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Paper des Monats
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ISO 14837-32:2015 and DIN EN 1998-1/NA:2021 as well as prEN 1997-2:2022 allow for us-ing correlations between the results of in-situ soil penetration tests and shear wave velocity (or shear modulus) to determine soil properties to be used in dynamic analyses. While the ISO and prEN standards even provide some recommendations on specific correlations to be used, the DIN standard does not. Due to the statistical nature of such correlations their general applica-bility has to be verified. We collected data sets from test sites from Germany as well as New Zealand at which cone penetration tests (CPT) as well as seismic site investigation methods were conducted. These sites comprise sandy soils as well as clayey soils, mixed soils as well as glacial soils. We compare the results of several correlations between CPT results and shear wave velocity. The accuracy of such correlations is assessed with respect to the accuracy of seismic in-situ tests. It turns out that for clean sands such correlations between CPT and Vs have a similar order of variability as seismic in-situ tests conducted at the same site. The higher the fines portion of the soil, the higher the variability of the statistical correlations, and conse-quently the less the general applicability. For glacial soils and other special soil types usage of statistical correlations to determine dynamic soil properties is not recommended.
Automated computational workflows are a powerful concept that can improve the usability and reproducibility of simulation and data processing approaches. Although used very successfully in bioinformatics, workflow environments in materials science are currently commonly applied in the field of atomistic simulations. This work showcases the integration of a discrete element method (DEM) simulation of powder pressing in the convenient SimStack workflow environment. For this purpose, a Workflow active Node (WaNo) was developed to generate input scripts for the DEM solver using LIGGGHTS Open Source Discrete Element Method Particle Simulation code. Combining different WaNos in the SimStack framework makes it possible to build workflows and loop over different simulation or evaluation conditions. The functionality of the workflows is explained, and the added user value is discussed. The procedure presented here is an example and template for many other simulation methods and issues in materials science and engineering.
The injection of hydrogen into the natural-gas grid is an alternative during the process of a gradual decarbonization of the heat and power supply. When dealing with hydrogen-enriched natural gas mixtures, the performance of the reference equations of state habitually used for natural gas should be validated by using high-precision experimental thermophysical data from multicomponent reference mixtures prepared with the lowest possible uncertainty in composition. In this work, we present experimental density data for an 11-compound high-calorific (hydrogen-free) natural gas mixture and for two derived hydrogen-enriched natural gas mixtures prepared by adding (10 and 20) mol-% of hydrogen to the original standard natural gas mixture. The three mixtures were prepared gravimetrically according to ISO 6142–1 for maximum precision in their composition and thus qualify for reference materials. A single-sinker densimeter was used to determine the density of the mixtures from (250–350) K and up to 20 MPa. The experimental density results of this work have been compared to the densities calculated by three different reference equations of state for natural gas related mixtures: the AGA8-DC92 EoS, the GERG-2008 EoS, and an improved version of the GERG-2008 EoS. While relative deviations of the experimental density data for the hydrogen-free natural gas mixture are always within the claimed uncertainty of the three considered equations of state, larger deviations can be observed for the hydrogen-enriched natural gas mixtures from any of the three equations of state, especially for the lowest temperature and the highest pressures.
The systematic transfer of solvent-free, additive flame retardant (FR) formulations from epoxy resins to glass fiber-reinforced epoxy composites (GFRECs) through prepregs is difficult. Additionally, obtaining data on their post-fire mechanics is often challenging. Utilizing melamine polyphosphate (MPP), ammonium polyphosphate (APP), and silane-coated ammonium polyphosphate (SiAPP) FRs with low-melting inorganic silicates (InSi) in an 8:2 proportion and 10% loading by weight in a diglycidyl ether of bisphenol A (DGEBA) resin, a systematic investigation of the processing properties, room-temperature mechanics, and temperature-based mechanics of the systems was performed. The resin was cured with a dicyandiamide hardener (DICY) and a urone accelerator. The results revealed no substantial impact of these FRs at the current loading on the resin's glass transition temperature or processability. However, the fire residues from cone calorimetry tests of the composites containing FRs were found to be only 15-20% of the thickness of the resins, implying a suppression of intumescence upon transfer. At room temperature, the decrease in the flexural modulus for the composites containing FRs was negligible. Exposure of the composites in a furnace at 400°C as a preliminary study before ignition tests was shown to cause significant flexural moduli reductions after 2.5 min of exposure and complete delamination after 3 min making further testing unviable. This study emphasizes the need for future research on recovering modes of action upon transfer of FR formulations from resins to composites. Based on the challenges outlined in this investigation, sample adaptation methods for post-fire analysis will be developed in a future study.
