile and brittle copolymers, while tensile strength was maintained throughout the studied range. Finally, accelerated abiotic degradation was shown to be slowed down with an increasing HHx fraction decreasing from 70 % to 55 % in 12 h. KW - Molecular Biology KW - General Medicine KW - Biochemistry KW - Structural Biology PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595636 DO - https://doi.org/10.1016/j.ijbiomac.2024.130188 VL - 263 SP - 1 EP - 9 PB - Elsevier B.V. AN - OPUS4-59563 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Villajos Collado, José Antonio A1 - Balderas‐Xicohténcatl, Rafael A1 - Al Shakhs, Ali N. A1 - Berenguer‐Murcia, Ángel A1 - Buckley, Craig E. A1 - Cazorla‐Amorós, Diego A1 - Charalambopoulou, Georgia A1 - Couturas, Fabrice A1 - Cuevas, Fermin A1 - Fairen‐Jimenez, David A1 - Heinselman, Karen N. A1 - Humphries, Terry D. A1 - Kaskel, Stefan A1 - Kim, Hyunlim A1 - Marco‐Lozar, Juan P. A1 - Oh, Hyunchul A1 - Parilla, Philip A. A1 - Paskevicius, Mark A1 - Senkovska, Irena A1 - Shulda, Sarah A1 - Silvestre‐Albero, Joaquin A1 - Steriotis, Theodore A1 - Tampaxis, Christos A1 - Hirscher, Michael A1 - Maiwald, Michael T1 - Establishing ZIF‐8 as a reference material for hydrogen cryoadsorption: An interlaboratory study N2 - AbstractHydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal‐organic framework ZIF‐8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF‐8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3–4 % between pressures of 10–100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF‐8 pellets, which we want to propose as a reference material. KW - Physical and theoretical chemistry KW - Atomic and molecular physics, and optics PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594788 DO - https://doi.org/10.1002/cphc.202300794 SN - 1439-7641 SP - 1 EP - 7 PB - Wiley CY - Weinheim AN - OPUS4-59478 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bühling, Benjamin A1 - Maack, Stefan T1 - Improving onset picking in ultrasonic testing by using a spectral entropy criterion N2 - In ultrasonic testing, material and structural properties of a specimen can be derived from the time-of-flight (ToF). Using signal features, such as the first peak or envelope maximum, to calculate the ToF is error-prone in multipath arrangements or dispersive and attenuating materials, which is not the case for the signal onset. Borrowing from seismology, researchers used the Akaike information criterion (AIC) picker to automatically determine onset times. The most commonly used formulation, Maeda's AIC picker, is reassessed and found to be based on inappropriate assumptions for signals often used in ultrasonic testing and dependent on arbitrary parameters. Consequently, an onset picker for ultrasonic through-transmission measurements is proposed, based on a spectral entropy criterion (SEC) to model the signal using the AIC framework. This SEC picker takes into account the spectral properties of the ultrasonic signal and is virtually free of arbitrary parameters. Synthetic and experimental data are used to compare the performance of SEC and AIC pickers. It is shown that the accuracy of onset picking is improved for densely sampled data. KW - Akaike information criterion picker KW - Nondestructive testing KW - Ultrasound KW - Time of flight PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594284 UR - https://pubs.aip.org/asa/jasa/article/155/1/544/3061576/Improving-onset-picking-in-ultrasonic-testing-by DO - https://doi.org/10.1121/10.0024337 SN - 0001-4966 VL - 155 IS - 1 SP - 544 EP - 554 PB - AIP Publishing CY - Melville, NY, USA AN - OPUS4-59428 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Timofeev, Juri A1 - Azari, H. A1 - Satyanarayana, R. T1 - Controlled Creating of Delaminations in Concrete for Nondestructive Testing N2 - Locating and sizing delaminations is a common inspection task in the maintenance and quality control of construction and rehabilitation. Their detection is an important area of application of nondestructive testing in civil engineering (NDT-CE). To improve this application, NDT test systems and test solutions must be compared, for which specimens containing well-defined delaminations are needed to serve as a reference. Currently, there are no widely accepted procedures available for creating such flaws locally and reproducibly. This study presents procedures for creating artificial delaminations repeatably and as close as possible to natural delaminations. To produce the discontinuities only substances were used which can occur in concrete components and do not affect the application of NDT-CE methods. Ultrasonic pulse-echo (UPE) was used to test the flaws in the specimens. The delaminations were created by applying expansive mortar in prepared through holes. Three specimens with two delaminations each were built and tested using UPE. KW - Concrete KW - Reference KW - Delamination KW - Test specimen KW - Non-destructive testing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595201 DO - https://doi.org/10.1007/s10921-023-01044-7 SN - 0195-9298 VL - 43 IS - 1 SP - 1 EP - 13 PB - Springer Science and Business Media LLC AN - OPUS4-59520 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bühling, Benjamin A1 - Maack, Stefan A1 - Strangfeld, Christoph T1 - Fluidic Ultrasound Generation for Non‐Destructive Testing N2 - AbstractAir‐coupled ultrasonic testing (ACU) is a pioneering technique in non‐destructive testing (NDT). While contact testing and fluid immersion testing are standard methods in many applications, the adoption of ACU is progressing slowly, especially in the low ultrasonic frequency range. A main reason for this development is the difficulty of generating high amplitude ultrasonic bursts with equipment that is robust enough to be applied outside a laboratory environment. This paper presents the fluidic ultrasonic transducer as a solution to this challenge. This novel aeroacoustic source uses the flow instability of a sonic jet in a bistable fluidic switch to generate ultrasonic bursts up to 60 kHz with a mean peak pressure of 320 Pa. The robust design allows operation in adverse environments, independent of the operating fluid. Non‐contact through‐transmission experiments are conducted on four materials and compared with the results of conventional transducers. For the first time, it is shown that the novel fluidic ultrasonic transducer provides a suitable acoustic signal for NDT tasks and has potential of furthering the implementation of ACU in industrial applications.This article is protected by copyright. All rights reserved KW - Aeroacoustics KW - Air-coupled ultrasound KW - Fluidics KW - Harsh environment KW - Laser Doppler vibrometer KW - Non-destructive testing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594273 DO - https://doi.org/10.1002/adma.202311724 SN - 0935-9648 SP - 1 EP - 14 PB - Wiley AN - OPUS4-59427 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Grohmann, Maria A1 - Niederleithinger, Ernst A1 - Maack, Stefan A1 - Buske, Stefan T1 - Application of iterative elastic SH reverse time migration to synthetic ultrasonic echo data N2 - The ultrasonic echo technique is widely used in non-destructive testing (NDT) of concrete objects for thickness measurements, geometry determinations and localization of built-in components. To improve ultrasonic imaging of complex concrete structures, we transferred a seismic imaging technique, the Reverse Time Migration (RTM), to NDT in civil engineering. RTM, in contrast to the conventionally used synthetic aperture focusing technique (SAFT) algorithms, considers all wavefield types and thus, can handle complex wave propagations in any direction with no limit on velocity variations and reflector dip. In this paper, we focused on the development, application and evaluation of a two-dimensional elastic RTM algorithm considering horizontally polarized shear (SH) waves only. We applied the elastic SH RTM routine to synthetic ultrasonic echo SH-wave data generated with a concrete model incorporating several steps and circular cavities. As these features can often be found in real-world NDT use cases, their imaging is extremely important. By using elastic SH RTM, we were able to clearly reproduce almost all reflectors inside the concrete model including the vertical step edges and the cross sections of the cavities.We were also capable to show that more features could be mapped compared to SAFT, and that imaging of complex reflectors could be sharpened compared to elastic P-SV (compressional-vertically polarized shear) RTM. Our promising results illustrate that elastic SH RTM has the potential to significantly enhance the reconstruction of challenging concrete structures, representing an important step forward for precise, high-quality ultrasonic NDT in civil engineering. KW - Ultrasonic echo technique KW - Concrete structures KW - Elastic reverse time migration KW - Synthetic aperture focusing technique KW - Horizontally polarized shear waves PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-591716 DO - https://doi.org/10.1007/s10921-023-01010-3 SN - 1573-4862 VL - 43 SP - 1 EP - 16 PB - Springer Science and Business Media CY - Dordrecht AN - OPUS4-59171 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schröpfer, Dirk A1 - Witte, Julien A1 - Kromm, Arne A1 - Kannengießer, Thomas T1 - Stresses in repair welding of high-strength steels—part 1: restraint and cold cracking risk N2 - AbstractThe sustainable and resource-efficient production of wind energy plants requires the use of modern high-strength fine-grain structural steels. This applies to both foundation and erection structures, like mobile or ship cranes. During the assembly of steel structures, unacceptable defects can occasionally be found in the weld area. In most cases, the economical solution would be local thermal gouging of the affected areas and re-welding. Due to the high shrinkage restraint of the joint groove in the overall structure, the superposition of global and local welding-induced stresses may lead to crack formation and component failure, particularly in interaction with the degradation of the microstructure and mechanical properties of high-strength steels during the repair process. However, manufacturers hardly have any information about these issues and there is a lack of recommendations and guidelines to take these safety-relevant aspects into account in adequate repair concepts. The aim of this research is to derive recommendations for repair concepts appropriate to the stresses and materials involved providing a basis for standards and guidelines to avoid cold cracking, damage and expensive reworking especially for high-strength steels. Part 1 of this study involves systematic investigations of influences of shrinkage restraint during repair welding of two high-strength steels S500MLO for offshore application and S960QL for mobile crane structures. The quantification of the shrinkage restraint of repair weld joints was achieved by means of experimental and numerical restraint intensity analysis. In welding experiments with self-restrained slot specimens, restraint intensity and introduction of hydrogen via the welding arc using anti spatter spray were varied systematically to analyse the effect on welding result, residual stresses and cold cracking. It could be shown that increasing restraint intensities result in significantly higher transverse residual stress levels. In the case of hydrogen introduction S500MLO showed no cold cracking independent of the restraint conditions. However, S960QL was found to be considerably cold cracking sensitive if hydrogen is introduced. With increasing restraint intensity length and number of cold cracks increases significantly. Part 2 [1] of this study is focussed on microstructure and residual stresses due to gouging and stress optimization via adequate heat control parameters in repair welding. KW - Metals and Alloys KW - Mechanical Engineering KW - Mechanics of Materials PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595212 DO - https://doi.org/10.1007/s40194-024-01691-y SN - 0043-2288 SP - 1 EP - 13 PB - Springer Science and Business Media LLC AN - OPUS4-59521 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Konert, Florian A1 - Wieder, Frank A1 - Nietzke, Jonathan A1 - Meinel, Dietmar A1 - Böllinghaus, Thomas A1 - Sobol, Oded T1 - Evaluation of the impact of gaseous hydrogen on pipeline steels utilizing hollow specimen technique and μCT N2 - The high potential of hydrogen as a key factor on the pathway towards a climate neutral economy, leads to rising demand in technical applications, where gaseous hydrogen is used. For several metals, hydrogen-metal interactions could cause a degradation of the material properties. This is especially valid for low carbon and highstrength structural steels, as they are commonly used in natural gas pipelines and analyzed in this work. This work provides an insight to the impact of hydrogen on the mechanical properties of an API 5L X65 pipeline steel tested in 60 bar gaseous hydrogen atmosphere. The analyses were performed using the hollow specimen technique with slow strain rate testing (SSRT). The nature of the crack was visualized thereafter utilizing μCT imaging of the sample pressurized with gaseous hydrogen in comparison to one tested in an inert atmosphere. The combination of the results from non-conventional mechanical testing procedures and nondestructive imaging techniques has shown unambiguously how the exposure to hydrogen under realistic service pressure influences the mechanical properties of the material and the appearance of failure. KW - Energy Engineering and Power Technology KW - Condensed Matter Physics KW - Fuel Technology KW - Renewable Energy, Sustainability and the Environment KW - µCT KW - Hollow Specimen Technique KW - Hydrogen Embrittlement PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595077 DO - https://doi.org/10.1016/j.ijhydene.2024.02.005 SN - 0360-3199 VL - 59 SP - 874 EP - 879 PB - Elsevier B.V. AN - OPUS4-59507 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Glienke, R. A1 - Kalkowsky, F. A1 - Hobbacher, A. F. A1 - Holch, A. A1 - Thiele, Marc A1 - Marten, F. A1 - Kersten, R. A1 - Henkel, K.-M. T1 - Evaluation of the fatigue resistance of butt‑welded joints in towers of wind turbines - A comparison of experimental studies with small scale and component tests as well as numerical based approaches with local concepts N2 - Wind turbines are exposed to a high number of load cycles during their service lifetime. Therefore, the fatigue strength verification plays an important role in their design. In general, the nominal stress method is used for the fatigue verification of the most common used butt-welded joints. The Eurocode 3 part 1–9 is the current design standard for this field of application. This paper presents recent results of fatigue tests on small-scaled specimens and large components with transverse butt welds to discuss the validity of the FAT-class. Furthermore, results from numerical simulations for the verification with the effective notch stress and the crack propagation approach are used for comparison. Based on the consistency between the numerical results and the fatigue tests, the influence of the seam geometry on the fatigue resistance was investigated. Finally, a prediction of the fatigue strength of butt-welded joints with plate thicknesses up to 80 mm was carried out. KW - Transverse butt weld KW - Weld imperfections KW - Wind turbine tower KW - Fatigue strength KW - Local approaches KW - Large components KW - Wind energy PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596648 DO - https://doi.org/10.1007/s40194-023-01630-3 SN - 1878-6669 SP - 1 EP - 26 PB - Springer CY - Berlin AN - OPUS4-59664 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tambara, R. F. A1 - Durlo Tambara, Luis Urbano A1 - Venquiaruto, S. D. A1 - Pereira da Costa, F. B. T1 - Evaluation of the mechanical performance and capillary absorption of concretes with incorporation of crystallizing admixtures and subjected to damage at early ages T1 - Avaliação do desempenho mecânico e absorção capilar de concretos com incorporação de aditivos cristalizante submetidos a danos nas primeiras idades N2 - This study assessed the self-healing phenomenon in the mechanical properties and capillary absorption of structural concretes. Two crystalline powder additives were evaluated, dosed according to the manufacturers’ recommendations. Crystalline additives increase the density of the C-S-H gel and form insoluble crystals, effectively blocking fissures. Three concrete mixes were produced: a reference mix, additive-X with 0.8%, and additive-Y with 2.0%, relative to the mass of cement. 75% of the rupture load was applied at 3- and 14-days to induce microfissures for comparison with the reference mix. Subsequently, self-healing was assessed at 28- and 76-days. The property of axial compressive strength was determined at 28-days, revealing that crystalline additives contributed to an average increase of 12% in this property. While the age of loading did not significantly impact axial compressive strength, there were significant variations among the types of additives studied, as indicated by ANOVA. Water absorption properties through capillarity were evaluated at 28- and 76-days, showing an average reduction of 42% in water absorption due to the use of crystalline additives. In conclusion, the inclusion of crystalline additives positively contributed to the self-healing of the studied concretes, suggesting a partial recovery of microfissures. N2 - Esta pesquisa avaliou o fenômeno de autocicatrização nas propriedades mecânicas e absorção capilar de concretos estruturais. Foram avaliados dois aditivos cristalizantes em pó, dosados de acordo com o teor recomendado pelos fabricantes. Aditivos cristalizantes aumentam a densidade do gel C-S-H e formam cristais insolúveis, bloqueando fissuras. Três traços de concreto foram produzidos: referência, aditivo-X com 0,8% e aditivo-Y com 2,0% em relação a massa do cimento. Aplicou-se 75% da carga de ruptura aos 3- e 14-dias para gerar microfissuras e comparar com a referência. Posteriormente, a autocicatrização foi avaliada aos 28- e 76-dias. A propriedade de resistência à compressão axial foi determinada aos 28-dias, revelando que os aditivos cristalizantes contribuíram para um aumento médio de 12% desta propriedade. A idade do carregamento dos concretos não apresentou um impacto significativo na resistência à compressão axial, mas apontou resultados significativos entre os tipos de aditivos estudados, conforme ANOVA. As propriedades de absorção de água por capilaridade foram avaliadas aos 28- e 76-dias, indicando uma redução de absorção de água média de 42% devido ao uso dos aditivos cristalizantes. Em conclusão, a incorporação dos aditivos cristalizantes contribuiu de maneira positiva para a autocicatrização dos concretos estudados, indicando uma recuperação parcial das microfissuras. KW - Self-healing KW - Crystalline admixture KW - Concrete KW - Cracks PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599140 DO - https://doi.org/10.1590/1517-7076-RMAT-2023-0355 SN - 1517-7076 VL - 29 IS - 1 SP - 1 EP - 20 CY - Rio de Janeiro AN - OPUS4-59914 LA - por AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Jovičević-Klug, Matic A1 - Souza Filho, Isnaldi R. A1 - Springer, Hauke A1 - Adam, Christian A1 - Raabe, Dierk T1 - Green steel from red mud through climate-neutral hydrogen plasma reduction N2 - AbstractRed mud is the waste of bauxite refinement into alumina, the feedstock for aluminium production1. With about 180 million tonnes produced per year1, red mud has amassed to one of the largest environmentally hazardous waste products, with the staggering amount of 4 billion tonnes accumulated on a global scale1. Here we present how this red mud can be turned into valuable and sustainable feedstock for ironmaking using fossil-free hydrogen-plasma-based reduction, thus mitigating a part of the steel-related carbon dioxide emissions by making it available for the production of several hundred million tonnes of green steel. The process proceeds through rapid liquid-state reduction, chemical partitioning, as well as density-driven and viscosity-driven separation between metal and oxides. We show the underlying chemical reactions, pH-neutralization processes and phase transformations during this surprisingly simple and fast reduction method. The approach establishes a sustainable toxic-waste treatment from aluminium production through using red mud as feedstock to mitigate greenhouse gas emissions from steelmaking. KW - Multidisciplinary PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594424 DO - https://doi.org/10.1038/s41586-023-06901-z SN - 0028-0836 VL - 625 IS - 7996 SP - 703 EP - 709 PB - Springer Science and Business Media LLC AN - OPUS4-59442 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fantin, Andrea A1 - Manzoni, Anna Maria A1 - Springer, H. A1 - Darvishi Kamachali, Reza A1 - Maaß, Robert T1 - Local lattice distortions and chemical short-range order in MoNbTaW N2 - Extended X-ray absorption fine structure (EXAFS) conducted on an equiatomic MoNbTaW bcc medium-entropy alloy that was annealed at 2273 K reveals unexpectedly small 1st and 2nd shell element-specific lattice distortions. An experimental size-mismatch parameter, δexp, is determined to be ca. 50% lower than the corresponding calculated value. Around W, short-range order (SRO) preferring 4d elements in the 1st and 2nd shells persists. A Nb-W ordering is found, which is reminiscent of ordering emerging at lower temperatures in the B2(Mo,W;Ta,Nb)- and B32(Nb,W)-phases. With high-temperature ordering preferences in fcc also foreshadowing low-temperature phase, these findings suggest a general feature of high-temperature SRO. KW - High Entropy Alloys KW - Short-range order KW - Lattice distortions KW - EXAFS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598164 DO - https://doi.org/10.1080/21663831.2024.2326014 SN - 2166-3831 VL - 12 IS - 5 SP - 346 EP - 354 PB - Taylor & Francis AN - OPUS4-59816 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Polycondensation of poly(L-lactide) alkyl esters combined with disproportionation and symproportionation of the chain lengths N2 - Ring-opening polymerizations (ROPs) of l-lactide (LA) were performed with ethyl l-lactate or 11-bromoundecanol as initiators (In) and tin(II) ethyl hexanoate (SnOct2) as catalyst (Cat) using four different LA/In ratios (20/1, 40/1, 60/1, and 100/1). One series of ROPs was conducted in bulk at 120 °C, yielding PLAs with low dispersities (Ð ~ 1.2–1.4), and a second series was conducted in bulk at 160 °C, yielding higher dispersities (Ð ~ 1.3–1.9). Samples from both series were annealed for 1 or 14 days at 140 °C in the presence of SnOct2. Both polycondensation and disproportionation reactions occurred, so that all four samples tended to form the same type of molar mass distribution below 10,000 Da, regardless of their initially different number average molar masses (Mn). Both initiators gave nearly identical results. The thermodynamic control of all reversible transesterification processes favored the formation of crystallites composed of chains with a Mn around 3500–3700, corresponding to a crystal thickness of 10–13 nm. