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Eingeladener Vortrag
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The new recommended definition of a nanomaterial, 2022/C 229/01, adopted by the European Commission in 2022, will have a considerable impact on European Union legislation addressing chemicals, and therefore tools to implement this new definition are urgently needed. The updated NanoDefiner framework and its e-tool implementation presented here are such instruments, which help stakeholders to find out in a straightforward way whether a material is a nanomaterial or not. They are two major outcomes of the NanoDefine project, which is explicitly referred to in the new definition. This work revisits the framework and e-tool, and elaborates necessary adjustments to make these outcomes applicable for the updated recommendation. A broad set of case studies on representative materials confirms the validity of these adjustments. To further foster the sustainability and applicability of the framework and e-tool, measures for the FAIRification of expert knowledge within the e-tool’s knowledge base are elaborated as well. The updated framework and e-tool are now ready to be used in line with the updated recommendation. The presented approach may serve as an example for reviewing existing guidance and tools developed for the previous definition 2011/696/EU, particularly those adopting NanoDefine project outcomes.
In this review article, the impact of dissolved water on the viscous properties of soda lime silicate melts is addressed against the background of the upcoming switch from natural gas to hydrogen combustion. This change will lead to an increase in the total water content of the glasses by up to 0.4 mol%. In order to better define possible influences of water speciation, water-rich glasses were synthesised under increasing pressure up to the kbar range. It is shown that a distinction must be made between the influence of dissolved OH-groups and H2Omolecules in order to accurately reflect the dependence of isokom temperatures on water content. In addition, an increase of one order of magnitude in the tolerance to higher deformation rates was observed for the range of expected increased water contents during isothermal deformation processes, which is based on the timetemperature superposition principle, i.e. congruent flow curves were determined under isokomal conditions.
The permeation of hydrogen gas was studied in meta-aluminous (tectosilicate) glass powders of Li2O×Al2O3×SiO2 (LAS), Na2O×Al2O3×SiO2 (NAS) and MgO×Al2O3×SiO2 (MAS) systems by pressure loading and vacuum extraction in the temperatures range 210–310 °C. With this method, both the solubility S and the diffusivity D were determined, while the permeability was given by the product SD. For all glasses, S was found to decrease with temperature, while D increased. Since the activation energy of diffusion of H2 molecules exceeded that of dissolution, permeation increased slightly with temperature. When extrapolated to standard conditions (25 °C), the permeability of tectosilicate glasses was found to be only 10-22–10-24 mol H2 (m s Pa)-1, which is 8–10 magnitudes lower than most polymers. Thin glass liners of these compositions are expected to be the most effective barrier for tanks of pressurised hydrogen.
Comparative study of the co-assembly behaviour of 3-chloro-4-hydroxy-phenylazo dyes with DTAB
(2023)
The co-assembly of three one-fold negatively charged 3-chloro-4-hydroxy-phenylazo dyes (Yellow, Blue and Red) with the cationic surfactant dodecyltrimethylammoniumbromide (DTAB) was studied to probe dye–DTAB binding stoichiometry and assembly morphology. For each dye, phase separation was observed above a given dye : DTAB ratio with the ratio depending on the dye. While Yellow and DTAB showed liquid/liquid phase separation above Yellow : DTAB = 1 : 1.67, crystalline dye–DTAB complexes were observed for Blue–DTAB and Red–DTAB above Blue : DTAB = 1 : 2.56 and Red : DTAB = 1 : 2.94 respecively. In homogeneous solution, UV/vis spectroscopic investigations suggest stochiometries of Yellow : DTAB = 1 : 2, Blue : DTAB = 1 : 3 and Red : DTAB = 1 : 4. It was concluded, that Yellow exhibits the highest dye : DTAB binding stoichiometry in both, dye–surfactant complexes in the 2-phase region and in solution, whereas the lowest dye : DTAB binding stoichiometry was observed for Red–DTAB in both cases. The observed stoichiometries are inversely correlated to the impact dye addition has on the morphology of DTAB micelles. Generally, addition of dye to DTAB micelles leads to a reduction in spontaneous curvature of these micelles and to the formation of triaxial ellipsoidal or cylindrical micelles from oblate ellipsoidal DTAB micelles. At a DTAB concentration of 30 mM and a dye concentration of 5 mM, this effect was most pronounced for Red and least pronounced for Yellow, whilst Blue showed an intermediate effect.