Addressing a strategy for publishing open and digital research data, this article presents the approach for streamlining and automating the process of storage and conversion of research data to those of semantically queryable data on the web. As the use case for demonstrating and evaluating the digitalization process, the primary datasets from low‐cycle‐fatigue testing of several copper alloys are prepared. The fatigue test ontology (FTO) and ckan.kupferdigital data management system are developed as two main prerequisites of the data digitalization process. FTO has been modeled according to the content of the fatigue testing standard and by reusing the basic formal ontology, industrial ontology foundry core ontology, and material science and engineering ontology. The ckan.kupferdigital data management system is also constructed in such a way that enables the users to prepare the protocols for mapping the datasets into the knowledge graph and automatically convert all the primary datasets to those machine‐readable data which are represented by the web ontology language. The retrievability of the converted digital data is also evaluated by querying the example competency questions, confirming that ckan.kupferdigital enables publishing open data that can be highly reused in the semantic web.
Manufacturing and Application of Lightweight Aggregates from Construction and Demolition Waste
(2024)
The objective of the REALight project is the development of a thermal process to produce lightweight aggregates in pilot scale and the implantation of a method to recover gypsum. Beside construction and demolition waste, various industrial by‐products are studied as raw materials. The raw materials have so far been unused or used in applications with lower quality requirements. To prove the performance of the lightweight aggregates, their technical properties are tested and their use in different applications is studied, e.g., for lightweight mortars as well as lightweight concretes.
Despite the physiological and pathophysiological significance of microenvironmental gradients, e.g., for diseases such as cancer, tools for generating such gradients and analyzing their impact are lacking. Here, we present an integrated microfluidic-based workflow that mimics extracellular pH gradients characteristic of solid tumors while enabling high-resolution live imaging of, e.g., cell motility and chemotaxis, and preserving the capacity to capture the spatial transcriptome. Our microfluidic device generates a pH gradient that can be rapidly controlled to mimic spatiotemporal microenvironmental changes over cancer cells embedded in a 3D matrix. The device can be reopened allowing immunofluorescence analysis of selected phenotypes, as well as the transfer of cells and matrix to a Visium slide for spatially resolved analysis of transcriptional changes across the pH gradient. This workflow is easily adaptable to other gradients and multiple cell types and can therefore prove invaluable for integrated analysis of roles of microenvironmental gradients in biology.
AbstractThe correlation between altered extracellular pH and various pathological conditions, including cancer, inflammation and metabolic disorders, is well known. Bulk pH measurements cannot report the extracellular pH value at the cell surface. However, there is a limited number of suitable tools for measuring the extracellular pH of cells with high spatial resolution, and none of them are commonly used in laboratories around the world. In this study, a versatile ratiometric nanosensor for the measurement of extracellular pH was developed. The nanosensor consists of biocompatible polystyrene nanoparticles loaded with the pH-inert reference dye Nile red and is surface functionalized with a pH-responsive fluorescein dye. Equipped with a targeting moiety, the nanosensor can adhere to cell membranes, allowing direct measurement of extracellular pH at the cell surface. The nanosensor exhibits a sensitive ratiometric pH response within the range of 5.5–9.0, with a calculated pKa of 7.47. This range optimally covers the extracellular pH (pHe) of most healthy cells and cells in which the pHe is abnormal, such as cancer cells. In combination with the nanosensors ability to target cell membranes, its high robustness, reversibility and its biocompatibility, the pHe nanosensor proves to be well suited for in-situ measurement of extracellular pH, even over extended time periods. This pH nanosensor has the potential to advance biomedical research by improving our understanding of cellular microenvironments, where extracellular pH plays an important role.
AbstractLithium‐ion batteries, essential for electronics and electric vehicles, predominantly use cathodes made from critical materials like cobalt. Sulfur‐based cathodes, offering a high theoretical capacity of 1675 mAh g−1 and environmental advantages due to sulfur's abundance and lower toxicity, present a more sustainable alternative. However, state‐of‐the‐art sulfur‐based electrodes do not reach the theoretical capacities, mainly because conventional electrode production relies on mixing of components into weakly coordinated slurries. Consequently, sulfur‘s mobility leads to battery degradation—an effect known as the “sulfur‐shuttle”. This study introduces a solution by developing a microporous, covalently‐bonded, imine‐based polymer network grown in situ around sulfur particles on the current collector. The polymer network (i) enables selective transport of electrolyte and Li‐ions through pores of defined size, and (ii) acts as a robust host to retain the active component of the electrode (sulfur species). The resulting cathode has superior rate performance from 0.1 C (1360 mAh g−1) to 3 C (807 mAh g−1). Demonstrating a high‐performance, sustainable sulfur cathode produced via a simple one‐pot process, our research underlines the potential of microporous polymers in addressing sulfur diffusion issues, paving the way for sulfur electrodes as viable alternatives to traditional metal‐based cathodes.