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600081 DO - https://doi.org/10.1002/pol.20240118 SN - 2642-4150 SP - 1 EP - 12 PB - Wiley AN - OPUS4-60008 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bayerlein, Bernd A1 - Schilling, Markus A1 - von Hartrott, Philipp A1 - Waitelonis, Jörg T1 - Semantic integration of diverse data in materials science: Assessing Orowan strengthening N2 - AbstractThis study applies Semantic Web technologies to advance Materials Science and Engineering (MSE) through the integration of diverse datasets. Focusing on a 2000 series age-hardenable aluminum alloy, we correlate mechanical and microstructural properties derived from tensile tests and dark-field transmission electron microscopy across varied aging times. An expandable knowledge graph, constructed using the Tensile Test and Precipitate Geometry Ontologies aligned with the PMD Core Ontology, facilitates this integration. This approach adheres to FAIR principles and enables sophisticated analysis via SPARQL queries, revealing correlations consistent with the Orowan mechanism. The study highlights the potential of semantic data integration in MSE, offering a new approach for data-centric research and enhanced analytical capabilities. KW - Semantic Interoperability KW - Knowledge Graph KW - Orowan Mechanism KW - Aluminum Alloy Aging KW - Ontology KW - Semantic Data Integration PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599780 DO - https://doi.org/10.1038/s41597-024-03169-4 VL - 11 IS - 1 SP - 1 EP - 12 PB - Springer Science and Business Media LLC AN - OPUS4-59978 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Temgoua, Ranil C.T. A1 - Dontsi, Fabiola T. A1 - Lebègue, Estelle A1 - Thobie-Gautier, Christine A1 - Tonlé, Ignas K. A1 - Boujtita, Mohammed T1 - Understanding the behavior of phenylurazole-tyrosine-click electrochemical reaction using hybrid electroanalytical techniques N2 - In this work, the electrochemical behavior of 4-phenylurazole (Ph-Ur) was studied and the latter was used as a molecular anchor for the electrochemical bioconjugation of tyrosine (Y). Cyclic voltammetry (CV) and controlled potential coulometry (CPC) allowed the in-situ generation of the PTAD (4-phenyl-3 H-1,2,4-triazole-3,5(4 H)-dione) species from phenylurazole on demand for tyrosine electrolabeling. The chemoselectivity of the reaction was studied with another amino acid (lysine, Lys) and no changes in Lys were observed. To evaluate the performance of tyrosine electrolabeling, coulometric analyses at controlled potentials were performed on solutions of phenylurazole and the phenylurazole-tyrosine mixture in different proportions (2:1, 1:1, and 1:2). The electrolysis of the phenylurazole-tyrosine mixture in the ratio (1:2) produced a charge of 2.07 C, very close to the theoretical value (1.93 C), with high reaction kinetics, a result obtained here for the first time. The products obtained were identified and characterized by liquid chromatography coupled to high-resolution electrospray ionization mass spectrometry (LC-HRMS and LC- HRMS2). Two products were formed from the click reactions, one of which was the majority. Another part of this work was to study the electrochemical degradation of the molecular anchor 4-phenylazole (Ph-Ur). Four stable degradation products of phenylurazole were identified (C7H9N2O, C6H8N, C6H8NO, C14H13N4O2) based on chromatographic profiles and mass spectrometry results. The charge generated during the electrolysis of phenylurazole (two-electron process) (2.85 C) is inconsistent with the theoretical or calculated charge (1.93 C), indicating that secondary/parasitic reactions occurred during the electrolysis of the latter. In conclusion, the electrochemically promoted click phenylurazole-tyrosine reactions give rise to click products with high reaction kinetics and yields in the (1:2) phenylurazole-tyrosine ratios, and the presence of side reactions is likely to affect the yield of the click phenylurazole-tyrosine reaction. KW - Clinical Biochemistry KW - Spectroscopy KW - Drug Discovery KW - Pharmaceutical Science KW - Analytical Chemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599267 DO - https://doi.org/10.1016/j.jpba.2024.116147 VL - 245 SP - 1 EP - 8 PB - Elsevier BV AN - OPUS4-59926 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Strobl, Dominic A1 - Unger, Jörg F. A1 - Ghnatios, C. A1 - Klawoon, Alexander A1 - Pittner, Andreas A1 - Rethmeier, Michael A1 - Robens-Radermacher, Annika T1 - Efficient bead-on-plate weld model for parameter estimation towards effective wire arc additive manufacturing simulation N2 - Despite the advances in hardware and software techniques, standard numerical methods fail in providing real-time simulations, especially for complex processes such as additive manufacturing applications. A real-time simulation enables process control through the combination of process monitoring and automated feedback, which increases the flexibility and quality of a process. Typically, before producing a whole additive manufacturing structure, a simplified experiment in the form of a beadon-plate experiment is performed to get a first insight into the process and to set parameters suitably. In this work, a reduced order model for the transient thermal problem of the bead-on-plate weld simulation is developed, allowing an efficient model calibration and control of the process. The proposed approach applies the proper generalized decomposition (PGD) method, a popular model order reduction technique, to decrease the computational effort of each model evaluation required multiple times in parameter estimation, control, and optimization. The welding torch is modeled by a moving heat source, which leads to difficulties separating space and time, a key ingredient in PGD simulations. A novel approach for separating space and time is applied and extended to 3D problems allowing the derivation of an efficient separated representation of the temperature. The results are verified against a standard finite element model showing excellent agreement. The reduced order model is also leveraged in a Bayesian model parameter estimation setup, speeding up calibrations and ultimately leading to an optimized real-time simulation approach for welding experiment using synthetic as well as real measurement data. KW - Proper generalized decomposition KW - Model order reduction KW - Hardly separable problem KW - Additive manufacturing KW - Model calibration KW - Wire arc additive manufacturing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596502 DO - https://doi.org/10.1007/s40194-024-01700-0 SN - 0043-2288 SP - 1 EP - 18 PB - Springer AN - OPUS4-59650 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Feng, W. A1 - Gemming, T. A1 - Giebeler, L. A1 - Qu, J. A1 - Weinel, Kristina A1 - Agudo Jácome, Leonardo A1 - Büchner, B. A1 - Gonzalez-Martinez, I. T1 - Influence of magnetic field on electron beam-induced Coulomb explosion of gold microparticles in transmission electron microscopy N2 - In this work we instigated the fragmentation of Au microparticles supported on a thin amorphous carbon film by irradiating them with a gradually convergent electron beam inside the Transmission Electron Microscope. This phenomenon has been generically labeled as ‘‘electron beam-induced fragmentation’’ or EBIF and its physical origin remains contested. On the one hand, EBIF has been primarily characterized as a consequence of beam-induced heating. On the other, EBIF has been attributed to beam-induced charging eventually leading to Coulomb explosion. To test the feasibility of the charging framework for EBIF, we instigated the fragmentation of Au particles under two different experimental conditions. First, with the magnetic objective lens of the microscope operating at full capacity, i.e. background magnetic field 𝐵 = 2 T, and with the magnetic objective lens switched off (Lorenz mode), i.e. 𝐵 = 0 T. We observe that the presence or absence of the magnetic field noticeably affects the critical current density at which EBIF occurs. This strongly suggests that magnetic field effects play a crucial role in instigating EBIF on the microparticles. The dependence of the value of the critical current density on the absence or presence of an ambient magnetic field cannot be accounted for by the beam-induced heating model. Consequently, this work presents robust experimental evidence suggesting that Coulomb explosion driven by electrostatic charging is the root cause of EBIF. KW - Electron beam-induced fragmentation KW - Coulomb explosion KW - X-ray diffraction KW - Lorenz transmission electron microscopy KW - Electron beam-induced charging PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600170 DO - https://doi.org/10.1016/j.ultramic.2024.113978 VL - 262 SP - 1 EP - 8 PB - Elsevier B.V. AN - OPUS4-60017 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herter, Sven-Oliver A1 - Koch, Matthias A1 - Haase, Hajo T1 - First Synthesis of Ergotamine-13CD3 and Ergotaminine-13CD3 from Unlabeled Ergotamine N2 - Ergot alkaloids (EAs) formed by Claviceps fungi are one of the most common food contaminants worldwide, affecting cereals such as rye, wheat, and barley. To accurately determine the level of contamination and to monitor EAs maximum levels set by the European Union, the six most common EAs (so-called priority EAs) and their corresponding epimers are quantified using high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The quantification of EAs in complex food matrices without appropriate internal tandards is challenging but currently carried out in the standard method EN 7425:2021 due to their commercial unavailability. To address the need for isotopically labeled EAs, we focus on two semi-synthetic approaches for the synthesis of these reference standards. Therefore, we investigate the feasibility of the N6-demethylation of native ergotamine to yield norergotamine, which can subsequently be remethylated with an isotopically labeled methylating reagent, such as iodomethane (13CD3-I), to yield isotopically labeled ergotamine and its C8-epimer ergotaminine. Testing the isotopically labeled ergotamine/-inine against native ergotamine/-inine with HPLC coupled to high-resolution HR-MS/MS proved the structure of ergotamine-13CD3 and ergotaminine-13CD3. Thus, for the first time, we can describe their synthesis from unlabeled, native ergotamine. Furthermore, this approach is promising as a universal way to synthesize other isotopically labeled EAs. KW - Reference Material KW - HPLC-MS/MS KW - Mycotoxins KW - Standards KW - Organic Synthesis KW - Isotope PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600167 DO - https://doi.org/10.3390/toxins16040199 VL - 16 IS - 4 SP - 1 EP - 12 PB - MDPI AN - OPUS4-60016 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dalgic, Mete-Sungur A1 - Weidner, Steffen T1 - Solvent-free sample preparation for matrix-assisted laserdesorption/ionization time-of-flight mass spectrometry ofpolymer blends N2 - Solvent-free sample preparation offers some advantages over solvent-based techniques, such as improved accuracy, reproducibility and sensitivity, for matrix-assisted laser desorption/ionization (MALDI) analysis. However, little or no information is available on the application of solvent-free techniques for the MALDI analysis of polymer blends. Solvent-free sample preparation by ball milling was applied with varying sample-to-matrix ratios for MALDI time-of-flight mass spectrometry analysis of various polymers, including polystyrenes, poly(methyl methacrylate)s and poly(ethylene glycol)s. The peak intensity ratios were compared with those obtained after using the conventional dried droplet sample preparation method. In addition, solvent-assisted milling was also applied to improve sample homogeneities. Depending on the sample preparation method used, different peak intensity ratios were found, showing varying degrees of suppression of the signal intensities of higher mass polymers. Ball milling for up to 30 min was required to achieve constant intensity ratios indicating homogeneous mixtures. The use of wet-assisted grinding to improve the homogeneity of the blends was found to be disadvantageous as it caused partial degradation and mass-dependent segregation of the polymers in the vials.The results clearly show that solvent-free sample preparation must be carefully considered when applied to synthetic polymer blends, as it may cause additional problems with regard to homogeneity and stability of the blends. KW - MALDI TOF MS KW - Sample preparation KW - Polymer blends KW - Solvent-free PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598570 DO - https://doi.org/10.1002/rcm.9756 SN - 0951-4198 VL - 38 IS - 12 SP - 1 EP - 9 PB - Wiley online library AN - OPUS4-59857 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von Törne, Wipert Jannik A1 - Steinhäuser, Lorin A1 - Klyk-Seitz, Urszula-Anna A1 - Piechotta, Christian T1 - High-resolution mass spectrometric elucidation of electron ionization induced fragmentation pathways of methylated warfarin and selected hydroxylated species N2 - The plant secondary metabolite families of coumarin and 4-hydroxy coumarin have a broad pharmacological spectrum ranging from antibacterial to anticancer properties. One prominent member of this substance class is the synthetic but naturally inspired anticoagulant drug and rodenticide warfarin (coumadin). A vast number of publications focus on the identification of warfarin and its major cytochrome P450-mediated phase I metabolites by liquid chromatography (LC) with mass spectrometry (MS) and tandem mass spectrometric (MS/MS) detection techniques. For the first time, electron ionization (EI) induced high-resolution quadrupole time-of-flight mass spectrometric (HR-qToF-MS) data of in-liner derivatized warfarin and selected hydroxylated species is provided in this study as an alternative to LC-MS/MS approaches. Furthermore, the characteristic fragments and fragmentation pathways of the analyzed methyl ethers are concluded. The obtained data of analytical standards, specific deuterated and 13C-labeled compounds prove inductive cleavage of the acyl or acetonyl side chain, methyl migration, and H-migration, along with consequential inductive cleavage as predominant fragmentation routes. Based on the HR-spectral data, commonalities and differences between the analyzed compounds and fragment groups were evaluated with future applicability in structure elucidation and spectra prediction of related compounds. KW - High-resolution mass spectrometry KW - Warfarin KW - Hydroxy warfarin KW - Fragmentation pathway PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596025 DO - https://doi.org/10.1016/j.ijms.2024.117220 SN - 1387-3806 VL - 499 SP - 1 EP - 7 PB - Elsevier B.V. AN - OPUS4-59602 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schilling, Markus A1 - Bayerlein, Bernd A1 - von Hartrott, Philipp A1 - Waitelonis, Jörg A1 - Birkholz, Henk A1 - Portella, Pedro Dolabella A1 - Skrotzki, Birgit T1 - FAIR and Structured Data: A Domain Ontology Aligned with Standard‐Compliant Tensile Testing N2 - The digitalization of materials science and engineering (MSE) is currently leading to remarkable advancements in materials research, design, and optimization, fueled by computer‐driven simulations, artificial intelligence, and machine learning. While these developments promise to accelerate materials innovation, challenges in quality assurance, data interoperability, and data management have to be addressed. In response, the adoption of semantic web technologies has emerged as a powerful solution in MSE. Ontologies provide structured and machine‐actionable knowledge representations that enable data integration, harmonization, and improved research collaboration. This study focuses on the tensile test ontology (TTO), which semantically represents the mechanical tensile test method and is developed within the project Plattform MaterialDigital (PMD) in connection with the PMD Core Ontology. Based on ISO 6892‐1, the test standard‐compliant TTO offers a structured vocabulary for tensile test data, ensuring data interoperability, transparency, and reproducibility. By categorizing measurement data and metadata, it facilitates comprehensive data analysis, interpretation, and systematic search in databases. The path from developing an ontology in accordance with an associated test standard, converting selected tensile test data into the interoperable resource description framework format, up to connecting the ontology and data is presented. Such a semantic connection using a data mapping procedure leads to an enhanced ability of querying. The TTO provides a valuable resource for materials researchers and engineers, promoting data and metadata standardization and sharing. Its usage ensures the generation of finable, accessible, interoperable, and reusable data while maintaining both human and machine actionability. KW - Data Interoperability KW - Domain Ontology Development KW - FAIR Data Management KW - Knowledge Representation KW - Tensile Test Ontology KW - Semantic Web Technologies PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598142 DO - https://doi.org/10.1002/adem.202400138 SN - 1438-1656 SP - 1 EP - 19 PB - Wiley VHC-Verlag AN - OPUS4-59814 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fardan, Ahmed A1 - Fazi, Andrea A1 - Peng, Ru Lin A1 - Mishurova, Tatiana A1 - Thuvander, Mattias A1 - Bruno, Giovanni A1 - Brodin, Håkan A1 - Hryha, Eduard T1 - Fine-Tuning Melt Pools and Microstructures: Taming Cracks in Powder Bed Fusion—Laser Beam of a non-weldable Ni-base Superalloy N2 - Powder Bed Fusion – Laser Beam (PBF-LB) of high γ’ strengthened Ni-base superalloys, such as CM247LC, is of great interest for high temperature applications in gas turbines. However, PBF-LB of CM247LC is challenging due to the high cracking susceptibility during PBF-LB processing (solidification cracking) and heat treatment (strain age cracking, mostly caused by residual stresses). This study focuses on understanding the impact of process parameters on microstructure, residual stresses and solidification cracking. Laser power (P), speed (v) and hatch spacing (h) were varied while the layer thickness (t) was fixed. The melt pool size and shape were found to be key factors in minimizing solidification cracking. Narrower and shallower melt pools, achieved using a low line energy density (LED = P/v ≤ 0.1 J/mm), gave low crack densities (0.7 mm/mm2). A tight hatch spacing (h = 0.03 mm) resulted in reduced lack of fusion porosity. Electron backscatter diffraction investigations revealed that parameters giving finer microstructure with 〈100〉crystallographic texture had low crack densities provided they were processed with a low LED. Atom probe tomography elucidated early stages of spinodal decomposition in the as-built condition, where Cr and Al cluster separately. The extent of spinodal decomposition was found to be affected by the LED and the hatch spacing. Samples with low LED and small hatch spacing showed higher degrees of spinodal decomposition. X-ray diffraction residual stress investigations revealed that the residual stress is proportional to the volumetric energy density (VED = P/(v. h. t)). Although low residual stresses can be achieved by using low VED, there is a high risk of lack of fusion. Hence, other parameters such as modified scan strategy, build plate pre-heating and pulsed laser mode, must be further explored to minimize the residual stresses to reduce the strain age cracking susceptibility. KW - Additive manufacturing KW - X-ray CT KW - Non-weldable superalloy KW - Solidification cracking PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597340 DO - https://doi.org/10.1016/j.mtla.2024.102059 SN - 2589-1529 VL - 34 IS - 102059 SP - 1 EP - 16 PB - Elsevier B.V. AN - OPUS4-59734 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hoffmann, Moritz A1 - Stawarczyk, Bogna A1 - Günster, Jens A1 - Zocca, Andrea T1 - Influence of additives and binder on the physical properties of dental silicate glass-ceramic feedstock for additive manufacturing N2 - Objectives The aim of the study was to investigate the impact of organic additives (binder, plasticizer, and the cross-linking ink) in the formulation of water-based feedstocks on the properties of a dental feldspathic glass-ceramic material developed for the slurry-based additive manufacturing technology “LSD-print.” Material and methods Three water-based feldspathic feedstocks were produced to study the effects of polyvinyl alcohol (AC1) and poly (sodium 4-styrenesulfonate) (AC2) as binder systems. A feedstock without organic additives was tested as the control group (CG). Disc-shaped (n = 15) and bar (n = 7) specimens were slip-cast and characterized in the green and fired states. In the green state, density and flexural strength were measured. In the fired state, density, shrinkage, flexural strength (FS), Weibull modulus, fracture toughness (KIC), Martens parameters, and microstructure were analyzed. Disc-shaped and bar specimens were also cut from commercially available CAD/CAM blocks and used as a target reference (TR) for the fired state. Results In the green state, CG showed the highest bulk density but the lowest FS, while the highest FS in the green state was achieved with the addition of a cross-linking ink. After firing, no significant differences in density and a similar microstructure were observed for all slip-cast groups, indicating that almost complete densification could be achieved. The CAD/CAM specimens showed the highest mean FS, Weibull modulus, and KIC, with significant differences between some of the slip-cast groups. Significance These results suggest that the investigated feedstocks are promising candidates for the slurry-based additive manufacturing of restorations meeting the class 1a requirements according to DIN EN ISO 6871:2019–01. KW - Firing KW - 3D-printing KW - Silicate glass-ceramics KW - Debinding PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600516 DO - https://doi.org/10.1016/j.jmbbm.2024.106563 SN - 1751-6161 VL - 155 SP - 1 EP - 12 PB - Elsevier B.V. AN - OPUS4-60051 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Yi A1 - Danischewski, Julia A1 - Molnar, Brian A1 - Riedel, Jens A1 - Shelley, Jacob T1 - Manipulation of Gaseous Ions with Acoustic Fields at Atmospheric Pressure N2 - The ability to controllably move gaseous ions is an essential aspect of ion-based spectrometry (e.g., mass spectrometry and ion mobility spectrometry) as well as materials processing. At higher pressures, ion motion is largely governed by diffusion and multiple collisions with neutral gas molecules. Thus, high-pressure ion optics based on electrostatics require large fields, radio frequency drives, complicated geometries, and/or partially transmissive grids that become contaminated. Here, we demonstrate that low-power standing acoustic waves can be used to