Für die Sicherheit von Spannbetonbauwerken ist eine Empfindlichkeitsprüfung von Spannstahlprodukten gegenüber der wasserstoffinduzierten Spannungsrisskorrosion zwingend erforderlich. Die derzeitig normativ festgelegten Prüfmethoden nach DIN EN ISO 15630-3 zeigen nachweislich Schwächen hinsichtlich der Reproduzierbarkeit der Ergebnisse und erschweren damit die eindeutige Bewertung der Empfindlichkeit. Ziel des Forschungsvorhabens der Förderinitiative WIPANO des BMWK war es, die Prüfmethode hinsichtlich der Reproduzierbarkeit und Aussagesicherheit zu verbessern. Im Projekt wurden durch materialseitige, elektrolytische und verfahrenstechnische Parameteränderungen konstante und reproduzierbare Prüfbedingungen geschaffen. Dies ermöglichte eine eindeutige Differenzierung zwischen Gut- und Schlechtprodukten. Innerhalb des Projekts wurde ein Ringversuch initiiert, welcher die Anwendbarkeit und Reproduzierbarkeit der neuen Prüfmethode bestätigte. Das neue Prüfverfahren wurde hinsichtlich der Anwendbarkeit für das Spannstahlerzeugnis Draht evaluiert. Ein entsprechender Normentwurf mit einem Vorschlag für ein Konformitätskriterium dieser Erzeugnisse wurde dem zuständigen ISO-Gremium präsentiert und zur Abstimmung überlassen. Nach aktueller Rückmeldung seitens des Gremiums wird der Normentwurf den Eingang in den informativen Anhang der Prüfnorm finden, dies könnte den Weg für eine Spiegelung auf europäischer und nationaler Normungsebene ebnen.
Bulk metallic glasses (BMG) are amorphous metal alloys known for their unique physical and mechanical properties. In the present study, the formation of femtosecond (fs) laser-induced periodic surface structures (LIPSS) on the Zr-based BMGs Zr46Cu46Al8, Zr61Cu25Al12Ti2, Zr52.5Cu17.9Al10Ni14.6Ti5 (Vit105) and Zr57Cu15.4Al10Ni12.6Nb5 (Vit106) was investigated as a function of their different chemical composition. For this purpose, LIPSS were generated on the sample surfaces in an air environment by fs-laser irradiation (λ = 1025 nm, τ = 300 fs, frep = 100 kHz). The surface topography was characterized by scanning electron microscopy and atomic force microscopy. Moreover, the impact of LIPSS formation on the structure and chemical surface composition was analyzed before and after fs-laser irradiation by X-ray diffraction and X-ray photoelectron spectroscopy as well as by transmission electron microscopy in combination with energy dispersive X-ray spectroscopy. Despite the different chemical composition of the investigated BMGs, the fs-laser irradiation resulted in almost similar properties of the generated LIPSS patterns. In the case of Zr61Cu25Al12Ti2, Vit105 and Vit106, the surface analysis revealed the preservation of the amorphous state of the materials during fs-laser irradiation. The study demonstrated the presence of a native oxide layer on all pristine BMGs. In addition, fs-laser irradiation results in the formation of laser-induced oxide layers of larger thickness consisting of an amorphous ZrAlCu-oxide. The precise laser-structuring of BMG surfaces on the nanoscale provides a versatile alternative to thermoplastic forming of BMG surfaces and is of particular interest for the engineering of functional material surfaces.