High‐Entropy Alloys and Their Affinity with Hydrogen: From Cantor to Platinum Group Elements Alloys
(2024)
AbstractProperties of high‐entropy alloys are currently in the spotlight due to their promising applications. One of the least investigated aspects is the affinity of these alloys to hydrogen, its diffusion, and reactions. In this study, high pressure is applied at ambient temperature and stress‐induced diffusion of hydrogen is investigated into the structure of high‐entropy alloys (HEA) including the famous Cantor alloy as well as less known, but nevertheless important platinum group (PGM) alloys. By applying X‐ray diffraction to samples loaded into diamond anvil cells, a comparative investigation of transition element incorporating HEA alloys in Ne and H2 pressure‐transmitting media is performed at ambient temperature. Even under stresses far exceeding conventional industrial processes, both Cantor and PGM alloys show exceptional resistance to hydride formation, on par with widely used industrial grade Cu–Be alloys. The observations inspire optimism for practical HEA applications in hydrogen‐relevant industry and technology (e.g., coatings, etc), particularly those related to transport and storage.
Revolutionizing our polymer industry for adaption to a sustainable carbon circular economy has become one of today’s most demanding challenges. Exploiting renewable resources to replace fossil-fuel—based plastics with biopolymers such as poly(lactic acid) (PLA) is inevitable while using waste streams as a raw material resource at least is promising. When it comes to using PLA as technical polymer, its high flammability must be addressed by flame retardants compatible with the thermoplastic processing of PLA and its compostability. This study proposes microalgae enriched with phosphorus from wastewater (P-Algae) as an elegant way towards a kind of sustainable organophosphorus flame retardant. The concept is demonstrated by investigating the processing, pyrolysis, flammability, and fire behavior of PLA/P-Algae, while varying the P-Algae content and comparing P-Algae with four alternative bio-fillers (phosphorylated lignin, biochar, thermally treated sewage sludge, and metal phytate) with different P-contents as meaningful benchmarks.
Polymers of intrinsic microporosity exhibit a combination of high gas permeability and reasonable permselectivity, which makes them attractive candidates for gas separation membrane materials. The diffusional selective gas transport properties are connected to the molecular mobility of these polymers in the condensed state. Incoherent quasielastic neutron scattering was carried out on two polymers of intrinsic microporosity, PIM-EA-TB(CH3) and its demethylated counterpart PIM-EA-TB(H2), which have high Brunauer–Emmett–Teller surface area values of 1030 m2 g-1 and 836 m2 g-1, respectively. As these two polymers only differ in the presence of two methyl groups at the ethanoanthracene unit, the effect of methyl group rotation can be investigated solely. To cover a broad dynamic range, neutron time-of-flight was combined with neutron backscattering. The demethylated PIM-EA-TB(H2) exhibits a relaxation process with a weak intensity at short times. As the backbone is rigid and stiff this process was assigned to bendand-flex fluctuations. This process was also observed for the PIM-EA-TB(CH3). A further relaxation process is found for PIM-EA-TB(CH3), which is the methyl group rotation. It was analyzed by a jump-diffusion in a three-fold potential considering also the fact that only a fraction of the present hydrogens in PIM-EATB(CH3) participate in the methyl group rotation. This analysis can quantitatively describe the q dependence of the elastic incoherent structure factor. Furthermore, a relaxation time for the methyl group rotation can be extracted. A high activation energy of 35 kJ mol-1 was deduced. This high activation energy evidences a strong hindrance of the methyl group rotation in the bridged PIM-EA-TB(CH3) structure.