guide, block, focus, and separate beams of ions akin to electrostatic ion optics. Ions preferentially travel through the static-pressure regions (“nodes”) while neutral gas does not appear to be impacted by the acoustic field structure and continues along a straight trajectory. This acoustic ion manipulation (AIM) approach has broad implications for ion manipulation techniques at high pressure, while expanding our fundamental understanding of the behavior of ions in gases. KW - Ion mobility spectrometry KW - Acoustic KW - Mass spectrometry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600704 DO - https://doi.org/10.1021/jacs.4c01224 SP - 1 EP - 6 PB - ACS Publications AN - OPUS4-60070 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Maulas, Kryzzyl M. A1 - Paredes, Charla S. A1 - Tabelin, Carlito Baltazar A1 - Jose, Mark Anthony A1 - Opiso, Einstine M. A1 - Arima, Takahiko A1 - Park, Ilhwan A1 - Mufalo, Walubita A1 - Ito, Mayumi A1 - Igarashi, Toshifumi A1 - Phengsaart, Theerayut A1 - Villas, Edrhea A1 - Dagondon, Sheila L. A1 - Metillo, Ephrime B. A1 - Uy, Mylene M. A1 - Manua, Al James A. A1 - Villacorte-Tabelin, Mylah T1 - Isolation and Characterization of Indigenous Ureolytic Bacteria from Mindanao, Philippines: Prospects for Microbially Induced Carbonate Precipitation (MICP) N2 - Microbially induced carbonate precipitation (MICP), a widespread phenomenon in nature, is gaining attention as a low-carbon alternative to ordinary Portland cement (OPC) in geotechnical engineering and the construction industry for sustainable development. In the Philippines, however, very few works have been conducted to isolate and identify indigenous, urease-producing (ureolytic) bacteria suitable for MICP. In this study, we isolated seven, ureolytic and potentially useful bacteria for MICP from marine sediments in Iligan City. DNA barcoding using 16s rDNA identified six of them as Pseudomonas stutzeri, Pseudomonas pseudoalcaligenes, Bacillus paralicheniformis, Bacillus altitudinis, Bacillus aryabhattai, and Stutzerimonas stutzeri but the seventh was not identified since it was a bacterial consortium. Bio-cementation assay experiments showed negligible precipitation in the control (without bacteria) at pH 7, 8, and 9. However, precipitates were formed in all seven bacterial isolates, especially between pH 7 and 8 (0.7–4 g). Among the six identified bacterial species, more extensive precipitation (2.3–4 g) and higher final pH were observed in S. stutzeri, and B. aryabhattai, which indicate better urease production and decomposition, higher CO2 generation, and more favorable CaCO3 formation. Characterization of the precipitates by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR) confirmed the formation of three carbonate minerals: calcite, aragonite, and vaterite. Based on these results, all six identified indigenous, ureolytic bacterial species from Iligan City are suitable for MICP provided that the pH is controlled between 7 and 8. To the best of our knowledge, this is the first report of the urease-producing ability and potential for MICP of P. stutzeri, P. pseudoalcaligenes, S. stutzeri, and B. aryabhattai. KW - Calcium carbonate KW - Microbially induced carbonate precipitation (MICP) KW - Ureolytic bacteria PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600888 DO - https://doi.org/10.3390/min14040339 VL - 14 IS - 4 SP - 1 EP - 15 PB - MDPI AN - OPUS4-60088 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hartwig, Philipp A1 - Bakir, Nasim A1 - Gumenyuk, Andrey A1 - Scheunemann, Lisa A1 - Schröder, Jörg A1 - Rethmeier, Michael T1 - A Physically Motivated Heat Source Model for Laser Beam Welding N2 - In this contribution, we present a physically motivated heat source model for the numerical modeling of laser beam welding processes. Since the calibration of existing heat source models, such as the conic or Goldak model, is difficult, the representation of the heat source using so-called Lamé curves has been established, relying on prior Computational Fluid Dynamics (CFD) simulations. Lamé curves, which describe the melting isotherm, are used in a subsequent finite-element (FE) simulation to define a moving Dirichlet boundary condition, which prescribes a constant temperature in the melt pool. As an alternative to this approach, we developed a physically motivated heat source model, which prescribes the heat input as a body load directly. The new model also relies on prior CFD simulations to identify the melting isotherm. We demonstrate numerical results of the new heat source model on boundary-value problems from the field of laser beam welding and compare it with the prior CFD simulation and the results of the Lamé curve model and experimental data. KW - Welding simulation KW - Heat source models KW - Laser beam welding KW - Thermal analysis PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600899 DO - https://doi.org/10.3390/met14040430 VL - 14 IS - 4 SP - 1 EP - 26 PB - MDPI CY - Basel AN - OPUS4-60089 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schlögl, Johanna A1 - Goldammer, Ole A1 - Bader, Julia A1 - Emmerling, Franziska A1 - Riedel, Sebastian T1 - Introducing AFS ([Al(SO3F)3]x) – a thermally stable, readily available, and catalytically active solid Lewis superacid N2 - This paper introduces the thermally stable, solid Lewis superacid aluminium tris(fluorosulfate) (AFS), that is easy-to-synthesize from commercially available starting materials. Its applicability, e.g. in catalytic C–F bond activations, is shown. KW - Lewis Acid KW - C-F activation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601001 DO - https://doi.org/10.1039/D4SC01753F SN - 2041-6520 SP - 1 EP - 7 PB - Royal Society of Chemistry (RSC) AN - OPUS4-60100 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fiedler, Saskia A1 - Frenzel, Florian A1 - Würth, Christian A1 - Tavernaro, Isabella A1 - Grüne, M. A1 - Schweizer, S. A1 - Engel, A. A1 - Resch-Genger, Ute T1 - Interlaboratory Comparison on Absolute Photoluminescence Quantum Yield Measurements of Solid Light Converting Phosphors with Three Commercial Integrating Sphere Setups N2 - Scattering luminescent materials dispersed in liquid and solid matrices and luminescent powders are increasingly relevant for fundamental research and industry. Examples are luminescent nano- and microparticles and phosphors of different compositions in various matrices or incorporated into ceramics with applications in energy conversion, solid-state lighting, medical diagnostics, and security barcoding. The key parameter to characterize the performance of these materials is the photoluminescence/fluorescence quantum yield (Φf), i.e., the number of emitted photons per number of absorbed photons. To identify and quantify the sources of uncertainty of absolute measurements of Φf of scattering samples, the first interlaboratory comparison (ILC) of three laboratories from academia and industry was performed by following identical measurement protocols. Thereby, two types ofcommercial stand-alone integrating sphere setups with different illumination and detection geometries were utilized for measuring the Φf of transparent and scattering dye solutions and solid phosphors, namely, YAG:Ce optoceramics of varying surface roughness, used as converter materials for blue light emitting diodes. Special emphasis was dedicated to the influence of the measurement geometry, the optical properties of the blank utilized to determine the number of photons of the incident excitation light absorbed by the sample, and the sample-specific surface roughness. While the Φf values of the liquid samples matched between instruments, Φf measurements of the optoceramics with different blanks revealed substantial differences. The ILC results underline the importance of the measurement geometry, sample position, and blank for reliable Φf data of scattering the YAG:Ce optoceramics, with the blank’s optical properties accounting for uncertainties exceeding 20%. KW - Nano KW - Fluorescence KW - Reference material KW - Luminescence KW - Quantitative spectroscopy KW - Particle KW - Quantum yield KW - Quality assurance KW - Phosphor KW - Converter material KW - Lifetime KW - Interlaboratory comparison KW - Method KW - Uncertainty PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600945 DO - https://doi.org/10.1021/acs.analchem.4c00372 SN - 0003-2700 SP - 6730 EP - 6737 PB - ACS Publications AN - OPUS4-60094 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Camplese, Davide A1 - Scarponi, Giordano Emrys A1 - Chianese, Carmela A1 - Hajhariri, Aliasghar A1 - Eberwein, Robert A1 - Otremba, Frank A1 - Cozzani, Valerio T1 - Modeling the performance of multilayer insulation in cryogenic tanks undergoing external fire scenarios N2 - Multilayer Insulation (MLI) is frequently used in vacuum conditions for the thermal insulation of cryogenic storage tanks. The severe consequences of the degradation of such materials in engulfing fire scenarios were recently evidenced by several large-scale experimental tests. In the present study, an innovative modelling approach was developed to assess the performance of heat transfer in polyester-based MLI materials for cryogenic applications under fire conditions. A specific layer-by-layer approach was integrated with an apparent kinetic thermal degradation model based on thermogravimetric analysis results. The modeling results provided a realistic simulation of the experimental data obtained by High-Temperature Thermal Vacuum Chamber tests reproducing fire exposure conditions. The model was then applied to assess the behavior of MLI systems for liquid hydrogen tanks in realistic fire scenarios. The results show that in intense fire scenarios degradation occurs rapidly, compromising the thermal insulation performances of the system within a few minutes. KW - Multilayer Insulation KW - Cryogenic Vessels KW - Liquefied Hydrogen KW - Liquefied Natural Gas KW - Safety KW - Fire PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599418 DO - https://doi.org/10.1016/j.psep.2024.04.061 SN - 0957-5820 VL - 186 SP - 1169 EP - 1182 PB - Elsevier B.V. AN - OPUS4-59941 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Taghavi Kalajahi, Sara A1 - Misra, Archismita A1 - Koerdt, Andrea T1 - Nanotechnology to mitigate microbiologically influenced corrosion (MIC) N2 - Microbiologically influenced corrosion (MIC) is a crucial issue for industry and infrastructure. Biofilms are known to form on different kinds of surfaces such as metal, concrete, and medical equipment. However, in some cases the effect of microorganisms on the material can be negative for the consistency and integrity of the material. Thus, to overcome the issues raised by MIC on a system, different physical, chemical, and biological strategies have been considered; all having their own advantages, limitations, and sometimes even unwanted disadvantages. Among all the methods, biocide treatments and antifouling coatings are more common for controlling MIC, though they face some challenges. They lack specificity for MIC microorganisms, leading to cross-resistance and requiring higher concentrations. Moreover, they pose environmental risks and harm non-target organisms. Hence, the demand for eco-friendly, long-term solutions is increasing as regulations tighten. Recently, attentions have been directed to the application of nanomaterials to mitigate or control MIC due to their significant antimicrobial efficiency and their potential for lower environmental risk compared to the conventional biocides or coatings. Use of nanomaterials to inhibit MIC is very new and there is a lack of literature review on this topic. To address this issue, we present a review of the nanomaterials examined as a biocide or in a form of a coating on a surface to mitigate MIC. This review will help consolidate the existing knowledge and research on the use of nanomaterials for MIC mitigation. It will further contribute to a better understanding of the potential applications and challenges associated with using nanomaterials for MIC prevention and control. KW - Microbiologically influenced corrosion (MIC) KW - Biofilm KW - Biofouling KW - Nanobiocide KW - Nanocoating PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599335 DO - https://doi.org/10.3389/fnano.2024.1340352 VL - 6 SP - 1 EP - 25 AN - OPUS4-59933 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dittmar, Stefan A1 - Ruhl, Aki S. A1 - Altmann, Korinna A1 - Jekel, Martin T1 - Settling Velocities of Small Microplastic Fragments and Fibers N2 - There is only sparse empirical data on the settling velocity of small, non-buoyant microplastics thus far, although it is an important parameter governing their vertical transport within aquatic environments. This study reports the settling velocities of 4031 exemplary microplastic particles. Focusing on the environmentally most prevalent particle shapes, irregular microplastic fragments of four different polymer types (9–289 µm) as well as five discrete length fractions (50–600 µm) of common nylon and polyester fibers were investigated, respectively. All settling experiments were carried out in quiescent water using a specialized optical imaging setup. The method has been previously validated in order to minimize disruptive factors, e.g. thermal convection or particle interactions, and thus enable the precise measurements of the velocities of individual microplastic particles (0.003–9.094 mm/s). Based on the obtained data, ten existing models for predicting a particle’s terminal settling velocity were assessed. It is concluded that models, which were specifically deduced from empirical data on larger microplastics, fail to provide accurate predictions for small microplastics. Instead, a different approach is highlighted as a viable option for computing settling velocities across the microplastics continuum in terms of size, density and shape. KW - Microplastics KW - Microplastic fibers KW - Settling velocity KW - Sinking velocity KW - Sedimentation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597455 DO - https://doi.org/10.1021/acs.est.3c09602 SN - 0013-936X VL - 58 IS - 14 SP - 6359 EP - 6369 PB - American Chemical Society (ACS) AN - OPUS4-59745 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sieg, Holger A1 - Schaar, Caroline A1 - Fouquet, Nicole A1 - Böhmert, Linda A1 - Thünemann, Andreas A1 - Braeuning, Albert T1 - Particulate iron oxide food colorants (E 172) during artificial digestion and their uptake and impact on intestinal cells N2 - Iron oxide of various structures is frequently used as food colorant (E 172). The spectrum of colors ranges from yellow over orange, red, and brown to black, depending on the chemical structure of the material. E 172 is mostly sold as solid powder. Recent studies have demonstrated the presence of nanoscaled particles in E 172 samples, often to a very high extent. This makes it necessary to investigate the fate of these particles after oral uptake. In this study, 7 differently structured commercially available E 172 food colorants (2 x Yellow FeO(OH), 2 x Red Fe2O3, 1 x Orange Fe2O3 + FeO(OH) and 2 x Black Fe3O4) were investigated for particle dissolution, ion release, cellular uptake, crossing of the intestinal barrier and toxicological impact on intestinal cells. Dissolution was analyzed in water, cell culture medium and artificial digestion fluids. Small-angle X-ray scattering (SAXS) was employed for determination of the specific surface area of the colorants in the digestion fluids. Cellular uptake, transport and toxicological effects were studied using human differentiated Caco-2 cells as an in vitro model of the intestinal barrier. For all materials, a strong interaction with the intestinal cells was observed, albeit there was only a limited dissolution, and no toxic in vitro effects on human cells were recorded. KW - Toxicology KW - Nanoparticles KW - Small-angle X-ray scattering KW - SAXS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593935 DO - https://doi.org/10.1016/j.tiv.2024.105772 VL - 96 SP - 1 EP - 12 PB - Elsevier BV AN - OPUS4-59393 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Heyn, A. A1 - Meist, M. A1 - Michael, O. A1 - Babutzka, M. A1 - Valet, Svenja A1 - Ebell, Gino T1 - Electrochemical characterization of surfaces of galvanized steels under different exposure conditions using gel electrolytes N2 - The corrosion behavior of galvanized steels and zinc components under atmospheric exposure depends mostly on the corrosion product‐based cover layer formation under the prevailing conditions. The use of agar‐based gel electrolytes makes it possible to use electrochemical methods to obtain a characteristic value from these cover layers that describe their current and future protective capacity. It is shown here that different states of galvanized steel can be distinguished very well under laboratory conditions and that this method is also suitable for use under practical conditions. Based on the characteristic values and assuming future time of wetness, it is very easy to draw up a forecast for the future corrosion rate, which provides plausible values. KW - Materials Chemistry KW - Metals and Alloys KW - Surfaces, Coatings and Films KW - Mechanical Engineering KW - Mechanics of Materials KW - Environmental Chemistry KW - Corrosion KW - Znc PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599234 DO - https://doi.org/10.1002/maco.202414389 SP - 1 EP - 16 PB - Wiley VHC-Verlag AN - OPUS4-59923 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Paul, Maxi B. A1 - Böhmert, Linda A1 - Thünemann, Andreas A1 - Loeschner, Katrin A1 - Givelet, Lucas A1 - Fahrenson, Christoph A1 - Braeuning, Albert A1 - Sieg, Holger T1 - Influence of artificial digestion on characteristics and intestinal cellular effects of micro-, submicro- and nanoplastics N2 - The production of plastics is rising since they have been invented. Micro, submicro- and nanoplastics are produced intentionally or generated by environmental processes, and constitute ubiquitous contaminants which are ingested orally by consumers. Reported health concerns include intestinal translocation, inflammatory response, oxidative stress and cytotoxicity. Every digestive milieu in the gastrointestinal tract does have an influence on the properties of particles and can cause changes in their effect on biological systems. In this study, we subjected plastic particles of different materials (polylactic acid, polymethylmethacrylate, melamine formaldehyde) and sizes (micro- to nano-range) to a complex artificial digestion model consisting of three intestinal fluid simulants (saliva, gastric and intestinal juice). We monitored the impact of the digestion process on the particles by performing Dynamic Light Scattering, Scanning Electron Microscopy and Asymmetric Flow Field-Flow Fractionation. An in vitro model of the intestinal epithelial barrier was used to monitor cellular effects and translocation behavior of (un)digested particles. In conclusion, artificial digestion decreased cellular interaction and slightly increased transport of all particles across the intestinal barrier. The interaction with organic matter resulted in clear differences in the agglomeration behavior. Moreover, we provide evidence for polymer-, size- and surface-dependent cellular effects of the test particles. KW - Toxicology KW - General Medicine KW - Food Science KW - Nanoplastics KW - Nanoparticle KW - Dynamic Light Scattering KW - DLS PY - 2024 DO - https://doi.org/10.1016/j.fct.2023.114423 VL - 184 SP - 1 EP - 16 PB - Elsevier AN - OPUS4-59298 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gluth, Gregor A1 - Mundra, Shishir A1 - Henning, Ricky T1 - Chloride binding by layered double hydroxides (LDH/AFm phases) and alkali-activated slag pastes: an experimental study by RILEM TC 283-CAM N2 - Chloride binding by the hydrate phases of cementitious materials influences the rate of chloride ingress into these materials and, thus, the time at which chloride reaches the steel reinforcement in concrete structures. Chloride binding isotherms of individual hydrate phases would be required to model chloride ingress but are only scarcely available and partly conflicting. The present study by RILEM TC 283-CAM ‘Chloride transport in alkali-activated materials’ significantly extends the available database and resolves some of the apparent contradictions by determining the chloride binding isotherms of layered double hydroxides (LDH), including AFm phases (monosulfate, strätlingite, hydrotalcite, and meixnerite), and of alkali-activated slags (AAS) produced with four different activators (Na2SiO3, Na2O·1.87SiO2, Na2CO3, and Na2SO4), in NaOH/NaCl solutions at various liquid/solid ratios. Selected solids after chloride binding were analysed by X-ray diffraction, and thermodynamic modelling was applied to simulate the phase changes occurring during chloride binding by the AFm phases. The results of the present study show that the chloride binding isotherms of LDH/AFm phases depend strongly on the liquid/solid ratio during the experiments. This is attributed to kinetic restrictions, which are, however, currently poorly understood. Chloride binding by AAS pastes is only moderately influenced by the employed activator. A steep increase of the chloride binding by AAS occurs at free chloride concentrations above approx. 