Hierarchically porous, high‐surface‐area silica materials are excellent candidates for multiple applications like catalysis and environmental remediation. Shaping these materials with additive manufacturing (AM) techniques, like robocasting, could enable their use with the benefit of on‐demand, customized shaping and maximizing performance. Herein, ordered mesoporous silica COK‐12 slurries were robocasted into monoliths, containing different ratios of uncalcined COK‐12 and sodium bentonite (0–25 wt.%). The rheology of the mixed slurries is characterized by lower flow indexes (0.69 vs. 0.32) and higher yield stresses (96 vs. 259 Pa) compared to pure COK‐12 ones. Monoliths were printed in woodpile structures and calcined at 600°C. Micro‐CT measurements showed a linear shrinkage of 25% after calcination. Mechanical characterization showed increased uniaxial strength (0.20 ± 0.07 to 1.0 ± 0.3 MPa) with increasing binder/solids ratio from 13 to 25%. The amorphous, mesoporous structure of COK‐12 was retained. The structures exhibited open porosities of 52 ± 4% and showed higher specific mesopore volumes, and increased average mesopore size (6 vs. 8 nm) compared to COK‐12. Small‐angle x‐ray scattering analysis revealed an increased lattice parameter (10.3 vs. 11.0 nm) and reduced wall thickness (3.1 nm vs. 4.1 nm) of the COK‐12 in the monoliths. These properties indicate suitability for their application as porous supports and adsorbents.
REALight ‐ Leichtgranulate und REA‐Gips aus feinkörnigen sulfatbelasteten Bau‐ und Abbruchabfällen
(2023)
Ziel des Projekts REALight ist die Entwicklung einer Referenzanlage zur Herstellung von Leichtgranulaten (leichte Gesteinskörnungen) aus Bau‐ und Abbruchabfällen und zur Gipsrückgewinnung. Als Rohstoffe werden bisher ungenutzte oder auf niedrigem Niveau eingesetzte Bau‐ und Abbruchabfälle und industrielle Nebenprodukte verwendet. Als Produkte werden leichte Gesteinskörnungen hergestellt. Die Sulfatabtrennung durch eine thermische Zersetzung bildet die Grundlage für die zusätzliche Gewinnung von Rauchgasentschwefelungs‐Gips (REA‐Gips). Das Projekt wird im Rahmen der Fördermaßnahme „Ressourceneffiziente Kreislaufwirtschaft – Bauen und Mineralische Stoffkreisläufe (ReMin)” gefördert. ReMin ist eine Maßnahme zur Umsetzung des BMBF‐Forschungskonzepts „Ressourceneffiziente Kreislaufwirtschaft” als Teil der BMBF Strategie „Forschung für nachhaltige Entwicklung – FONA”. Ziel der Förderung ist es, den Ausbau der Kreislaufwirtschaft voranzutreiben. Im Mittelpunkt steht dabei die Bauwirtschaft mit ihrer hohen Nachfrage nach Rohstoffen und gleichzeitig großen Mengen an anfallenden mineralischen Abfällen. Am Projekt REALight sind 12 Partner aus verschiedenen Bereichen der Baustoffherstellung und ‐anwendung, Abfallaufbereitung, Verfahrenstechnik sowie Forschung und Entwicklung beteiligt.
Asymmetrically bridged aroyl-S,N-ketene acetals and aroyl-S,N-ketene acetal multichromophores can be readily synthesized in consecutive three-, four-, or five-component syntheses in good to excellent yields by several successive Suzuki-couplings of aroyl-S,N-ketene acetals and bis(boronic)acid esters. Different aroyl-S,N-ketene acetals as well as linker molecules yield a library of 23 multichromophores with substitution and linker pattern-tunable emission properties. This allows control of different communication pathways between the chromophores and of aggregation-induced emission (AIE) and energy transfer (ET) properties, providing elaborate aggregation-based fluorescence switches.
We present an easy-to-apply method to predict structural trends in the internal nucleation tendency of oxide glasses. The approach is based on calculated crystal fracture surface energies derived from easily accessible diatomic bond energy and crystal lattice data. The applicability of the method is demonstrated on literature nucleation data for isochemically crystallizing oxide glasses.