Multicomponent reactions (MCRs) offer a platform to create different chemical structures and linkages for highly stable covalent organic frameworks (COFs). As an illustrative example, the multicomponent Povarov reaction generates 2,4-phenylquinoline from aldehydes and amines in the presence of electron-rich alkenes. In this study, we introduce a new domino reaction to generate unprecedented 2,3-phenylquinoline COFs in the presence of epoxystyrene. This work thus presents, for the first time, structural isomeric COFs produced by multicomponent domino and Povarov reactions. Furthermore, 2,3-phenylquinolines can undergo a Scholl reaction to form extended aromatic linkages. With this approach, we synthesize two thermally and chemically stable MCR-COFs and two heteropolyaromatic COFs using both domino and in situ domino and Scholl reactions. The structure and properties of these COFs are compared with the corresponding 2,4-phenylquinoline-linked COF and imine-COF, and their activity toward benzene and cyclohexane sorption and separation is investigated. The position of the pendant phenyl groups within the COF pore plays a crucial role in facilitating the industrially important sorption and separation of benzene over cyclohexane. This study opens a new avenue to construct heteropolyaromatic COFs via MCR reactions.
In materials science, traditional techniques for analyzing layered structures are essential for obtaining information about local structure, electronic properties and chemical states. While valuable, these methods often require high vacuum environments and have limited depth profiling capabilities. The grazing exit x-ray absorption near-edge structure (GE-XANES) technique addresses these limitations by providing depth-resolved insight at ambient conditions, facilitating in situ material analysis without special sample preparation. However, GE-XANES is limited by long data acquisition times, which hinders its practicality for various applications. To overcome this, we have incorporated Bayesian optimization (BO) into the GE-XANES data acquisition process. This innovative approach potentially reduces measurement time by a factor of 50. We have used a standard GE-XANES experiment, which serve as reference, to validate the effectiveness and accuracy of the BO-informed experimental setup. Our results show that this optimized approach maintains data quality while significantly improving efficiency, making GE-XANES more accessible to a wider range of materials science applications.
Flexible anisotropic magnetoresistive sensors for novel magnetic flux leakage testing capabilities
(2024)
Rigid magnetic field sensors such as anisot Hall sensors have been used for years and have become industry standard for electromagnetic non-destructive testing (NDT). Recent technological developments in the field of flexible electronics allow for the fabrication of reshapeable magnetic field sensors on flexible substrates via thin-film deposition or printing. The magnetic properties of these sensors have comparable characteristics to industry-standard rigid magnetic field sensors, with the added ability of adapting to the surface of complex components and scanning in contact with the sample surface. This improves defect detectability and magnetic signal strength by minimizing the scanning lift-off (LO) distance. In this article flexible AMR sensors mounted on a rotative mechanical holder were used to scan a semi-circular ferromagnetic sample with 3 reference defects via magnetic flux leakage (MFL) testing, thus demonstrating the applicability of this type of sensors for the scanning of curved samples. In order to benchmark the performance of these sensors in comparison to industry standard rigid magnetic field sensors, a ferromagnetic sample with 10 reference defects of different depths was scanned employing flexible AMR and rigid GMR sensors. Defects with depths ranging from 110 μm up to 2240 μm were detected with an signal-tonoise ratio (SNR) of 2.7 up to 27.9 (for flexible AMR sensors) and 6.2 up to 72.3 (for rigid GMR sensors), respectively. A 2D magnetometer mapping of the sample with a spatial scanning step of 10 × 50 μm2 (flexible AMR) and 16 × 100 μm2 (rigid GMR) was obtained. The results show that this type of sensor can be used for high-resolution and high-detail mapping of defects on the surface of planar and non-planar ferromagnetic samples since the scanning lift-off distance is equal to the substrate thickness of 20 μm for in-contact scanning. The SNR comparison between flexible and rigid sensors shows that the performance of the flexible AMR sensors employed is not very far behind the performance of the rigid GMR sensors used.
It is an essential requirement for all building products to ensure durability of their fire safety. Throughout the working life of products, intumescent coatings are aged by certain climatic factors. To predict a lifetime of several years, generally the behaviour of the intumescent coating is extrapolated based on accelerated artificial ageing. The established German and European procedures to assess the durability assume a working life of at least 10 years. For a longer period, additional evidence is required; yet the procedure and the specifications to justify this are not described. In addition to addressing this formal lack, from a scientific point of view it is necessary to investigate the degradation of intumescent coatings in detail and to propose a reliable test concept to assess durability for more than 10 years. This paper summarises the existing knowledge about the ageing of intumescent coatings. The results of various demanding weathering approaches are presented for two intumescent coatings tested in a joint research project. Moreover, formulations with a reduced amount of functionally relevant components were analysed to gain insight into the associated effects. Derived from these research results and knowledge, recommendations are proposed to assess the durability of intumescent coatings for more than 10 years based on a combination of verifications.