1.0 M, which is possibly related to chloride binding by the C–(N–)A–S–H gel in the AAS. KW - Chloride binding KW - Sorption isotherm KW - Layered double hydroxide KW - AFm phase KW - Alkali-activated materials PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599370 DO - https://doi.org/10.1617/s11527-024-02311-3 SN - 1359-5997 SN - 1871-6873 VL - 57 IS - 4 SP - 1 EP - 17 PB - Springer Nature AN - OPUS4-59937 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kindrachuk, Vitaliy A1 - Darvishi Kamachali, Reza T1 - Mean-field modeling and phase-field simulation of grain growth under directional driving forces N2 - Directional grain growth is a common phenomenon in the synthetic and natural evolution of various polycrystals. It occurs in the presence of an external driving force, such as a temperature gradient, along which grains show a preferred, yet competitive, growth. Novel additive manufacturing processes, with intense, localized energy deposition, are prominent examples of when directional grain growth can occur, beneath the melting pool. In this work, we derive a phenomenological mean-field model and perform 3D phase-field simulations to investigate the directional grain growth and its underlying physical mechanisms. The effect of the intensity of driving force is simulated and systematically analyzed at the evolving growth front as well as various cross-sections perpendicular to the direction of the driving force. We found that although the directional growth significantly deviates from normal grain growth, it is still governed by a power law relation α tⁿ with an exponent n ~ 0.6–0.7. The exponent n exhibits a nontrivial dependence on the magnitude of the directional driving force, such that the lowest growth exponent is observed for intermediate driving forces. We elaborate that this can originate from the fact that the forces at grain boundary junctions evolve out of balance under the influence of the directional driving force. With increasing the driving forces, the growth exponent asymptotically approaches a value of n ≈ 0.63, imposed by the largest possible grain aspect ratio for given grain boundary energies. The current combined mean-field and phase-field framework pave the way for future exploration in broader contexts such as the evolution of complex additively manufactured microstructures. KW - Additive manufacturing KW - Phase-field simulation KW - Grain growth KW - Mean-field modelling KW - Directional grain growth PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593210 DO - https://doi.org/10.1016/j.mtla.2023.101989 SN - 2589-1529 VL - 33 SP - 1 EP - 10 PB - Elsevier AN - OPUS4-59321 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Geißler, Daniel A1 - Wegner, Karl David A1 - Fischer, C. A1 - Resch-Genger, Ute T1 - Exploring Simple Particle-Based Signal Amplification Strategies in a Heterogeneous Sandwich Immunoassay with Optical Detection N2 - Heterogeneous sandwich immunoassays are widely used for biomarker detection in bioanalysis and medical diagnostics. The high analyte sensitivity of the current “gold standard” enzyme-linked immunosorbent assay (ELISA) originates from the signal-generating enzymatic amplification step, yielding a high number of optically detectable reporter molecules. For future point-of-care testing (POCT) and point-of-need applications, there is an increasing interest in more simple detection strategies that circumvent time-consuming and temperature-dependent enzymatic reactions. A common concept to aim for detection limits comparable to those of enzymatic amplification reactions is the usage of polymer nanoparticles (NP) stained with a large number of chromophores. We explored different simple NP-based signal amplification strategies for heterogeneous sandwich immunoassays that rely on an extraction-triggered release step of different types of optically detectable reporters. Therefore, streptavidinfunctionalized polystyrene particles (PSP) are utilized as carriers for (i) the fluorescent dye coumarin 153 (C153) and (ii) hemin (hem) molecules catalyzing the luminol reaction enabling chemiluminescence (CL) detection. Additionally, (iii) NP labeling with hemin-based microperoxidase MP11 was assessed. For each amplification approach, the PSP was first systematically optimized regarding size, loading concentration, and surface chemistry. Then, for an immunoassay for the inflammation marker C- eactive protein (CRP), the analyte sensitivity achievable with optimized PSP ystems was compared with the established ELISA concept for photometric and CL detection. Careful optimization led to a limit of detection (LOD) of 0.1 ng/mL for MP11-labeled PSP and CL detection, performing similarly well to a photometric ELISA (0.13 ng/mL), which demonstrates the huge potential of our novel assay concept. KW - Nanoparticle KW - Fluorescence KW - Immunoassay KW - Quality assurance KW - Antibody KW - Polymer KW - Dye KW - Signal enhancement KW - CRP KW - Biosensing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597853 DO - https://doi.org/10.1021/acs.analchem.3c03691 SN - 1520-6882 VL - 96 IS - 13 SP - 5078 EP - 5085 PB - American Chemical Society CY - Columbus, Ohio AN - OPUS4-59785 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wegner, Karl David A1 - Resch-Genger, Ute T1 - The 2023 Nobel Prize in Chemistry: Quantum dots N2 - The 2023 Nobel Prize in Chemistry was awarded to Aleksey I. Ekimov (prize share 1/3), Louis E. Brus (prize share 1/3), and Moungi G. Bawendi (prize share 1/3) for groundbreaking inventions in the field of nanotechnology, i.e., for the discovery and synthesis of semiconductor nanocrystals, also termed quantum dots, that exhibit size-dependent physicochemical properties enabled by quantum size effects. This feature article summarizes the main milestones of the discoveries and developments of quantum dots that paved the road to their versatile applications in solid-state lighting, display technology, energy conversion, medical diagnostics, bioimaging, and image-guided surgery. KW - Quantum dots KW - Semiconductor nanocrystals KW - Luminescence KW - Quantitative spectroscopy KW - Quantum yield KW - Advanced nanomaterials KW - Quality assurance KW - Energy transfer PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597843 DO - https://doi.org/10.1007/s00216-024-05225-9 VL - 2024 SP - 1 EP - 11 PB - Springer CY - Cham AN - OPUS4-59784 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Silvestroni, L. A1 - Kupsch, Andreas A1 - Müller, B. R. A1 - Ulbricht, Alexander A1 - Wieder, Frank A1 - Fritsch, Tobias A1 - Sciti, D. A1 - Bruno, Giovanni T1 - Determination of short carbon fiber orientation in zirconium diboride ceramic matrix composites N2 - In fiber-reinforced components, the fiber alignment and orientation have paramount influence on the thermomechanical properties of the resulting composite, for both short and continuous fiber. Here we present the case of an ultra-refractory matrix intended for extreme environment applications, ZrB2, reinforced with 20 vol% and 50 vol% short carbon fibers. In both cases, fibers tend to align perpendicular to the uniaxial pressure applied during shaping and sintering of a pellet, although the fiber tilt across the pellet thickness is difficult to determine. Moreover, for high volume fractions of reinforcement, the spatial distribution of the fibers is heterogeneous and tends to have domains of preferential orientations. We compare the information on the fiber distribution as collected by scanning electron microscopy images, X-ray computed tomography and synchrotron X-ray refraction radiography (SXRR). The three techniques prove to be complementary. Importantly, we demonstrate that SXRR yields the most statistically significant information due to the largest field of view, yet with a sensitivity down to the nanometer, and that can be successfully applied also to heavy matrix materials, such as zirconium boride. KW - Ceramic matrix composites KW - Synchrotron X-ray refraction radiography KW - X-ray computed tomography KW - Scanning electron microscopy KW - High-temperature ceramics PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597712 DO - https://doi.org/10.1016/j.jeurceramsoc.2024.02.048 SN - 0955-2219 VL - 44 IS - 8 SP - 4853 EP - 4862 PB - Elsevier Ltd. CY - Amsterdam AN - OPUS4-59771 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, Hans R. A1 - Weidner, Steffen T1 - Ring-ring equilibration (RRE) of cyclic poly(L-lactide)s by means of cyclic tin catalysts N2 - With 2,2-dibutyl-2-stanna-1,3-dithiolane (DSTL) and 2-stanna-1,3-dioxa-4,5,6,7-dibenzoxepane (SnBiPh) as catalysts ring-expansion polymerizations (REP) were performed either in 2 M solution using three different solvents and two different temperatures or in bulk at 140 and 120 ◦C. A kinetically controlled rapid REP up to weight average molecular masses (Mẃs) above 300 000 was followed by a slower degradation of the molecular masses at 140 ◦C, but not at 120 ◦C Furthermore, a low molecular mass cyclic poly(L-lactide) (cPLA) with a Mn around 16 000 was prepared by polymerization in dilute solution and used as starting material for ring-ring equilibration at 140 ◦C in 2 M solutions. Again, a decrease of the molecular mass was detectable, suggesting that the equilibrium Mn is below 5 000. The degradation of the molecular masses via RRE was surprisingly more effective in solid cyclic PLA than in solution, and a specific transesterification mechanism involving loops on the surface of crystallites is proposed. This degradation favored the formation of extended-ring crystallites, which were detectable by a “saw-tooth pattern” in their MALDI mass spectra. KW - Organic Chemistry KW - Polymers and Plastics KW - MALDI-TOF MS KW - Materials Chemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593819 DO - https://doi.org/10.1016/j.eurpolymj.2024.112765 SN - 0014-3057 VL - 206 SP - 1 EP - 8 PB - Elsevier B.V. AN - OPUS4-59381 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Potopnyk, M. A1 - Mech-Piskorz, J. A1 - Angulo, G. A1 - Ceborska, M. A1 - Luboradzki, R. A1 - Andresen, Elina A1 - Gajek, A. A1 - Wisniewska, A. A1 - Resch-Genger, Ute T1 - Aggregation/Crystallization-Induced Emission in Naphthyridine-Based Carbazolyl-Modified Donor-Acceptor Boron Dyes Tunable by Fluorine Atoms N2 - Four donor-acceptor boron difluoride complexes based on the carbazole electron donor and the [1,3,5,2]oxadiazaborinino[3,4-a][1,8]naphthyridine acceptor were designed, synthesized, and systematically spectroscopically investigated in solutions, in the solid states, and dye-doped polymer films. The dyes exhibit an intense blue to red solid-state emission with photoluminescence quantum yields of up to 56% in pure dye samples and 86% in poly(methyl methacrylate) films. All boron complexes show aggregation-induced emission and reversible mechanofluorochromism. The optical properties of these dyes and their solid state luminescence can be tuned by substitution pattern, i.e., the substituents at the naphthyridine unit. Exchange of CH3- for CF3-groups does not only increase the intramolecular charge transfer character, but also provides a crystallization-induced emission enhancement. KW - Spectroscopy KW - Dye KW - Luminescence KW - Sensor KW - Fluorescence KW - Quantum yield KW - Lifetime KW - Quality assurance KW - Synthesis PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597426 DO - https://doi.org/10.1002/chem.202400004 SN - 0947-6539 SP - 1 EP - 12 PB - Wiley VHC-Verlag AN - OPUS4-59742 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Minenkov, Alexey A1 - Hollweger, Sophia A1 - Duchoslav, Jiri A1 - Erdene-Ochir, Otgonbayar A1 - Weise, Matthias A1 - Ermilova, Elena A1 - Hertwig, Andreas A1 - Schiek, Manuela T1 - Monitoring the Electrochemical Failure of Indium Tin Oxide Electrodes via Operando Ellipsometry Complemented by Electron Microscopy and Spectroscopy N2 - Transparent conductive oxides such as indium tin oxide (ITO) are standards for thin film electrodes, providing a synergy of high optical transparency and electrical conductivity. In an electrolytic environment, the determination of an inert electrochemical potential window is crucial to maintain a stable material performance during device operation. We introduce operando ellipsometry, combining cyclic voltammetry (CV) with spectroscopic ellipsometry, as a versatile tool to monitor the evolution of both complete optical (i.e., complex refractive index) and electrical properties under wet electrochemical operational conditions. In particular, we trace the degradation of ITO electrodes caused by electrochemical reduction in a pH-neutral, water-based electrolyte environment during electrochemical cycling. With the onset of hydrogen evolution at negative bias voltages, indium and tin are irreversibly reduced to the metallic state, causing an advancing darkening, i.e., a gradual loss of transparency, with every CV cycle, while the conductivity is mostly conserved over multiple CV cycles. Post-operando analysis reveals the reductive (loss of oxygen) formation of metallic nanodroplets on the surface. The reductive disruption of the ITO electrode happens at the solid–liquid interface and proceeds gradually from the surface to the bottom of the layer, which is evidenced by cross-sectional transmission electron microscopy imaging and complemented by energy-dispersive X-ray spectroscopy mapping. As long as a continuous part of the ITO layer remains at the bottom, the conductivity is largely retained, allowing repeated CV cycling. We consider operando ellipsometry a sensitive and nondestructive tool to monitor early stage material and property changes, either by tracing failure points, controlling intentional processes, or for sensing purposes, making it suitable for various research fields involving solid–liquid interfaces and electrochemical activity. KW - General Materials Science PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597625 DO - https://doi.org/10.1021/acsami.3c17923 SN - 1944-8252 VL - 16 IS - 7 SP - 9517 EP - 9531 PB - American Chemical Society (ACS) AN - OPUS4-59762 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Peters, Stefan A1 - Bartling, Stephan A1 - Parlinska-Wojtan, Magdalena A1 - Wotzka, Alexander A1 - Guilherme Buzanich, Ana A1 - Wohlrab, Sebastian A1 - Abdel-Mageed, Ali M. T1 - Stabilization of intermediate Mo oxidation states by Nb doping enhancing methane aromatization on Mo/HZSM-5 catalysts N2 - The dehydroaromatization of methane is a promising process to produce aromatics and ultra-pure hydrogen. Increased yields and stability of Mo/HZSM-5 against irreversible deactivation were achieved via a redox interaction by doping with otherwise inert Nb. KW - General Materials Science KW - Sustainability and the Environment KW - General Chemistry KW - Renewable Energy PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597670 DO - https://doi.org/10.1039/D3TA07532J SN - 2050-7488 SP - 1 EP - 16 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59767 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Cabo Rios, Alberto A1 - Mishurova, Tatiana A1 - Cordova, Laura A1 - Persson, Mats A1 - Bruno, Giovanni A1 - Olevsky, Eugene A1 - Hryha, Eduard T1 - Ex-situ characterization and simulation of density fluctuations evolution during sintering of binder jetted 316L N2 - Efficient density evolution during sintering of the as-printed component is vital to reach full densification and required properties of binder jet (BJT) components. However, due to the high porosity and brittle nature of the green compact, analysis of the microstructure development during sintering is very difficult, resulting in lack of understanding of the densification process. Density development from green state (57 ± 1.6 %) up to full density (99 ± 0.3 %) was characterized by high-resolution synchrotron X-Ray computed tomography (SXCT) on BJT 316L samples from ex-situ interrupted sintering tests. Periodicity of density fluctuations along the building direction was revealed for the first time and was related to the layer thickness of ~ 42 μm during printing that decreased down to ~ 33 μm during sintering. Sintering simulations, utilizing a continuum sintering model developed for BJT, allowed to replicate the density evolution during sintering with a mean error of 2 % and its fluctuation evolution from green (1.66 %) to sintered (0.56 %) state. Additionally, simulation of extreme particle size segregation (1 μm to 130 μm) suggested that non-optimized printing could lead to undesirable density fluctuation amplitude rapid increase (~10 %) during sintering. This might trigger the nucleation of defects (e.g., layer delamination, cracking, or excessive residual porosity) during the sintering process. KW - Additive manufacturing KW - Synchrotron X-ray CT KW - Binder Jetting KW - Sintering KW - FEM Simulation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594389 DO - https://doi.org/10.1016/j.matdes.2024.112690 SN - 0264-1275 VL - 238 SP - 1 EP - 18 PB - Elsevier AN - OPUS4-59438 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Theiler, Géraldine A1 - Cano Murillo, Natalia A1 - Halder, Karabi A1 - Balasooriya, Winoj A1 - Hausberger, Andreas A1 - Kaiser, Andreas T1 - Effect of high-pressure hydrogen environment on the physical and mechanical properties of elastomers N2 - This study presents the influence of high-pressure hydrogen environment on the physical and mechanical properties of two types of cross-linked hydrogenated acrylonitrile butadiene rubbers. Based on the CSA/ANSI standard, static exposures in hydrogen experiments were performed up to 100 MPa at 120 °C. Characterization before and after exposure was conducted by means of density and hardness measurements, dynamic mechanical analysis (DMA), tensile tests, compression set, FT-IR and AFM analyses to assess effects after decompression. While the effect of high-pressure exposure is significant immediately after exposure, most of the physical and mechanical properties recover after 48 hours. FT-IR, AFM, SEM and compression set results indicate, however, permanent effects. KW - Hydrogen KW - Mechanical properties KW - Elastomers KW - High-pressure hydrogen environment PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597102 DO - https://doi.org/10.1016/j.ijhydene.2024.01.148 SN - 0360-3199 VL - 58 SP - 389 EP - 399 PB - Elsevier Ltd. AN - OPUS4-59710 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Asna Ashari, Parsa A1 - Blind, Knut T1 - The effects of hydrogen research and innovation on international hydrogen trade N2 - Climate change and the pressure to decarbonize, as well as energy security concerns, have drawn the attention of policymakers and the industry to hydrogen energy. To ad-vance the hydrogen economy at a global scale, research and innovation progress is of significant importance, among others. However, previous studies have provided only lim-ited quantitative evidence of the effects of research and innovation on the formation of a global hydrogen market. Instead, they postulate rather than empirically support this rela-tionship. Therefore, this study analyzes the effects of research and innovation measured by scientific publications, patents, and standards on bilateral hydrogen trade flows for 32 countries between 1995 and 2019 in a gravity model of trade, using regression analyses and Poisson Pseudo Maximum Likelihood (PPML) estimation. The main results of the PPML estimation show that research and innovation progress is indeed associated with increased trade, especially with patenting and (international) standardization enhancing hydrogen export volumes. As policy implications, we derive that increased public R&D funding can help increase the competitiveness of hydrogen energy and boost market growth, along with infrastructure support and harmonized standards and regulations. KW - Hydrogen supply KW - Global hydrogen market KW - Research and innovation KW - Push and pull effects KW - Hydrogen policies PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594875 DO - https://doi.org/10.1016/j.enpol.2023.113974 SN - 0301-4215 VL - 186 SP - 1 EP - 15 PB - Elsevier B.V. AN - OPUS4-59487 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wang, Zengquan A1 - Riechers, Birte A1 - Derlet, Peter M. A1 - Maaß, Robert T1 - Atomic cluster dynamics causes intermittent aging of metallic glasses N2 - In the past two decades, numerous relaxation or physical aging experiments of metallic glasses have revealed signatures of intermittent atomic-scale processes. Revealed via intensity cross-correlations from coherent scattering using X-ray photon correlation spectroscopy (XPCS), the observed abrupt changes in the time-domain of atomic motion does not fit the picture of gradual slowing down of relaxation times and their origin continues to remain unclear. Using a binary Lennard-Jones model glass subjected to microsecond-long isotherms, we show here that temporally and spatially heterogeneous atomic-cluster activity at different length-scales drive the emergence of highly non-monotonous intensity cross-correlations. The simulated XPCS experiments reveal a variety of time-dependent intensity-cross correlations that, depending on both the structural evolution and the 𝑞-space sampling, give detailed insights into the possible structural origins of intermittent aging measured with XPCS. KW - Metallic glasses KW - Aging KW - Molecular dynamics KW - XPCS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595415 DO - https://doi.org/10.1016/j.actamat.2024.119730 SN - 1359-6454 VL - 267 SP - 1 EP - 9 PB - Elsevier B.V. CY - Amsterdam, Niederlande AN - OPUS4-59541 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Karapanagiotis, Christos A1 - Schukar, Marcus A1 - Krebber, Katerina T1 - Verteilte faseroptische Sensoren zur Zustandsüberwachung von Verbundwerkstoff-Druckbehältern T1 - Distributed fiber optic sensors for structural health monitoring of composite pressure vessels N2 - In diesem Beitrag geben wir einen umfassenden Überblick über unsere Forschung auf dem Gebiet der verteilten faseroptischen Sensorik für die strukturelle Zustandsüberwachung von Wasserstoffdruckbehältern aus Verbundwerkstoffen. Insbesondere zeigen wir, wie die Integration von faseroptischen Sensoren in Druckbehälter aus Verbundwerkstoffen die Sicherheit erhöht und gleichzeitig die Wartungskosten senkt. Die geringe Größe von Lichtwellenleitern ermöglicht ihre Integration in Verbundwerkstoffstrukturen während des Herstellungsprozesses, wodurch eine kontinuierliche Überwachung sowie eine präzise Erkennung und Lokalisierung von Strukturschäden während des Betriebs der Druckbehälter ermöglicht wird. Wir erörtern auch das Potenzial modernster Signalverarbeitungsmethoden und des maschinellen Lernens für die Weiterentwicklung der vorausschauenden Instandhaltung. Die von uns vorgestellten Anwendungen von faseroptischen Sensoren zeigen, dass sie einen wichtigen Beitrag zur Energiewende hin zu erneuerbaren Energien leisten können. KW - Verteilte faseroptische Sensoren KW - Verbundwerkstoffe KW - Wasserstoff-Druckbehälter KW - Strukturüberwachung KW - Maschinelles Lernen PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596290 DO - https://doi.org/10.1515/teme-2023-0170 SN - 0171-8096 SP - 1 EP - 12 AN - OPUS4-59629 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Emamverdi, Farnaz A1 - Huang, J. A1 - Mosane Razavi, Negar A1 - Bojdys, M. J. A1 - Forster, A. B. A1 - Budd, P. M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Molecular Mobility and Gas Transport Properties of Mixed Matrix Membranes Based on PIM‑1 and a Phosphinine Containing Covalent Organic Framework N2 - Polymers with intrinsic microporosity (PIMs) are gaining attention as gas separation membranes. Nevertheless, they face limitations due to pronounced physical aging. In this study a covalent organic framework containing λ5-phosphinine moieties, CPSF-EtO were incorporated as a nanofiller (concentration range 0-10 wt%) into a PIM-1 matrix forming dense films with a thickness of ca. 100 μm. The aim of the investigation was to investigate possible enhancements of gas transport properties and mitigating effects on physical aging. The incorporation of the nanofiller occurred on aggregate level with domains up to 100 nm as observed by T-SEM and confirmed by X-ray scattering. Moreover, the X-ray data show that the structure of the microporous network of the PIM-1 matrix is changed by the nanofiller. As the molecular mobility is fundamental for gas transport as well as for physical aging, the study includes dielectric investigations of pure PIM-1 and PIM-1/CPSF-EtO mixed matrix membranes to establish a correlation between the molecular mobility and the gas transport properties. Using the time-lag method the gas permeability and the permselectivity were determined for N2, O2, CH4 and CO2 for samples with variation in filler content. A significant increase in the permeability of CH4 and CO2 (50 % increase compared to pure PIM-1) was