Quantum dots (QDs) are remarkable semiconductor nanoparticles, whose optical properties are strongly size-dependent. Therefore, the real-time monitoring of crystal growth pathway during synthesis gives an excellent opportunity to a smart design of the QDs luminescence. In this work, we present a new approach for monitoring the formation of QDs in aqueous solution up to 90 °C, through in situ luminescence analysis, using CdTe as a model system. This technique allows a detailed examination of the evolution of their light emission. In contrast to in situ absorbance analysis, the in situ luminescence measurements in reflection geometry are particularly advantageous once they are not hindered by the concentration increase of the colloidal suspension. The synthesized particles were additionally characterized using X-ray diffraction analysis, transition electron microscopy, UV-Vis absorption and infrared spectroscopy. The infrared spectra showed that 3-mercaptopropionic acid (MPA)-based thiols are covalently bound on the surface of QDs and microscopy revealed the formation of CdS. Setting a total of 3 h of reaction time, for instance, the QDs synthesized at 70, 80 and 90 °C exhibit emission maxima centered at 550, 600 and 655 nm. The in situ monitoring approach opens doors for a more precise achievement of the desired emission wavelength of QDs.
The glass system (50NaPO3–20BaF2–10CaF2–20GdF3)-xTbCl3 with x = 0.3, 1, 3, 5, and 10 wt % was investigated. We successfully produced transparent glass ceramic (GC) scintillators with x = 1 through a melt-quenching process followed by thermal treatment. The luminescence and crystallization characteristics of these materials were thoroughly examined using various analytical methods. The nanocrystallization of Tb3+-doped Na5Gd9F32 within the doped fluoride-phosphate glasses resulted in enhanced photoluminescence (PL) and radioluminescence (RL) of the Tb3+ ions. The GC exhibited an internal PL quantum yield of 33 % and the integrated RL intensity across the UV-visible range was 36 % of that reported for the commercial BGO powder scintillator. This research showcases that Tb-doped fluoridephosphate GCs containing nanocrystalline Na5Gd9F32 have the potential to serve as efficient scintillators while having lower melting temperature compared to traditional silicate and germanate glasses.
Upconverting nanoparticles are essential in modern photonics due to their ability to convert infrared light to visible light. Despite their significance, they exhibit limited brightness, a key drawback that can be addressed by combining them with plasmonic nanoparticles. Plasmon-enhanced upconversion has been widely demonstrated in dry environments, where upconverting nanoparticles are immobilized, but constitutes a challenge in liquid media where Brownian motion competes against immobilization.
This study employs optical tweezers for the three-dimensional manipulation of an individual upconverting nanoparticle, enabling the exploration of plasmon-enhanced upconversion luminescence in water. Contrary to expectation, experiments reveal a long-range (micrometer scale) and moderate (20%) enhancement in upconversion luminescence due to the plasmonic resonances of gold nanostructures. Comparison between experiments and numerical simulations evidences the key role of Brownian motion. It is demonstrated how the three-dimensional Brownian fluctuations of the upconverting nanoparticle lead to an “average effect” that explains the magnitude and spatial extension of luminescence enhancement.
Silicon isotope fractionation during silicification is poorly understood and impedes our ability to decipher paleoenvironmental conditions from Si isotopes in ancient cherts. To investigate isotope fractionation during silica-for-carbonate replacement we analyzed the microscale Si and O isotope composition in different silica phases in a silicified zebra dolostone as well as their bulk δ18O and Δ’17O compositions. The subsequent replacement of carbonate layers is mimicked by decreasing δ18O and δ30Si. The textural relationship and magnitude of Si and O isotope fractionation is best explained by near-quantitative silica precipitation in an open system with finite Si. A Rayleigh model for silicification suggests positive Ɛ30/28Si during silicification, conforming with predictions for isotope distribution at chemical equilibrium from ab-initio models. Application of the modelled Ɛ30Si-T relationship yields silicification temperatures of approx. 50°C. To reconcile the δ18Ochert composition with these temperatures, the δ18O of the fluid must have been between -2.5 and -4 ‰, compositions for which the quartz phases fall close to the oxygen equilibrium fractionation line in three-isotope space. Diagenetic silica replacement appears to occur in O and Si isotopic equilibrium allowing reconstructions of temperatures of silicification from Si isotopes and derive the δ18O composition of the fluid – a highly desired value needed for accurate reconstructions of the temperature- and δ18O histories of the oceans.