observed for a concentration of 5 wt% of the nanofiller. Furthermore, the most pronounced change in the permselectivity was found for the gas pair CO2/N2 at a filler concentration of 7 wt%. KW - Polymers of Intrinsic Microporosity KW - Nanocomposites PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595031 DO - https://doi.org/10.1021/acs.macromol.3c02419 SN - 0024-9297 VL - 57 IS - 4 SP - 1829 EP - 1845 PB - ACS Publications AN - OPUS4-59503 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bonse, Jörn A1 - Sokolowski‐Tinten, Klaus T1 - Probing Laser‐Driven Structure Formation at Extreme Scales in Space and Time N2 - Irradiation of solid surfaces with high intensity, ultrashort laser pulses triggers a variety of secondary processes that can lead to the formation of transient and permanent structures over a large range of length scales from mm down to the nano‐range. One of the most prominent examples are LIPSS – Laser‐Induced Periodic Surface Structures. While LIPSS have been a scientific evergreen for of almost 60 years, experimental methods that combine ultrafast temporal with the required nm spatial resolution have become available only recently with the advent of short pulse, short wavelength free electron lasers. Here, the current status and future perspectives in this field are discussed by exploiting the unique possibilities of these 4th‐generation light sources to address by time‐domain experimental techniques the fundamental LIPSS‐question, namely why and how laser irradiation can initiate the transition of a “chaotic” (rough) surface from an aperiodic into a periodic structure. KW - Laser-induced periodic surface structures (LIPSS) KW - Free electron laser KW - Pump-probe experiments KW - Time-resolved scattering KW - Capillary waves PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595048 DO - https://doi.org/10.1002/lpor.202300912 SN - 1863-8899 VL - 18 SP - 1 EP - 11 PB - Wiley-VCH GmbH CY - Weinheim AN - OPUS4-59504 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kromm, Arne A1 - Thomas, Maximilian A1 - Kannengiesser, Thomas A1 - Gibmeier, Jens T1 - On the interpretation of Varestraint and Transvarestraint hot cracking test results N2 - The Varestraint test and its variant Transvarestraint are one of the most widely used techniques for evaluating a material solidification cracking sensitivity during welding. The result of such tests is a crack length which is proportional to the material’s cracking susceptibility. Nevertheless, the welding and load parameters can unintentionally influence the crack length, which in some cases can distort the material evaluation. An approach is described as to how these effects can be assessed with the aid of a digital crack analysis. The crack lengths are compared position-dependently with their possible propagation due to the weld pool movement during continuous loading. The index derived from this can be used by the operator to evaluate his test parameters. In addition, a comparison of the results of different Varestraint setups is made possible. Alongside experimental results, a numerical sensitivity analysis is presented on how individual welding and loading parameters can affect the crack lengths. KW - Varestraint test KW - Solidification cracking KW - Weldability PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595089 DO - https://doi.org/10.1007/s40194-024-01706-8 SN - 0043-2288 SP - 1 EP - 13 PB - Springer Science and Business Media LLC AN - OPUS4-59508 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mansurova, Maria A1 - Johann, Sergej A1 - Kohlhoff, Harald A1 - Rurack, Knut A1 - Bartholmai, Matthias A1 - Bell, Jérémy T1 - On-Site Analytical Tool Based on Crude Oil Fluorescence and Chemometrics for the Rapid Determination of the Nature and Essential Properties of Oil Spills N2 - With the reduction of large oil spills because of stricter regulations and safety measures, the question of how to manage smaller oil spills arises. Few on-site analytical tools are available for first responders or other law enforcement personnel to rapidly test for crude oil in the early management of localized polluted areas. The approach reported here relies on well-described computer-assisted multivariate data analysis of the intrinsic fluorescence fingerprints of crude oils to build a multivariate model for the rapid classification of crude oils and the prediction of their properties. Thanks to a dedicated robust portable reader, the method allowed classification and accurate prediction of various properties of crude oil samples like density (according to API, the American Petroleum Institute and viscosity as well as composition parameters such as volume fractions of paraffins or aromatics. In this way, autonomous operation in on-site or in-the-field applications becomes possible based on the direct (undiluted and untreated) measurement of samples and a rapid, tablet-operated readout system to yield a robust and simple analytical test with superior performance. Testing in real-life scenarios allowed the successful classification and prediction of a number of oil spill samples as well as weathered samples that closely resemble samples collected by first responders. KW - Oil spills KW - Fluorescence KW - PCA KW - Petroleum KW - Rapid test KW - Portable PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595442 DO - https://doi.org/10.1021/acsestwater.3c00648 VL - 4 IS - 2 SP - 621 EP - 627 PB - American Chemical Society (ACS) AN - OPUS4-59544 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von Törne, Wipert Jannik A1 - Klyk-Seitz, Urszula-Anna A1 - Piechotta, Christian T1 - Developing a GC-EI-MS/MS method for quantifying warfarin and five hydroxylated metabolites generated by the Fenton reaction N2 - AbstractSince the 1950s, Warfarin has been used globally as both a prescription drug and a rodenticide. Research has shown that warfarin and other rodenticides are present in the environment and food chain. However, emerging contaminants are subject to degradation by biotic and abiotic processes and advanced oxidation processes. In some cases, detecting the parent compound may not be possible due to the formation of structurally changed species. This approach aims to identify hydroxylated transformation products of warfarin in a laboratory setting, even after the parent compound has undergone degradation. Therefore, the Fenton reaction is utilized to insert hydroxylation into the parent compound, warfarin, by hydroxyl and hydroperoxyl radicals generated by Fe2+/Fe3+ redox reaction with hydrogen peroxide. Using multiple reaction monitoring, a GC–MS/MS method, incorporating isotopically labeled reference compounds, is used to quantify the expected derivatized species. The analytes are derivatized using trimethyl-3-trifluoromethyl phenyl ammonium hydroxide, and the derivatization yield of warfarin is determined by using isotopically labeled reference compounds. The method has a linear working range of 30 to 1800 ng/mL, with detection limits ranging from 18.7 to 67.0 ng/mL. The analytes are enriched using a C18-SPE step, and the recovery for each compound is calculated. The Fenton reaction generates all preselected hydroxylated transformation products of warfarin. The method successfully identifies that 4′-Me-O-WAR forms preferentially under the specified experimental conditions. By further optimizing the SPE clean-up procedures, this GC–MS-based method will be suitable for detecting transformation products in more complex matrices, such as environmental water samples. Overall, this study provides a better understanding of warfarin’s degradation and offers a robust analytical tool for investigating its transformation products. KW - Health, Toxicology and Mutagenesis KW - Pollution KW - Environmental Chemistry KW - General Medicine PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595737 DO - https://doi.org/10.1007/s11356-024-32133-3 SN - 0944-1344 VL - 31 SP - 16986 EP - 16994 PB - Springer Science and Business Media LLC AN - OPUS4-59573 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rhode, Michael A1 - Erxleben, Kjell A1 - Richter, Tim A1 - Schroepfer, Dirk A1 - Mente, Tobias A1 - Michael, Thomas T1 - Local mechanical properties of dissimilar metal TIG welded joints of CoCrFeMnNi high entropy alloy and AISI 304 austenitic steel N2 - Multiple principal element alloys encompass the well-known high entropy alloys (HEA). The alloy system represents a new class of materials consisting of at least three alloying elements, each containing 5 to 35 at.%. Thus, this alloying concept differs fundamentally from conventional materials such as steel or nickel alloys. For this purpose, the alloying elements are specifically selected, the microstructures are adjusted in a single-phase and, in some cases, multi-phase manner. In particular, conflicting goals, such as the trade-off between strength and ductility in conventional steels, are overcome. However, in the last 20 years, the focus has been on material synthesis. With the increase in available material quantities, the focus is now on processing issues such as joining and welding processes. The weldability of HEAs has received very little attention so far. The experience with dissimilar metal welds is completely lacking but is essential for the application of these materials in combination with conventional materials. The present study presents comprehensive experimental results on the weldability of an equimolar CoCrFeMnNi-HEA in cold-rolled and heat-treated condition, which was joined by tungsten inert gas welding to an austenitic steel AISI 304. The mechanical properties of the dissimilar metal welds were characterized by cross-weld tensile samples, whereas the local deformation in the weld of the different welding zones was measured by digital image correlation. In accordance with the respective initial HEA condition (cold-rolled vs. heat-treated), the local strain behavior was divergent and influenced the global mechanical properties of both DMW types. Nonetheless, the experiments provided proof in principle of the weldability for dissimilar joints of the CoCrFeMnNi-HEA welded to conventional materials like austenitic stainless steels ensuring a corresponding capability for mechanical loading. This allows further considerations on the application of these innovative materials. KW - TIG welding KW - High-entropy alloys KW - Mechanical properties KW - Dissimilar metal weld PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595775 DO - https://doi.org/10.1007/s40194-024-01718-4 SN - 0043-2288 SP - 1 EP - 11 PB - Springer Science and Business Media LLC AN - OPUS4-59577 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Prabitz, Konstantin Manuel A1 - Antretter, Thomas A1 - Rethmeier, Michael A1 - El-Sari, Bassel A1 - Schubert, Holger A1 - Hilpert, Benjamin A1 - Gruber, Martin A1 - Sierlinger, Robert A1 - Ecker, Werner T1 - Numerical and experimental assessment of liquid metal embrittlement in externally loaded spot welds N2 - Zinc-based surface coatings are widely applied with high-strength steels in automotive industry. Some of these base materials show an increased brittle cracking risk during loading. It is necessary to examine electrogalvanized and uncoated samples of a high strength steel susceptible to liquid metal embrittlement during spot welding with applied external load. Therefore, a newly developed tensile test method with a simultaneously applied spot weld is conducted. A fully coupled 3D electrical, thermal, metallurgical and mechanical finite element model depicting the resistant spot welding process combined with the tensile test conducted is mandatory to correct geometric influences of the sample geometry and provides insights into the sample’s time dependent local loading. With increasing external loads, the morphology of the brittle cracks formed is affected more than the crack depth. The validated finite element model applies newly developed damage indicators to predict and explain the liquid metal embrittlement cracking onset and development as well as even ductile failure. KW - Resistance spot welding KW - Finite element simulation KW - Advanced high-strength steel KW - Liquid metal embrittlement KW - Damage prediction KW - Tensile resistance spot welding experiment PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594848 DO - https://doi.org/10.1007/s40194-024-01696-7 SN - 0043-2288 SP - 1 EP - 10 PB - Springer Science and Business Media LLC AN - OPUS4-59484 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhang, Kun A1 - Carrod, Andrew J. A1 - Del Giorgio, Elena A1 - Hughes, Joseph A1 - Rurack, Knut A1 - Bennet, Francesca A1 - Hodoroaba, Vasile-Dan A1 - Harrad, Stuart A1 - Pikramenou, Zoe T1 - Luminescence Lifetime-Based Sensing Platform Based on Cyclometalated Iridium(III) Complexes for the Detection of Perfluorooctanoic Acid in Aqueous Samples N2 - Luminescence lifetimes are an attractive analytical method for detection due to its high sensitivity and stability. Iridium probes exhibit luminescence with long excited-state lifetimes, which are sensitive to the local environment. Perfluorooctanoic acid (PFOA) is listed as a chemical of high concern regarding its toxicity and is classified as a “forever chemical”. In addition to strict limits on the presence of PFOA in drinking water, environmental contamination from industrial effluent or chemical spills requires rapid, simple, accurate, and cost-effective analysis in order to aid containment. Herein, we report the fabrication and function of a novel and facile luminescence sensor for PFOA based on iridium modified on gold surfaces. These surfaces were modified with lipophilic iridium complexes bearing alkyl chains, namely, IrC6 and IrC12, and Zonyl-FSA surfactant. Upon addition of PFOA, the modified surfaces IrC6-FSA@Au and IrC12-FSA @Au show the largest change in the red luminescence signal with changes in the luminescence lifetime that allow monitoring of PFOA concentrations in aqueous solutions. The platform was tested for the measurement of PFOA in aqueous samples spiked with known concentrations of PFOA and demonstrated the capacity to determine PFOA at concentrations >100 μg/L (240 nM). KW - Perfluorooctanoic Acid (PFOA) KW - Cyclometalated iridium (III) complexes KW - Luminescent lifetime KW - Optically active surfaces KW - ToF-SIMS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594535 UR - https://pubs.acs.org/doi/10.1021/acs.analchem.3c04289 DO - https://doi.org/10.1021/acs.analchem.3c04289 VL - 96 IS - 4 SP - 1565 EP - 1575 PB - American Chemical Society (ACS) AN - OPUS4-59453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Kricheldorf, H. T1 - Transformation of poly(L-lactide) crystals composed of linear chains into crystals composed of cycles N2 - A poly(L-lactide) with a trifluoroethyl ester end group and an average degree of polymerization (DP) of 50 was synthesized by ROP of L-lactide initiated with trifluoroethanol. Small-angle X-ray scattering (SAXS) in combination with differential scanning calorimetry (DSC) measurements revealed an average crystal thickness of 13 nm, corresponding to 45 repeat units. This suggests that most crystallites were formed by extended PLA chains, and both flat surfaces were covered by CF3 groups. The crystalline PLAs were annealed at 140 or 160 °C in the presence of two catalysts: tin(II) 2-ethylhexanoate, (SnOct2) or dibutyltin bis(pentafluorophenoxide) (BuSnPhF). The chemical reactions, such as polycondensation and cyclization, proceeded in the solid state and were monitored by matrix-assisted laser desorption/ionization time-offlight (MALDI TOF) mass spectrometry and gel permeation chromatography (GPC) measurements. Under optimal conditions a large fraction of linear chains was transformed into crystallites composed of extended cycles. Additionally, MALDI TOF MS analysis of GPC fractions from samples annealed for 28 or 42 days detected chain elongation of the linear species up to a factor of 20. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity KW - Transesterification PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597250 DO - https://doi.org/10.1039/D3PY01370G SN - 1759-9954 VL - 15 IS - 12 SP - 1173 EP - 1181 PB - Royal Society for Chemistry AN - OPUS4-59725 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brockmann, N. A1 - Sicken, A. A1 - Krüger, Jörg T1 - Effects of laser cleaning on the condition of different silk model samples using varying wavelengths and pulse durations N2 - The cleaning of aged silk fibers poses a common challenge in the conservation of textiles, since traditional cleaning techniques often yield unsatisfactory results or even harm objects. In this regard, cleaning objects with laser radiation is a promising addition to the range of available methods. Due to it being contactless, even brittle and touch-sensitive objects with disfiguring or harmful soiling could potentially be cleaned and therefore made accessible for research and presentation. Examples of treatment have sometimes shown spectacular results. Still there is some skepticism concerning the safety of this treatment for textile materials, which has been strengthened through previous 532 nm wavelength nanosecond laser cleaning studies on silk fibers. Taking these published results into account, the range of examined laser parameters has been extended in this study, from 532 nm nanosecond laser to 1064 nm nanosecond and even 800 nm femtosecond laser, reevaluating the effect of this treatment on the fibers. The physicochemical processes taking place on the silk fibers when cleaning with lasers are complex and still not fully understood. The aim of this project was therefore to bring more clarification about potential effects of those processes on the condition of silk samples treated with a set of different parameters for wavelength, pulse duration, energy density and number of pulses per spot. It also looks at the influence of the presence of soiling on the results. The analysis of potential effects was then carried out using statistical methods and advanced analytics. Scanning electron microscopy, Fourier-transform infrared spectroscopy and colorimetry technology provided the required insights to better assess the effects. Results show that laser cleaning of silk fibers, like most other conventional cleaning techniques, is not completely without risk, but knowing what the possible effects are helps making decisions on whether the benefits of the technique used justify these risks. KW - Laser cleaning KW - Cultural heritage KW - Conservation KW - Silk PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594601 DO - https://doi.org/10.1186/s40494-024-01152-1 SN - 2050-7445 VL - 12 IS - 1 SP - 1 EP - 15 PB - Springer AN - OPUS4-59460 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stawski, Tomasz A1 - Karafiludis, Stephanos A1 - Pimentel, Carlos A1 - Montes-Hernández, German A1 - Kochovski, Zdravko A1 - Bienert, Ralf A1 - Weimann, Karin A1 - Emmerling, Franziska A1 - Scoppola, Ernesto A1 - Van Driessche, Alexander E.S. T1 - Solution-driven processing of calcium sulfate: The mechanism of the reversible transformation of gypsum to bassanite in brines N2 - Here, we show that calcium sulfate dihydrate (gypsum) can be directly, rapidly and reversibly converted to calcium sulfate hemihydrate (bassanite) in high salinity solutions (brines). 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 better-known behaviour of the bassanite phase in low-salt environments. In low-salinity aqueous solutions, bassanite is considered to be metastable with respect to gypsum and anhydrite, and therefore gypsum-to-bassanite conversion does not occur in pure water. Interestingly, the high-salinity transformation of gypsum-to-bassanite has been reported by many authors and used in practice for several decades, although 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 was 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 phase for many hours before reverting into gypsum. This property is extremely advantageous for practical processing and efficient crystal extraction in industrial scenarios. KW - Industrial and Manufacturing Engineering KW - Strategy and Management KW - General Environmental Science KW - Renewable Energy, Sustainability and the Environment KW - Building and Construction KW - Calcium sulfate KW - Gypsum KW - Bassanite KW - Scattering KW - Raman KW - In situ KW - Synchrotron KW - BESSY KW - MySpot PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594698 UR - https://www.sciencedirect.com/science/article/pii/S0959652624004591#appsec1 DO - https://doi.org/10.1016/j.jclepro.2024.141012 SN - 0959-6526 VL - 440 SP - 1 EP - 12 PB - Elsevier B.V. AN - OPUS4-59469 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mrkwitschka, Paul A1 - Rühle, Bastian A1 - Kuchenbecker, Petra A1 - Löhmann, Oliver A1 - Lindemann, Franziska A1 - Hodoroaba, Vasile-Dan T1 - Embedding and cross-sectioning as a sample preparation procedure for accurate and representative size and shape measurement of nanopowders N2 - Reliable measurement of the size of polydisperse, complex-shaped commercial nanopowders is a difficult but necessary task, e.g., for regulatory requirements and toxicity risk assessment. Suitable methods exist for the accurate characterization of the size of non-aggregated, stabilized, spherical and monodisperse nanoparticles. In contrast, industrial nanoscale powders usually require dedicated sample preparation procedures developed for the analysis method of choice. These nano-powders tend to agglomerate and/or aggregate, a behavior which in combination with an innate broad particle size distribution and irregular shape often significantly alters the achievable accuracy of the measured size parameters. The present study systematically tests two commercially available nanoscale powders using different sample preparation methods for correlative analysis by scanning electron microscopy, dynamic light scattering, Brunauer–Emmet–Teller method and differential mobility analysis. One focus was set on the sample preparation by embedding nanoparticles in carbon-based hot-mounting resin. Literature on this topic is scarce and the accuracy of the data extracted from cross sections of these particles is unclearly stated. In this paper systematic simulations on the deviation of the size parameters of well-defined series of nanoparticles with different shapes from the nominal value were carried out and the contributing factors are discussed. KW - Nanopowder KW - Electron microscopy KW - Sample preparation KW - Cross-sectioning KW - Cerium oxide KW - Zinc oxide PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593289 DO - https://doi.org/10.1038/s41598-023-51094-0 SN - 2045-2322 VL - 14 SP - 1 EP - 10 PB - Springer Nature CY - London AN - OPUS4-59328 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Asna Ashari, Parsa A1 - Oh, Hyochan A1 - Koch, Claudia T1 - Pathways to the hydrogen economy: A multidimensional analysis of the technological innovation systems of Germany and South Korea N2 - The global trend towards decarbonization and the demand for energy security have put hydrogen energy into the spotlight of industry, politics, and societies. Numerous governments worldwide are adopting policies and strategies to facilitate the transition towards hydrogen-based economies. To assess the determinants of such transition, this study presents a comparative analysis of the technological innovation systems (TISs) for hydrogen technologies in Germany and South Korea, both recognized as global frontrunners in advancing and implementing hydrogen-based solutions. By providing a multidimensional assessment of pathways to the hydrogen economy, our analysis introduces two novel and crucial elements to the TIS analysis: (i) We integrate the concept of ‘quality infrastructure’ given the relevance of safety and quality assurance for technology adoption and social acceptance, and (ii) we emphasize the social perspective within the hydrogen TIS. To this end, we conducted 24 semi-structured expert interviews, applying qualitative open coding to analyze the data. Our results indicate that the hydrogen TISs in both countries have undergone significant developments across various dimensions. However, several barriers still hinder the further realization of a hydrogen economy. Based on our findings, we propose policy implications that can facilitate informed policy decisions for a successful hydrogen transition. KW - Hydrogen economy KW - Technological innovation system KW - Quality infrastructure KW - Multidimensional technology adoption KW - Social acceptance PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593312 DO - https://doi.org/10.1016/j.ijhydene.2023.08.286 IS - Volume 49, Part D SP - 405 EP - 421 PB - Elsevier AN - OPUS4-59331 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Alekseychuk, V. O. A1 - Kupsch, Andreas A1 - Plotzki, D. A1 - Bellon, Carsten A1 - Bruno, Giovanni T1 - Simulation-Assisted Augmentation of Missing Wedge and Region-of-Interest Computed Tomography Data N2 - This study reports a strategy to use sophisticated, realistic X-ray Computed Tomography (CT) simulations to reduce Missing Wedge (MW) and Region-of-Interest (RoI) artifacts in FBP (Filtered Back-Projection) reconstructions. A 3D model of the object is used to simulate the projections that include the missing information inside the MW and outside the RoI. Such information augments the experimental projections, thereby drastically improving the reconstruction results. An X-ray CT dataset of a selected object is modified to mimic various degrees of RoI and MW problems. The results are evaluated in comparison to a standard FBP reconstruction of the complete dataset. In all cases, the reconstruction quality is significantly improved. Small inclusions present in the scanned object are better localized and quantified. The proposed method has the potential to improve the results of any CT reconstruction algorithm. KW - Computed tomography KW - Missing wedge KW - Region of interest KW - Augmented data KW - CT simulation KW - aRTist PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593799 UR - https://www.mdpi.com/2313-433X/10/1/11 DO - https://doi.org/10.3390/jimaging10010011 SN - 2313-433X VL - 10 IS - 1 SP - 1 EP - 15 PB - MDPI CY - Basel AN - OPUS4-59379 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zia, Ghezal Ahmad Jan A1 - Hanke, Thomas A1 - Skrotzki, Birgit A1 - Völker, Christoph A1 - Bayerlein, Bernd T1 - Enhancing Reproducibility in Precipitate Analysis: A FAIR Approach with Automated Dark-Field Transmission Electron Microscope Image Processing N2 - AbstractHigh-strength aluminum alloys used in aerospace and automotive applications obtain their strength through precipitation hardening. Achieving the desired mechanical properties requires precise control over the nanometer-sized precipitates. However, the microstructure of these alloys changes over time due to aging, leading to a deterioration in strength. Typically, the size, number, and distribution of precipitates for a quantitative assessment of microstructural changes are determined by manual analysis, which is subjective and time-consuming. In our work, we introduce a progressive and automatable approach that enables a more efficient, objective, and reproducible analysis of precipitates. The method involves several sequential steps using an image repository containing dark-field transmission electron microscopy (DF-TEM) images depicting various aging states of an aluminum alloy. During the process, precipitation contours are generated and quantitatively evaluated, and the results are comprehensibly transferred into semantic data structures. The use and deployment of Jupyter Notebooks, along with the beneficial implementation of Semantic Web technologies, significantly enhances the reproducibility and comparability of the findings. This work serves as an exemplar of FAIR image and research data management. KW - Industrial and Manufacturing Engineering KW - General Materials Science KW - Automated image analysis KW - FAIR research data management KW - Reproducibility KW - microstructural changes PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593905 DO - https://doi.org/10.1007/s40192-023-00331-5 SN - 2193-9772 SP - 1 EP - 15 PB - Springer Science and Business Media LLC CY - Heidelberg AN - OPUS4-59390 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zuffa, Caterina A1 - Cappuccino, Chiara A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Maini, Lucia T1 - Liquid reagents are not enough for liquid assisted grinding in the synthesis of (AgBr)(n-pica) n N2 - This study investigates the mechanochemical reactions between AgBr 3-picolylamine and 4-picolylamine. The use of different stoichiometry ratios of the reagents allows [(AgBr)(n-pica)]n and [(AgBr)2(n-pica)]n to be obtained, and we report the new structures of [(AgBr)2(3-pica)]n and [(AgBr)2(4-pica)]n which are characterized by the presence of the following: (a) infinite inorganic chains, (b) silver atom coordinated only by bromide atoms and (c) argentophilic interactions. Furthermore, we studied the interconversion of [(AgBr)(n-pica)]n/[(AgBr)2(n-pica)]n by mechanochemical and thermal properties. The in situ experiments suggest that [(AgBr)(3-pica)]n is kinetically favoured while [(AgBr)2(3-pica)]n is converted into [(AgBr)(3-pica)]n only with a high excess of the ligand. Finally, the liquid nature of the ligands is not sufficient to assist the grinding process, and the complete reaction is observed with the addition of a small quantity of acetonitrile. KW - Mechanochemistry KW - Complex PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594755 DO - https://doi.org/10.1039/d3cp04791a SN - 1463-9076 SP - 1 EP - 10 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59475 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schwarz, I. A1 - Rieck, Arielle A1 - Mehmood, Asad A1 - Bublitz, R. A1 - Bongers, L. A1 - Weuster-Botz, D. A1 - Fellinger, Tim-Patrick T1 - PEM Electrolysis in a Stirred-Tank Bioreactor Enables Autotrophic Growth of Clostridium ragsdalei with CO2 and Electrons N2 - Acetogenic bacteria produce CO2-based chemicals in aqueous media by hydrogenotrophic conversion of CO2, but CO is the preferred carbon and electron source. Consequently, coupling CO2 electrolysis with bacterial fermentation within an integrated bio-electrocatalytical system (BES) is promising, if CO2 reduction catalysts are available for the generation of CO in the complex biotic electrolyte. A standard stirred-tank bioreactor was coupled to a zero-gap PEM electrolysis cell for CO2 conversion, allowing voltage control and separation of the anode in one single cell. The cathodic CO2 reduction and the competing hydrogen evolution enabled in-situ feeding of C. ragsdalei with CO and H2. Proof-of-concept was demonstrated in first batch processes with continuous CO2 gassing, as autotrophic growth and acetate formation was observed in the stirred BES in a voltage range of −2.4 to −3.0 V. The setup is suitable also for other bioelectrocatalytic reactions. Increased currents and lower overvoltages are however required. Atomically-dispersed M−N−C catalysts show promise, if degradation throughout autoclaving can be omitted. The development of selective and autoclavable catalysts resistant to contamination and electrode design for the complex electrolyte will enable efficient bioelectrocatalytic power-to-X systems based on the introduced BES. KW - Energy Conversion PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594766 DO - https://doi.org/10.1002/celc.202300344 SN - 2196-0216 SP - 1 EP - 10 PB - Wiley VHC-Verlag AN - OPUS4-59476 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Quackatz, Lukas A1 - Griesche, Axel A1 - Nietzke, Jonathan A1 - Kannengießer, Thomas T1 - In situ measurement of hydrogen concentration in steel using laser‑induced breakdown spectroscopy (LIBS) N2 - The ISO 3690 standard “Determination of hydrogen content in arc weld metal” requires a thermal activation of the diffusible hydrogen in a piece of weld metal for the subsequent ex situ concentration measurement by carrier gas hot extraction CGHE or thermal desorption spectroscopy (TCD). Laser-induced breakdown spectroscopy (LIBS) offers a time and spatially resolved, almost non-destructive, in situ measurement of hydrogen at surfaces without sample preparation. We measured hydrogen in steels, which were charged either electrochemically or by high-pressure hydrogen gas, and compared the results. Further, the feasibility of quantitative hydrogen line scan measurements with LIBS was demonstrated by measuring hydrogen at water jet cut surfaces. The hydrogen concentrations measured with the help of LIBS were compared with CGHE measurements. It was observed that hydrogen can be reliably measured with LIBS for concentrations larger than 2 wt.-ppm. The maximum hydrogen concentration achieved using electrochemical charging was 85.1 ppm. The results show that LIBS is a promising technique for time- and spatially resolved measurements of hydrogen in steels. T2 - IIW Annual Assembly 2023 CY - Singapore KW - LIBS KW - Hydrogen measurement KW - Welding KW - Stainless steel KW - Diffusible hydrogen PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593664 DO - https://doi.org/10.1007/s40194-023-01677-2 SP - 1 EP - 9 PB - Springer AN - OPUS4-59366 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Böllinghaus, Thomas A1 - Cross, Carl T1 - Obituary: Prof. Dr.-Ing. Hans Hoffmeister N2 - On November 3, 2023, our dear colleague, Prof. Dr.-Ing. Hans Hoffmeister, born in 1932 in Kassel, Germany, passed away in Ahrensburg, near Hamburg, Germany. KW - Metals and Alloys KW - Mechanical Engineering KW - Mechanics of Materials PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594160 DO - https://doi.org/10.1007/s40194-023-01675-4 SP - 1 EP - 2 PB - Springer Science and Business Media LLC AN - OPUS4-59416 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Falkenhagen, Jana A1 - Kricheldorf, H. R. T1 - Polycondensations and Cyclization of Poly(L-lactide) Ethyl Esters in the Solid State N2 - The usefulness of seven different Tin catalysts, Bismuth subsalicylate and Titan tetra(ethoxide) for the polycondensation of ethyl L-lactate (ELA) was examined at 150 °C/6 d. Dibutyltin bis(phenoxides) proved to be particularly effective. Despite the low reactivity of ELA, weight average molecular masses (Mw) up to 12 500 were found along with partial crystallization. Furthermore, polylactides (PLAs) of similar molecular masses were prepared via ELA-initiated ROPs of L-lactide by means of the four most effective polycondensation catalysts. The crystalline linear PLAs were annealed at 140 or 160 °C in the presence of these catalysts. The consequences of the transesterification reactions in the solid PLAs were studied by means of matrix-assisted laser desorption/ionization (MALDI TOF) mass spectrometry, gel permeation chromatography (GPC) and small-angle X-ray scattering (SAXS). The results indicate that polycondensation and formation of cycles proceed in the solid state via formation of loops on the surface of the crystallites. In summary, five different transesterification reactions are required to explain all results. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-592934 DO - https://doi.org/10.1039/d3py01232h SN - 1759-9962 VL - 15 IS - 2 SP - 71 EP - 82 PB - RSC Publ. CY - Cambridge AN - OPUS4-59293 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bayerlein, Bernd A1 - Schilling, Markus A1 - Birkholz, Henk A1 - Jung, Matthias A1 - Waitelonis, Jörg A1 - Mädler, Lutz A1 - Sack, Harald T1 - PMD Core Ontology: Achieving semantic interoperability in materials science N2 - Knowledge representation in the Materials Science and Engineering (MSE) domain is a vast and multi-faceted challenge: Overlap, ambiguity, and inconsistency in terminology are common. Invariant (consistent) and variant (context-specific) knowledge are difficult to align cross-domain. Generic top-level semantic terminology often is too abstract, while MSE domain terminology often is too specific. In this paper, an approach how to maintain a comprehensive MSE-centric terminology composing a mid-level ontology–the Platform MaterialDigital Core Ontology (PMDco)–via MSE community-based curation procedures is presented. The illustrated findings show how the PMDco bridges semantic gaps between high-level, MSE-specific, and other science domain semantics. Additionally, it demonstrates how the PMDco lowers development and integration thresholds. Moreover, the research highlights how to fuel it with real-world data sources ranging from manually conducted experiments and simulations with continuously automated industrial applications. KW - Ontology KW - Materials science and engineering KW - Knowledge representation KW - Reproducibility KW - Semantic interoperability KW - Semantic data integration PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-592948 DO - https://doi.org/10.1016/j.matdes.2023.112603 SN - 0264-1275 VL - 237 SP - 1 EP - 12 PB - Elsevier CY - Amsterdam AN - OPUS4-59294 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Klimek, André A1 - Stelzner, Ludwig A1 - Hothan, Sascha A1 - Zehfuß, Jochen T1 - Influence of thermal strain on concrete spalling N2 - Understanding the susceptibility to spalling of concrete members in case of fire is important to evaluate the residual load-bearing capacity. The investigations of the spalling phenomenon of a concrete mixture using real scale members are necessary but expensive to carry out. Reducing the specimen size leads to an increase of boundary effects that can result in a reduced spalling or absence of spalling. In this study, fire tests were carried out on unrestrained, single-sided exposed, cuboid shaped specimens (0.6 m x 0.6 m x 0.29 m) as well as unrestrained and steel ring restrained cylindrical specimens (Ø = 0.47 m, h = 0.29 m), which induce different boundary conditions. These fire tests were carried out on two ordinary concrete mixtures. The two mixtures differ only in the type of aggregates (quartz gravel and basalt grit) and were used to investigate the influence of the thermal expansion of the aggregate on the spalling behaviour of the concrete. The results show a significant increase of the spalling depth due to the restrained thermal expansion achieved by the applied steel rings. Additionally, the type of aggregate has a direct influence on the spalling behaviour of a concrete mixture. The reduction of the boundary effects by the steel rings recreate the test conditions in the centre of a large concrete member. Thus, this type of specimen is suitable to determine the susceptibility to spalling of a material (screening-tests) as preliminary investigations to full scale fire tests. KW - Spalling KW - Concrete KW - Fire test KW - Restraint KW - Screening test PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593350 DO - https://doi.org/10.1617/s11527-023-02274-x VL - 57 SP - 1 EP - 14 PB - Springer AN - OPUS4-59335 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Heinekamp, Christian A1 - Kneiske, Sönke A1 - Guilherme Buzanich, Ana A1 - Ahrens, Mike A1 - Braun, Thomas A1 - Emmerling, Franziska T1 - A fluorolytic sol-gel route to access an amorphous Zr fluoride catalyst: A useful tool for C-F bond activation N2 - A route to a ZrF4 catalyst active in room temperature Friedel–Crafts and dehydrofluorination reactions was developed via a fluorolytic sol–gel route, which was followed by a postfluorination step using a stream of CHClF2. The behaviour of different Zr(IV) precursors in a sol–gel reaction with anhydrous isopropanol/HF solution was investigated. The subsequent post-fluorination step was optimised in its temperature ramp and confirmed the necessity of a fluorination of the generated xerogels to obtain catalytic activity. The process is discussed in the context of the analysis of the materials using Brunauer–Emmett–Teller analysis (BET), powder X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The local structure of the amorphous catalyst was elucidated by extended X-ray absorption fine structure spectroscopy (EXAFS). KW - Catalysis KW - Heterogeneous catalysis KW - C-F bond activation KW - Postfluorination PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593433 DO - https://doi.org/10.1039/D3CY01439H SN - 2044-4761 SP - 1 EP - 8 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59343 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wandtke, Karsten ED - Becker, Amadeus ED - Schröpfer, Dirk ED - Kromm, Arne ED - Kannengießer, Thomas ED - Scharf-Wildenhain, R. ED - Hälsig, A. ED - Hensel, J. T1 - Residual Stress Evolution during Slot Milling for Repair Welding and Wire Arc Additive Manufacturing of High-Strength Steel Components N2 - High-strength steels offer potential for weight optimization due to reduced wall thicknesses in modern constructions. Additive manufacturing processes such as Wire Arc Additive Manufacturing (WAAM) enable the resource-efficient production of structures. In the case of defects occurring in weld seams orWAAM components due to unstable process conditions, the economical solution is local gouging or machining and repair welding. It is important to understand the effects of machining steps on the multiaxial stress state in conjunction with the design-related shrinkage restraints. Research into how welding and slot milling of welds andWAAM structures affects residual stresses is still lacking. For this reason, component-related investigations with high-strength steels with yield strengths ≥790 MPa are carried out in our research. In-situ digital image correlation (DIC) and ex-situ X-ray diffraction (XRD) were used to analyze the stresses and strains induced on specimens during and after milling. The systematic analyses revealed a significant interaction of the stiffness and microstructure of the specimens with the initial residual stresses induced by welding. Subsequent repair welds can result in significantly higher residual stresses. KW - High strength steels KW - Additive manufacturing KW - Residual stress KW - Repair welding KW - Ditigtal image correlation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593515 DO - https://doi.org/10.3390/met14010082 VL - 14 IS - 1 SP - 1 EP - 11 PB - MDPI CY - Basel AN - OPUS4-59351 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Andreoli, A. F. A1 - Fantin, Andrea A1 - Kasatikov, S. A1 - Bacurau, V. P. A1 - Widom, M. A1 - Gargarella, P. A1 - Mazzer, E. M. A1 - Woodcock, T. G. A1 - Nielsch, K. A1 - Coury, F. G. T1 - The impact of chemical short-range order on the thermophysical properties of medium- and high-entropy alloys N2 - The unusual behavior observed in the coefficient of thermal expansion and specific heat capacity of CrFeNi, CoCrNi, and CoCrFeNi medium/high-entropy alloys is commonly referred to as the K-state effect. It is shown to be independent of the Curie temperature, as demonstrated by temperature-dependent magnetic moment measurements. CoCrFeNi alloy is chosen for detailed characterization; potential reasons for the K-state effect such as texture, recrystallization, and second-phase precipitation are ruled out. An examination of the electronic structure indicates the formation of a pseudo-gap in the Density of States, which suggests a specific chemical interaction between Ni and Cr atoms upon alloying. Hybrid Monte Carlo/Molecular Dynamic (MC/MD) simulations indicate the presence of non-negligible chemical short-range order (CSRO). Local lattice distortions are shown to be negligible, although deviations around Cr and Ni elements from those expected in a fully disordered structure are experimentally observed by X-ray absorption spectroscopy. The determined bonding distances are in good agreement with MC/MD calculations. A mechanism is proposed to explain the anomalies and calorimetric experiments and their results are used to validate the mechanism. KW - Mechanical Engineering KW - Mechanics of Materials KW - General Materials Science PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595869 DO - https://doi.org/10.1016/j.matdes.2024.112724 SN - 0264-1275 VL - 238 SP - 1 EP - 15 PB - Elsevier B.V. AN - OPUS4-59586 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Was, G.S. A1 - Bahn, C.-B. A1 - Busby, J. A1 - Cui, B. A1 - Farkas, D. A1 - Gussev, M. A1 - Rigen He, M. A1 - Hesterberg, J. A1 - Jiao, Z. A1 - Johnson, D. A1 - Kuang, W. A1 - McMurtrey, M. A1 - Robertson, I. A1 - Sinjlawi, A. A1 - Song, M. A1 - Stephenson, K. A1 - Sun, K. A1 - Swaminathan, Srinivasan A1 - Wang, M. A1 - West, E. T1 - How irradiation promotes intergranular stress corrosion crack initiation N2 - Irradiation assisted stress corrosion cracking (IASCC) is a form of intergranular stress corrosion cracking that occurs in irradiated austenitic alloys. It requires an irradiated microstructure along with high temperature water and stress. The process is ubiquitous in that it occurs in a wide range of austenitic alloys and water chemistries, but only when the alloy is irradiated. Despite evidence of this degradation mode that dates back to the 1960s, the mechanism by which it occurs has remained elusive. Here, using high resolution electron backscattering detection to analyze local stress-strain states, high resolution transmission electron microscopy to identify grain boundary phases at crack tips, and decoupling the roles of stress and grain boundary oxidation, we are able to unfold the complexities of the phenomenon to reveal the mechanism by which IASCC occurs. The significance of the findings impacts the mechanical integrity of core components of both current and advanced nuclear reactor designs worldwide. KW - Irradiation KW - Stress corrosion cracking KW - Grain boundaries KW - Oxidation KW - Austenitic alloys PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595748 DO - https://doi.org/10.1016/j.pmatsci.2024.101255 SN - 0079-6425 VL - 143 SP - 1 EP - 15 PB - Elsevier AN - OPUS4-59574 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sun, Yijuan A1 - Gawlitza, Kornelia A1 - Valderrey, Virginia A1 - Bell, Jérémy A1 - Rurack, Knut T1 - Polymerizable BODIPY probe crosslinker for the molecularly imprinted polymer-based detection of organic carboxylates via fluorescence N2 - This contribution reports the development of a polymerizable BODIPY-type fluorescent probe targeting small-molecule carboxylates for incorporation into molecularly imprinted polymers (MIPs). The design of the probe crosslinker includes a urea recognition site p-conjugated to the 3-position of the BODIPY core and two methacrylate moieties. Titration experiments with a carboxylate-expressing antibiotic, levofloxacin (LEVO), showed a blue shift of the absorption band as well as a broadening and decrease in emission, attributed to hydrogen bonding between the probe’s urea group and the carboxylate group of the antibiotic. Using this probe crosslinker, core–shell particles with a silica core and a thin MIP shell were prepared for the detection of LEVO. The MIP exhibited highly selective recognition of LEVO, with an imprinting factor of 18.1 compared to the non-imprinted polymer. Transmission electron microscopy confirmed the core–shell structure and spectroscopic studies revealed that the receptor’s positioning leads to a unique perturbation of the polymethinic character of the BODIPY chromophore, entailing the favourable responses. These features are fully preserved in the MIP, whereas no such response was observed for competitors such as ampicillin. The sensory particles allowed to detect LEVO down to submicromolar concentrations in dioxane. We have developed here for the first time a BODIPY probe for organic carboxylates and incorporated it into polymers using the imprinting technique, paving the way for BODIPY-type fluorescent MIP sensors. KW - Fluorescence KW - BODIPY probe KW - Molecularly Imprinted Polymers KW - Sensor Materials KW - Dyes KW - Water analysis KW - Advanced materials PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598629 DO - https://doi.org/10.1039/D3MA00476G SP - 1 EP - 11 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59862 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Völker, Tobias A1 - Gornushkin, Igor B. T1 - Mass and mole fractions in calibration-free LIBS N2 - This technical note highlights the fact that CF-LIBS algorithms work in mole fractions, while results of spectrochemical analysis are usually reported in mass fractions or mass percent. Ignoring this difference and not converting mole fractions to mass fractions can lead to errors in reported concentrations determined by the CF-LIBS method and inadequate comparison of these concentrations with certified concentrations. Here, the key points of the CF-LIBS algorithm are reproduced and the formulae for converting a mole fraction to a mass fraction and vice versa are given. Several numerical examples are also given, which show that the greater the difference between the molar mass of an individual element in a sample and the average molar mass, the greater the discrepancy between the mole and mass fractions. KW - Spectroscopy KW - Analytical Chemistry KW - LIBS KW - Calibration PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598611 DO - https://doi.org/10.1039/d4ja00028e SN - 0267-9477 VL - 39 IS - 4 SP - 1030 EP - 1032 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59861 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Slotyuk, Lyubov A1 - Part, Florian A1 - Schlegel, Moritz-Caspar A1 - Akkerman, Floris T1 - Life Cycle Assessment of the Domestic Micro Heat and Power Generation Proton Exchange Membrane Fuel Cell in Comparison with the Gas Condensing Boiler Plus Electricity from the Grid N2 - The energy demand of private households contributes globally to 36.5% of the total CO2 emissions. To analyze the emissions reduction potential, we conducted a comparative life cycle assessment of a proton exchange membrane fuel cell in a residential application and a conventional system with a stand-alone gas condensing boiler and electricity from a grid mix. The period under review was referred to as the service life of the PEMFC and is assumed to be 10 years (83,038 h of PEMFC). The applicability of this in a single-family house built between 1991 and 2000 under German climatic conditions was investigated. The functional unit is set to the thermal energy demand of 16,244 kWh/a and electricity demand of 4919 kWh/a of a single-family house. The impact assessment method “CML 2001–August 2016” was used in this investigation. The manufacturing phase of the proton exchange membrane fuel cell showed disadvantages, whereby the use phase had significant advantages in most of the environmental impact categories as compared to the conventional energy supply system. Considering the whole life cycle, the advantages from the use phase could outperform the disadvantages from the manufacturing phase in most of the impact categories, except for ADP elements and TETP. KW - Sustainability KW - Circular Economy KW - Comparative life cycle assessment KW - Proton exchange membrane fuel cell KW - Gas condensing boiler KW - Micro heat and power generation KW - Residential application KW - Single-family house energy supply system PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598134 DO - https://doi.org/10.3390/su16062348 VL - 16 IS - 6 SP - 1 EP - 16 PB - MDPI AG AN - OPUS4-59813 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wetzel, Annica A1 - Morell, Daniel A1 - von der Au, Marcus A1 - Wittstock, Gunther A1 - Ozcan, Ozlem A1 - Witt, Julia T1 - Transpassive Metal Dissolution vs. Oxygen Evolution Reaction: Implication for Alloy Stability and Electrocatalysis T1 - Transpassive Metallauflösung vs. Sauerstoffentwicklung: Auswirkungen auf Legierungsstabilität und Elektrokatalyse N2 - Multi-principal element alloys (MPEAs) are gaining interest in corrosion and electrocatalysis research due to their electrochemical stability across a broad pH range and the design flexibility they offer. Using the equimolar CrCoNi alloy, we observe significant metal dissolution in a corrosive electrolyte (0.1 M NaCl, pH 2) concurrently with the oxygen evolution reaction (OER) in the transpassive region despite the absence of hysteresis in polarization curves or other obvious corrosion indicators. We present a characterization scheme to delineate the contribution of OER and alloy dissolution, using scanning electrochemical microscopy (SECM) for OER-onset detection, and quantitative chemical analysis with inductively coupled-mass spectrometry (ICP-MS) and ultraviolet visible light (UV-Vis) spectroscopy to elucidate metal dissolution processes. In-situ electrochemical atomic force microscopy (EC-AFM) revealed that the transpassive metal dissolution on CrCoNi is dominated by intergranular corrosion. These results have significant implications for the stability of MPEAs in corrosion systems, emphasizing the necessity of analytically determining metal ions released from MPEA electrodes into the electrolyte when evaluating Faradaic efficiencies of OER catalysts. The release of transition metal ions not only reduces the Faradaic efficiency of electrolyzers but may also cause poisoning and degradation of membranes in electrochemical reactors. N2 - Multi-Hauptelement-Legierungen (MPEAs) gewinnen in der Korrosions- und Elektrokatalyseforschung aufgrund ihrer elektrochemischen Stabilität über einen breiten pH-Bereich und der Vielfalt der möglichen chemischen Zusammensetzungen zunehmend an Interesse. In unseren Untersuchungen mit der äquimolaren CrCoNi-Legierung in einem sauren Elektrolyten (0.1 M NaCl, pH 2) beobachteten wir eine signifikante Metallauflösung, die mit der Sauerstoffentwicklungsreaktion (OER) im transpassiven Bereich einhergeht, obwohl in zyklischen Polarisationskurven keine Hysterese auftrat oder andere offensichtliche Korrosionsindikatoren vorlagen. In diesem Artikel wird ein Charakterisierungskonzept eingeführt, dass die Beiträge der OER und der Legierungsauflösung differenziert. Hierfür kommt die elektrochemische Rastermikroskopie (SECM) zum Nachweis des Beginns der OER und die quantitative chemische Analyse mit induktiv gekoppelter Massenspektrometrie (ICP-MS) und UV/Vis-Spektrometrie zur Aufklärung der Metallauflösungsprozesse zum Einsatz. Die elektrochemische In situ-Atomkraftmikroskopie (EC-AFM) zeigte, dass die intergranulare Korrosion der dominierende Mechanismus der transpassive Metallauflösung von CrCoNi ist. Diese Ergebnisse besitzen erhebliche Auswirkungen für die Beurteilung der Stabilität von MPEAs in Korrosionssystemen und der Stromausbeute von OER-Katalysatoren auf der Basis von MPEAs. Die Daten unterstreichen die Notwendigkeit der analytischen Bestimmung von Metallionen, die von MPEA-Elektroden freigesetzt werden. Die Freisetzung von Übergangsmetallionen verringert nicht nur die Stromausbeute von Elektrolyseuren, sondern kann zu einer Schädigung von Membranen in elektrochemischen Reaktoren führen. KW - Transpassive dissolution KW - Corrosion KW - Multi-prinicpal element alloys (MPEAs) KW - Passivation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597045 DO - https://doi.org/10.1002/anie.202317058 SP - 1 EP - 8 PB - Wiley VHC-Verlag AN - OPUS4-59704 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hoogendoorn, Levi A1 - Huertas, Mauricio A1 - Nitz, Phillip A1 - Qi, Naiyu A1 - Baller, Johannes A1 - Prinz, Carsten A1 - Graeber, Gustav T1 - Sustainable, Low‐Cost Sorbents Based on Calcium Chloride‐Loaded Polyacrylamide Hydrogels N2 - AbstractSorbents are promising materials for applications in atmospheric water harvesting, thermal energy storage, and passive cooling, thereby addressing central challenges related to water scarcity and the global energy transition. Recently, hygroscopic hydrogel composites have emerged as high‐performance sorbents. However, many of these systems are fabricated with unsustainable and costly sorbent materials, which hinders their wide deployment. Here, the synthesis of high‐performance, cost‐efficient polyacrylamide hydrogels loaded with unprecedented amounts of calcium chloride is demonstrated. To this end, the swelling procedure of polyacrylamide hydrogels in aqueous calcium chloride solutions is optimized. The achievable salt loading in the hydrogel is characterized as a function of temperature, calcium chloride concentration in the swelling solution, and the hydrogel preparation conditions. The obtained hydrogel‐salt composites are shown to be stable under repeated sorption‐desorption cycling and enable water uptakes of 0.92 and 2.38 grams of water per gram of dry materials at 30% and 70% relative humidity, respectively. The resulting cost‐performance ratio substantially exceeds lithium chloride‐based systems. Further, the mechanistic insights on hydrogel salt interactions can guide the design of sustainable and low‐cost sorbent materials for future applications in water and energy. KW - Electrochemistry KW - Condensed Matter Physics KW - Biomaterials KW - Electronic, Optical and Magnetic Materials PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598366 DO - https://doi.org/10.1002/adfm.202314680 SN - 1616-301X SP - 1 EP - 10 PB - Wiley VHC-Verlag AN - OPUS4-59836 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Böttcher, Nils A1 - Dayani, Shahabeddin A1 - Markötter, Henning A1 - Bau, Alexander A1 - Setzchen, Max A1 - Schmidt, Anita A1 - Kowal, Julia A1 - Krug von Nidda, Jonas T1 - High Precision Nail‐Penetration Setup for the Controlled Thermal Runaway Initiation of Lithium‐Ion Cells at Very Low Temperatures N2 - A high precision nail‐penetration (NP) tool for characterizing the mechanically induced thermal‐runaway (TR) of lithium‐ion battery (LIB) cells in a defined range of temperatures down to −140 °C was developed. To understand the cell specific behavior at low temperatures aiming at the determination of safe handling conditions, different scenarios are analyzed. First, accuracy tests of the NP‐tool regarding motion and penetration depth are conducted with cylindrical cells at different temperatures. Thus, postmortem computer tomographic (CT) images are compared to the data measured with the newly integrated 3‐axis force sensor which is further combined with a high‐resolution position sensor. The herein developed setup allows evaluation of the NP‐metrics at an accuracy of ±1 pierced electrode layer without CT‐scans. Further NP examinations at 20 °C of fully charged cylindrical lithium nickel manganese cobalt oxide cells reveal a reproducible minimum damage as a reliable TR‐trigger. Moreover, NP‐tests at low temperature disclose a relation of the short circuit conductivity and TR‐reactions during subsequent rethermalization to room temperature. Finally, the implementation of a novel fixture for a controlled very fast cooling of LIB‐cells during critical damage opens the way to investigate the individual steps during a TR and, thus, to gain important information of the specific TR‐mechanism of different LIB‐cells. KW - Battery Safety KW - High-precision nail penetration KW - Lithium-ion batteries KW - Abuse testing KW - Thermal runaway PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598127 DO - https://doi.org/10.1002/ente.202301379 SN - 2194-4288 SP - 1 EP - 13 PB - Wiley VHC-Verlag AN - OPUS4-59812 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Turski Silva Diniz, Analice A1 - Schartel, Bernhard T1 - The effects of property variation on the dripping behaviour of polymers during UL94 test simulated by particle finite element method N2 - The dripping behaviour of polymers is often observed experimentally through the UL94 flammability standard test. In this work, polymeric dripping under fire is investigated numerically using particle finite element method. A parametric analysis was carried out to observe the influence of a single property on overall dripping behaviour via a UL94 vertical test model. Surrogates and property ranges were defined for variation of the following parameters: glass transition temperature (Tg), melting temperature (Tm), decomposition temperature (Td), density (ρ), specific heat capacity (Cp), apparent effective heat of combustion of the volatiles, char yield (μ), thermal conductivity (k), and viscosity (η). Polyamide, poly(ether ether ketone), poly(methyl methacrylate), and polysulfone were used as benchmarks. Simulated results showed that specific heat capacity, thermal conductivity, and char yield allied with viscosity were the properties that most influenced dripping behaviour (starting time and occurrence). KW - Dripping KW - PFEM KW - UL 94 KW - Simulation KW - Fire behaviour PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597449 DO - https://doi.org/10.1515/epoly-2023-0194 SN - 1618-7229 VL - 24 IS - 1 PB - De Gruyter AN - OPUS4-59744 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Groschke, Matthias A1 - Becker, Roland T1 - Comparison of carrier gases for the separation and quantification of mineral oil hydrocarbon (MOH) fractions using online coupled high performance liquid chromatography-gas chromatography-flame ionisation detection N2 - On-line coupled high performance liquid chromatography-gas chromatography-flame ionisation detection (HPLC-GC-FID) was used to compare the effect of hydrogen, helium and nitrogen as carrier gases on the chromatographic characteristics for the quantification of mineral oil hydrocarbon (MOH) traces in food related matrices. After optimisation of chromatographic parameters nitrogen carrier gas exhibited characteristics equivalent to hydrogen and helium regarding requirements set by current guidelines and standardisation such as linear range, quantification limit and carry over. Though nitrogen expectedly led to greater peak widths, all required separations of standard compounds were sufficient and humps of saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) were appropriate to enable quantitation similar to situations where hydrogen or helium had been used. Slightly increased peak widths of individual hump components did not affect shapes and widths of the MOSH and MOAH humps were not significantly affected by the use of nitrogen as carrier gas. Notably, nitrogen carrier gas led to less solvent peak tailing and smaller baseline offset. Overall, nitrogen may be regarded as viable alternative to hydrogen or helium and may even extend the range of quantifiable compounds to highly volatile hydrocarbon eluting directly after the solvent peak. KW - Mineral oil hydrocarobons KW - Food KW - Liquid chromatography KW - Gas chromatography KW - MOSH/MOAH PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601450 DO - https://doi.org/10.1016/j.chroma.2024.464946 SN - 0021-9673 VL - 1726 SP - 1 EP - 7 PB - Elsevier CY - New York, NY AN - OPUS4-60145 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - López-Iglesias, C. A1 - Markovina, A. A1 - Nirmalananthan-Budau, N. A1 - Resch-Genger, Ute A1 - Klinger, D. T1 - Optically monitoring the microenvironment of a hydrophobic cargo in amphiphilic nanogels: influence of network composition on loading and release N2 - Amphiphilic nanogels (ANGs) are promising carriers for hydrophobic cargos such as drugs, dyes, and catalysts. Loading content and release kinetics of these compounds are controlled by type and number of hydrophobic groups in the amphiphilic copolymer network. Thus, understanding the interactions between cargo and colloidal carrier is mandatory for a tailor-made and cargo-specific ANG design. To systematically explore the influence of the network composition on these interactions, we prepared a set of ANGs of different amphiphilicity and loaded these ANGs with varying concentrations of the solvatochromic dye Nile Red (NR). Here, NR acts as a hydrophobic model cargo to optically probe the polarity of its microenvironment. Analysis of the NR emission spectra as well as measurements of the fluorescence quantum yields and decay kinetics revealed a decrease in the polarity of the NR microenvironment with increasing hydrophobicity of the hydrophobic groups in the ANG network and dye–dye interactions at higher loading concentrations. At low NR concentrations, the hydrophobic cargo NR is encapsulated in the hydrophobic domains. Increasing NR concentrations resulted in probe molecules located in a more hydrophilic environment, i.e., at the nanodomain border, and favored dye–dye interactions and NR aggregation. These results correlate well with release experiments, indicating first NR release from more hydrophilic network locations. Overall, our findings demonstrate the importance to understand carrier–drug interactions for efficient loading and controlled release profiles in amphiphilic nanogels. KW - Particle KW - Energy transfer KW - Limit of detection KW - Polymer KW - Luminescence KW - Quantitative spectroscopy KW - Nano KW - Quantum yield KW - Lifetime KW - Quality assurance KW - Dye KW - Probe KW - Sensor KW - Nile Red PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601603 DO - https://doi.org/10.1039/d4nr00051j SN - 2040-3364 IS - 16 SP - 9525 EP - 9535 PB - The Royal Society of Chemistry AN - OPUS4-60160 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Epping, Ruben A1 - Lisec, Jan A1 - Koch, Matthias T1 - Changes in Black Truffle (Tuber melanosporum) Aroma during Storage under Different Conditions N2 - The enticing aroma of truffles is a key factor for their culinary value. Although all truffle species tend to be pricy, the most intensely aromatic species are the most sought after. Research into the aroma of truffles encompasses various disciplines including chemistry, biology, and sensory science. This study focusses on the chemical composition of the aroma of black truffles (Tuber melanosporum) and the changes occurring under different storage conditions. For this, truffle samples were stored under different treatments, at different temperatures, and measured over a total storage time of 12 days. Measurements of the truffle aroma profiles were taken with SPME/GC–MS at regular intervals. To handle the ample data collected, a systematic approach utilizing multivariate data analysis techniques was taken. This approach led to a vast amount of data which we made publicly available for future exploration. Results reveal the complexity of aroma changes, with 695 compounds identified, highlighting the need for a comprehensive understanding. Principal component analyses offer initial insights into truffle composition, while individual compounds may serve as markers for age (formic acid, 1-methylpropyl ester), freshness (2-Methyl-1-propanal; 1-(methylthio)-propane), freezing (tetrahydrofuran), salt treatment (1-chloropentane), or heat exposure (4-hydroxy-3-methyl-2-butanone). This research suggests that heat treatment or salt contact significantly affects truffle aroma, while freezing and cutting have less pronounced effects in comparison. The enrichment of compounds showing significant changes during storage was investigated with a metabolomic pathway analysis. The involvement of some of the enriched compounds on the pyruvate/glycolysis and sulfur pathways was shown. KW - Mass Spectrometry KW - Metabolomics KW - Tuber melanosporum KW - Truffle Aroma PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601731 DO - https://doi.org/10.3390/jof10050354 VL - 10 IS - 5 SP - 1 EP - 22 PB - MDPI AN - OPUS4-60173 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bauer, L.J. A1 - Wieder, Frank A1 - Truong, V. A1 - Förste, F. A1 - Wagener, Y. A1 - Jonas, A. A1 - Praetz, S: A1 - Schlesiger, C. A1 - Kupsch, Andreas A1 - Müller, B.R. A1 - Kanngießer, B. A1 - Zaslansky, P. A1 - Mantouvalou, I. T1 - Absorption Correction for 3D Elemental Distributions of Dental Composite Materials Using Laboratory Confocal Micro-X-ray Fluorescence Spectroscopy N2 - Confocal micro-X-ray fluorescence (micro-XRF) spectroscopy facilitates three-dimensional (3D) elemental imaging of heterogeneous samples in the micrometer range. Laboratory setups using X-ray tube excitation render the method accessible for diverse research fields but interpretation of results and quantification remain challenging. The attenuation of X-rays in composites depends on the photon energy as well as on the composition and density of the material. For confocal micro-XRF, attenuation severely impacts elemental distribution information, as the signal from deeper layers is distorted by superficial layers. Absorption correction and quantification of fluorescence measurements in heterogeneous composite samples have so far not been reported. Here, an absorption correction approach for confocal micro-XRF combining density information from microcomputed tomography (micro-CT) data with laboratory X-ray absorption spectroscopy (XAS) and synchrotron transmission measurements is presented. The energy dependency of the probing volume is considered during the correction. The methodology is demonstrated on a model composite sample consisting of a bovine tooth with a clinically used restoration material. KW - Micro X-ray fluorescence spectroscopy KW - Dental composite materials KW - Computed tomography KW - Absorption correction PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601630 DO - https://doi.org/10.1021/acs.analchem.4c00116 SN - 0003-2700 SN - 1520-6882 VL - 96 IS - 21 SP - 8441 EP - 8449 PB - American Chemical Society Publications CY - Washington, DC AN - OPUS4-60163 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schilling, Markus A1 - Niebergall, Ute A1 - Marschall, Niklas A1 - Meinel, Dietmar A1 - Böhning, Martin T1 - Relation of craze to crack length during slow crack growth phenomena in high‐density polyethylene N2 - The craze‐crack mechanism occurring in high‐density polyethylene (HDPE) causing slow crack growth and environmental stress cracking is investigated in detail with respect to the relation of crack length and the related craze zone. This is essential for the understanding of the resulting features of the formed fracture surface and their interpretation in the context of the transition from crack propagation to ductile shear deformation. It turns out that an already formed craze zone does not inevitably result in formation of a propagating crack, but could also undergo ductile failure. For the examination, the full notch creep test (FNCT) was employed with a subsequent advanced fracture surface analysis that was performed using various imaging techniques: light microscopy, laser scanning microscopy, scanning electron microscopy, and X‐ray micro computed tomography scan. FNCT specimens were progressively damaged for increasing durations under standard test conditions applying Arkopal, the standard surfactant solution, and biodiesel as test media were used to analyze the stepwise growth of cracks and crazes. From considerations based on well‐established fracture mechanics approaches, a theoretical correlation between the length of the actual crack and the length of the preceding craze zone was established that could be evidenced and affirmed by FNCT fracture surface analysis. Moreover, the yield strength of a HDPE material exposed to a certain medium as detected by a classic tensile test was found to be the crucial value of true stress to induce the transition from crack propagation due to the craze‐crack mechanism to shear deformation during FNCT measurements. Highlights - Progress of crack formation in high‐density polyethylene is analyzed by different imaging techniques - Determined growth rates depend on distinction between craze zone and crack - The ratio of the present crack to the anteceding craze zone is validated theoretically - The transition from crack propagation to ductile shear deformation is identified - An already formed craze zone may still fail by ductile mechanisms KW - Craze-crack mechanism KW - Environmental stress cracking (ESC) KW - Full notch creep test (FNCT) KW - Laser scanning microscopy (LSM) KW - Slow crack growth (SCG) KW - X-ray computed tomography (CT) PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601831 DO - https://doi.org/10.1002/pen.26698 SN - 1548-2634 VL - 64 IS - 6 SP - 2387 EP - 2403 PB - Wiley AN - OPUS4-60183 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ji, Y. A1 - Becker, S. A1 - Lu, Z. A1 - Mezhov, Alexander A1 - von Klitzing, R. A1 - Schmidt, Wolfram A1 - Stephan, D. T1 - Effect of resting time on rheological properties of glass bead suspensions - Depletion and bridging force among particles N2 - The effect of resting time on the rheological properties of cement suspensions is generally explained by early formed structure and overconsumption of polycarboxylate superplasticizers (PCEs). In this paper, we propose that the influence of resting time on the rheological properties is closely related to size variation of non-absorbed PCE. To identify this, glass bead suspensions were prepared with various amounts of PCE and ionic solution, and their rheological properties were evaluated at various times. We found that the yield stress increases with time at higher PCE concentrations and higher ionic strength solutions. Adsorbed PCE during resting tends to bridge the particles rather than disperse them. In addition, it was found that hydrodynamic radius of PCE increased with resting time, and depletion forces resulting from non-absorbed PCE size changes correlate well with the increased yield stress. KW - Depletion force KW - Ionic stregth KW - PCE KW - Rheology KW - Resting time PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-587193 DO - https://doi.org/10.1111/jace.19469 SN - 0002-7820 SN - 1551-2916 VL - 107 IS - 1 SP - 624 EP - 639 PB - Wiley-Blackwell CY - Oxford AN - OPUS4-58719 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nawaz, Q. A1 - Blaeß, Carsten A1 - Mueller, Ralf A1 - Boccaccini, A.R. T1 - Processing and cytocompatibility of Cu-doped and undoped fluoride-containing bioactive glasses N2 - Sintered or additive-manufactured bioactive glass (BG) scaffolds are highly interesting for bone replacement applications. However, crystallization often limits the high-temperature processability of bioactive glasses (BGs). Thus, the BG composition must combine high bioactivity and processability. In this study, three BGs with nominal molar (%) compositions 54.6SiO2-1.7P2O3-22.1CaO-6.0Na2O-7.9K2O-7.7MgO (13–93), 44.8SiO2-2.5P2O3-36.5CaO-6.6Na2O-6.6K2O-3.0CaF2 (F3) and 44.8SiO2-2.5P2O3-35.5CaO-6.6Na2O-6.6K2O-3.0CaF2-1.0CuO (F3–Cu) were investigated. The dissolution and ion release kinetics were investigated on milled glass powder and crystallized particles (500–600 μm). All glasses showed the precipitation of hydroxyapatite (HAp) crystals after 7 days of immersion in simulated body fluid. No significant differences in ion release from glass and crystalline samples were detected. The influence of surface roughness on cytocompatibility and growth of preosteoblast cells (MC3T3-E1) was investigated on sintered and polished BG pellets. Results showed that sintered BG pellets were cytocompatible, and cells were seen to be well attached and spread on the surface after 5 days of incubation. The results showed an inverse relation of cell viability with the surface roughness of pellets, and cells were seen to attach and spread along the direction of scratches. KW - Bioactive glass KW - Crystallization KW - Solubility KW - Cytocompatibility KW - Surface roughness PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598257 DO - https://doi.org/10.1016/j.oceram.2024.100586 SN - 2666-5395 VL - 18 SP - 1 EP - 8 PB - Elsevier Ltd. AN - OPUS4-59825 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Becker, Tina A1 - Stark, T. A1 - Arduini, M. A1 - Manara, J. A1 - Altenburg, Simon T1 - Knowing the spectral directional emissivity of 316L and AlSi10Mg PBF-LB/M surfaces: Gamechanger for quantitative in situ monitoring N2 - For a deep process understanding of the laser powder bed fusion process (PBF-LB/M), recording of the occurring surface temperatures is of utmost interest and would help to pave the way for reliable process monitoring and quality assurance. A notable number of approaches for in-process monitoring of the PBF-LB/M process focus on the monitoring of thermal process signatures. However, due to the elaborate calibration effort and the lack of knowledge about the occurring spectral directional emissivity, only a few approaches attempt to measure real temperatures. In this study, to gain initial insights into occurring in the PBF-LB/M process, measurements on PBF-LB/M specimens and metal powder specimens were performed for higher temperatures up to T = 1290 °C by means of the emissivity measurement apparatus (EMMA) of the Center for Applied Energy Research (CAE, Wuerzburg, Germany). Also, measurements at ambient temperatures were performed with a suitable measurement setup. Two different materials—stainless steel 316L and aluminum AlSi10Mg—were examined. The investigated wavelength λ ranges from the visible range (λ-VIS= 0.40–0.75 µm) up to the infrared, λ = 20 µm. The influence of the following factors were investigated: azimuth angle φ, specimen temperature TS, surface texture as for PBF-LB/M surfaces with different scan angles α, and powder surfaces with different layer thicknesses t. T2 - Rapid.Tech 3D 2024 CY - Erfurt, Germany DA - 14.05.2024 KW - PBF-LB/M KW - In situ monitoring KW - Emissivity KW - Additive manufacturing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601471 DO - https://doi.org/10.1007/s40964-024-00665-2 SN - 2363-9520 SP - 1 EP - 10 PB - Springer CY - Cham, Switzerland AN - OPUS4-60147 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kingsbery, P. A1 - Manzoni, Anna M. A1 - Suarez Ocaño, Patricia A1 - Többens, D. M. A1 - Stephan‐Scherb, C. T1 - High‐temperature KCl‐induced corrosion of high Cr and Ni alloys investigated by in‐situ diffraction N2 - High‐temperature KCl‐induced corrosion in laboratory air was observed in situ utilizing X‐ray diffraction. High Cr‐containing model alloys (Fe‐13Cr, Fe‐18Cr‐12Ni, and Fe‐25Cr‐20Ni) were coated with KCl and exposed to dry air at 560°C. KCl‐free alloys were studied in the equivalent atmosphere as a reference. After exposure to KCl‐free environments, all alloys showed the formation of very thin oxide layers, indicating good corrosion resistance. In contrast, KCl‐bearing alloys showed distinct damage after exposure. KW - Corrosion KW - In-situ diffraction KW - High-temperature corrosion PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600831 DO - https://doi.org/10.1002/maco.202314224 SN - 0947-5117 SP - 1 EP - 10 PB - Wiley VHC-Verlag AN - OPUS4-60083 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hupp, Vitus A1 - Schartel, Bernhard A1 - Flothmeier, K. A1 - Hartwig, A. T1 - Fire Behavior of Pressure-sensitive Adhesive Tapes and Bonded Materials N2 - Pressure-sensitive adhesive tapes are used in several industrial applications such as con-struction, railway vehicles and the automotive sector,where the burning behavior is ofcrucial importance. Flame retarded adhesivetapes are developed and provided, however,often without considering the interaction of adhesive tapes and the bonded materialsduring burning nor the contribution of the tapes to fire protection goal of the bondedcomponents in distinct fire tests. This publication delivers an empirical comprehensiveknowledge how adhesive tapes and their flame retardancy effect the burning behaviorof bonded materials. With a special focus on the interaction between the single compo-nents, one flame retarded tape and one tapewithout flame retardant are examined inscenarios of emerging and developing fires, along with their bonds with the commonmaterials wood, zinc-plated steel, mineral wool, polycarbonate, and polymethylmethacry-late. The flame retardant significantly improved the flame retardancy of the tape as afree-standing object and yielded a V-2 rating in UL 94 vertical test and raised the OxygenIndex by 5 vol.%. In bonds, or rather laminates, the investigations prove that the choiceof carrier and substrates are the factors with the greatest impact on the fire propertiesand can change the peak of heat release rate and the maximum average rate of heatemission up to 25%. This research yielded a good empirical overall understanding of thefire behavior of adhesive tapes and bonded materials. Thus, it serves as a guide for tapemanufacturers and applicants to develop tapes and bonds more substrate specific. KW - Adhesives KW - Cone calorimeter KW - Flame retardancy KW - Laminates KW - Phosphorus flame retardants KW - Pressure-sensitive adhesive KW - Tapes PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593207 DO - https://doi.org/10.1002/fam.3171 SN - 0308-0501 SN - 1099-1018 VL - 48 IS - 1 SP - 114 EP - 127 PB - Wiley CY - New York, NY AN - OPUS4-59320 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weller, Michael G. T1 - The mystery of homochirality on earth N2 - Homochirality is an obvious feature of life on Earth. On the other hand, extraterrestrial samples contain largely racemic compounds. The same is true for any common organic synthesis. Therefore, it has been a perplexing puzzle for decades how these racemates could have formed enantiomerically enriched fractions as a basis for the origin of homochiral life forms. Numerous hypotheses have been put forward as to how preferentially homochiral molecules could have formed and accumulated on Earth. In this article, it is shown that homochirality of the abiotic organic pool at the time of formation of the first self-replicating molecules is not necessary and not even probable. It is proposed to abandon the notion of a molecular ensemble and to focus on the level of individual molecules. Although the formation of the first self-replicating, most likely homochiral molecule, is a seemingly improbable event, on a closer look, it is almost inevitable that some homochiral molecules have formed simply on a statistical basis. In this case, the non-selective leap to homochirality would be one of the first steps in chemical evolution directly out of a racemic “ocean”. Moreover, most studies focus on the chirality of the primordial monomers with respect to an asymmetric carbon atom. However, any polymer with a minimal size that allows folding to a secondary structure would spontaneously lead to asymmetric higher structures (conformations). Most of the functions of these polymers would be influenced by this inherently asymmetric folding. Furthermore, a concept of physical compartmentalization based on rock nanopores in analogy to nanocavities of digital immunoassays is introduced to suggest that complex cell walls or membranes were also not required for the first steps of chemical evolution. To summarize, simple and universal mechanisms may have led to homochiral self-replicating systems in the context of chemical evolution. A homochiral monomer pool is deemed unnecessary and probably never existed on primordial Earth. N2 - Homochiralität ist ein offensichtliches Merkmal des Lebens auf der Erde. Andererseits enthalten extraterrestrische Proben überwiegend racemische Verbindungen. Dasselbe gilt für jede gängige organische Synthese. Daher war es jahrzehntelang ein Rätsel, wie diese Racemate enantiomeren-angereicherte Fraktionen als Grundlage für den Ursprung homochiraler Lebensformen bilden konnten. Zahlreiche Hypothesen wurden aufgestellt, wie sich bevorzugt homochirale Moleküle auf der Erde gebildet und angereichert haben könnten. In diesem Artikel wird gezeigt, dass Homochiralität des abiotischen organischen Pools zum Zeitpunkt der Bildung der ersten selbstreplizierenden Moleküle nicht notwendig und nicht einmal wahrscheinlich ist. Es wird vorgeschlagen, die Vorstellung eines molekularen Ensembles aufzugeben und sich auf die Ebene der einzelnen Moleküle zu konzentrieren. Obwohl die Bildung des ersten selbstreplizierenden, höchstwahrscheinlich homochiralen Moleküls ein scheinbar unwahrscheinliches Ereignis ist, ist es bei näherer Betrachtung fast unvermeidlich, dass sich einige homochirale Moleküle einfach auf statistischer Basis gebildet haben. In diesem Fall wäre der nichtselektive Sprung zur Homochiralität einer der ersten Schritte der chemischen Evolution direkt aus einem racemischen "Ozean". Darüber hinaus konzentrieren sich die meisten Studien auf die Chiralität der ursprünglichen Monomere in Bezug auf ein asymmetrisches Kohlenstoffatom. Jedes Polymer mit einer Mindestgröße, die eine Faltung zu einer Sekundärstruktur erlaubt, würde jedoch spontan zu asymmetrischen höheren Strukturen (Konformationen) führen. Die meisten Funktionen dieser Polymere würden durch diese inhärent asymmetrische Faltung beeinflusst. Darüber hinaus wird ein Konzept der physikalischen Kompartimentierung auf der Basis von Gesteinsnanoporen in Analogie zu den Nanokavitäten digitaler Immunoassays vorgestellt, das darauf hindeutet, dass auch für die ersten Schritte der chemischen Evolution keine komplexen Zellwände oder Membranen notwendig waren. Zusammenfassend lässt sich sagen, dass einfache und universelle Mechanismen zu homochiralen selbstreplizierenden Systemen im Rahmen der chemischen Evolution geführt haben könnten. Ein homochiraler Monomerpool wird als unnötig angesehen, welcher auf der Urerde wahrscheinlich nie existiert hat. KW - Chemical evolution KW - Enantiomeric excess ee KW - Chirality KW - Racemate KW - Folding chirality KW - Self-assembly KW - self-replication KW - Single molecule KW - Prebiotic chemistry KW - Protein folding KW - Peptide folding KW - Proteinoid KW - Conformation KW - Segregation KW - Compartmentalization KW - Digital immunoassay KW - Porous rock KW - Miller and Urey KW - Primordial soup KW - Murchison meteorite KW - Micrometeorites KW - Tholins PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598349 DO - https://doi.org/10.3390/life14030341 SN - 2075-1729 VL - 14 IS - 3 SP - 1 EP - 13 PB - MDPI CY - Basel AN - OPUS4-59834 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tang, Chi-Long A1 - Seeger, Stefan T1 - Measurement of sub-4 nm particle emission from FFF-3D printing with the TSI Nano Enhancer and the Airmodus Particle Size Magnifier N2 - The emission of ultrafine particles from small desktop Fused Filament Fabrication (FFF) 3D printers has been frequently investigated in the past years. However, the vast majority of FFF emission and exposure studies have not considered the possible occurrence of particles below the typical detection limit of Condensation Particle Counters and could have systematically underestimated the total particle emission as well as the related exposure risks. Therefore, we comparatively measured particle number concentrations and size distributions of sub-4 nm particles with two commercially available diethylene glycol-based instruments – the TSI 3757 Nano Enhancer and the Airmodus A10 Particle Size Magnifier. Both instruments were evaluated for their suitability of measuring FFF-3D printing emissions in the sub-4 nm size range while operated as a particle counter or as a particle size spectrometer. For particle counting, both instruments match best when the Airmodus system was adjusted to a cut-off of 1.5 nm. For size spectroscopy, both instruments show limitations due to either the fast dynamics or rather low levels of particle emissions from FFF-3D printing in this range. The effects are discussed in detail in this article. The findings could be used to implement sub-4 nm particle measurement in future emission or exposure studies, but also for the development of standard test protocols for FFF-3D printing emissions. KW - Air pollution KW - Ultrafine particles KW - Sub-4nm particles KW - FFF-3D printing KW - Emission testing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595952 DO - https://doi.org/10.1080/02786826.2024.2320430 SN - 0278-6826 VL - 58 IS - 6 SP - 644 EP - 656 PB - Taylor & Francis CY - London AN - OPUS4-59595 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Piechnik, Kira A1 - Hofmann, Anja A1 - Klippel, Andrea T1 - Self‐ignition of forest soil samples demonstrated through hot storage tests N2 - AbstractThe increasing threat of forest fires on a global scale is not only a matter of concern due to the potential harm they may cause to both human and animal life but also due to their significant role in exacerbating climate change. In light of these circumstances, one might inquire as to whether forest soil can self‐ignite and, if so, under what conditions and at what temperatures this phenomenon may occur. This question is being addressed in the German pilot “Fire science of wildfires and safety measures” of the EU project TREEADS, and the first results are presented below. The importance of basic research into the self‐ignition of forest soil cannot be underestimated, as it provides crucial knowledge to prevent forest fires and protect human and animal health. Furthermore, mitigating the occurrence of forest fires can also play a role in reducing greenhouse gas emissions, contributing to global efforts to combat climate change. The procedure of the hot storage test is an effective means of determining whether a material can self‐ignite. During the investigation of six soil samples, it was found that five of them were indeed capable of self‐ignition. In addition to determining whether the material ignites, the modified hot storage test also analyzed the resulting smoke gases and measured their concentration. The research question of whether regional forest soil is capable of self‐ignition can be answered with yes based on these initial tests. Further experiments are needed to determine if self‐ignition causes forest fires. KW - FTIR KW - Hot storage KW - Ignition KW - Soil KW - Wildfire PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594617 DO - https://doi.org/10.1002/fam.3198 VL - 48 IS - 4 SP - 495 EP - 507 PB - Wiley AN - OPUS4-59461 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmidt, Stephan A1 - Hoffmann, Holger A1 - Garbe, Leif-Alexander A1 - Harrer, Andrea A1 - Steiner, Markus A1 - Himly, Martin A1 - Schneider, Rudolf T1 - Re-assessment of monoclonal antibodies against diclofenac for their application in the analysis of environmental waters N2 - The non-steroidal anti-inflammatory drug (NSAID) diclofenac (DCF) is an important environmental contaminant occurring in surface waters all over the world, because, after excretion, it is not adequately removed from wastewater in sewage treatment plants. To be able to monitor this pollutant, highly efficient analytical methods are needed, including immunoassays. In a medical research project, monoclonal antibodies against diclofenac and its metabolites had been produced. Based on this monoclonal anti-DCF antibody, a new indirect competitive enzyme-linked immunosorbent assay (ELISA) was developed and applied for environmental samples. The introduction of a spacer between diclofenac and the carrier protein in the coating conjugate led to higher sensitivity. With a test midpoint of 3 mg L−1 and a measurement range of 1–30 mg L−1, the system is not sensitive enough for direct analysis of surface water. However, this assay is quite robust against matrix influences and can be used for wastewater. Without adjustment of the calibration, organic solvents up to 5%, natural organic matter (NOM) up to 10 mg L−1, humic acids up to 2.5 mg L−1, and salt concentrations up to 6 g L−1 NaCl and 75 mg L−1 CaCl2 are tolerated. The antibody is also stable in a pH range from 3 to 12. Cross-reactivity (CR) of 1% or less was determined for the metabolites 40-hydroxydiclofenac (40-OH-DCF), 5-hydroxydiclofenac (5-OH-DCF), DCF lactam, and other NSAIDs. Relevant cross-reactivity occurred only with an amide derivative of DCF, 6-aminohexanoic acid (DCF-Ahx), aceclofenac (ACF) and DCF methyl ester (DCF-Me) with 150%, 61% and 44%, respectively. These substances, however, have not been found in samples. Only DCF-acyl glucuronide with a cross-reactivity of 57% is of some relevance. For the first time, photodegradation products were tested for cross-reactivity. With the ELISA based on this antibody, water samples were analysed. In sewage treatment plant effluents, concentrations in the range of 1.9–5.2 mg L−1 were determined directly, with recoveries compared to HPLC-MS/MS averaging 136%. Concentrations in lakes ranged from 3 to 4.4 ng L−1 and were, after pre-concentration, determined with an average recovery of 100% KW - Antikörper KW - Immunoassay KW - Wasser PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-602280 DO - https://doi.org/10.1039/d3ay01333b VL - 16 IS - 21 SP - 3349 EP - 3363 PB - Royal Society of Chemistry (RSC) CY - London AN - OPUS4-60228 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -