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Paper des Monats
- ja (32)
The mechanism of action of zirconium permanent modifiers on graphite surfaces was investigated in order to understand its influence on the analytical signal in atomic and molecular absorption spectrometry (AAS/MAS). For this, the molecule formation of CaF was studied, which is used for the indirect analytical determination of fluorine in high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). The kinetics of this reaction was established by monitoring its molecular spectrum at different atomisation temperatures. An Arrhenius plot showed a pseudo-first order reaction with respect to fluorine (n = 1). An intermediate state was isolated, and its structure was elucidated by spectroscopic methods: scanning electron microscopy with energy dispersive X-ray spectroscopy (SEMEDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XANES and EXAFS), and Raman microspectroscopy. We propose here a mechanism, where ZrO2 acts as a heterogeneous catalyst: after a pyrolytic step, an intermediate state of ZrO(OCaF) is activated, and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. No evidence of the formation of zirconium carbide was found. Consequently, as the CaF formation is catalysed by a heterogeneous catalyst, surface modifications with ZrO2 nanoparticles and ZrO xerogels were investigated in order to increase the surface area. Their influence was evaluated in the molecule formation of CaF, CaCl, CaBr, and CaI. Graphite furnace modification with zirconium oxide nanoparticles proves to be the best choice for fluorine analysis with a signal enhancement of more than eleven times with respect a non-coated graphite furnace. However, the influence of zirconium modifications in the analytical signals of Cl, and I is lower than the F signals or even negative in case of the Br. Understanding zirconium modifiers as heterogeneous catalysts offers a new perspective to AAS and MAS, and reveals the potential of surface analytical methods for development of improved permanent modifiers and graphite furnace coatings.
We report on the mechanical properties of Cu–Nb alloys produced by combinatorial magnetron sputtering.
Depending on the composition, the microstructure is either fully amorphous (~30–65 at.% Cu), a dispersion of Cu crystallites in an amorphous matrix (~70 at.%), or a dominant crystalline phase with separated nanoscale amorphous zones (~80 at.% Cu). Nanomechanical probing of the different microstructures reveals that the hardness of the fully amorphous alloy is much higher than a rule of mixture would predict. We further demonstrate a remarkable tunability of the resistance to plastic flow, ranging from ca. 9 GPa in the amorphous regime to ca. 2 GPa in the fully crystalline regime. We rationalize these findings based on fundamental structural considerations, thereby highlighting the vast structure-property design space that this otherwise immiscible binary alloy provides.
Herein, two polyurethane oligomers were successfully synthesized using a prepolymer mixing process. The prepolymers were synthesized based on the step-growth addition polymerization of polypropylene glycol, Methylene diphenyl diisocyanate and 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate. Isopropanol was functioned as the isocyanate blocking agent. Thereafter, different terpolymer emulsions were prepared by the emulsion graft copolymerization with the vinyl acetate monomer in presence of 2-ethylhexyl acrylate as a vinyl monomer. The chemical structures of the synthesized oligomeric monomers were probed by FTIR spectroscopy and found to vary with the content of acrylic monomer used in the oligomer synthesis phase (i.e.hydroxyethyl acrylate or hydroxyethyl methacrylate). The topography, thermal stability, and particle size of terpolymers were investigated by SEM, TGA, and zeta potential, respectively. The TGA results demonstrated marked enhancement in thermal stability of the synthesized terpolymers up to ca. 600°C, which was concurrent with enhanced surface homogeneity and film properties as evidenced by the SEM images. These terpolymers showed also property enhancement as binders for textile pigment printing in terms of rubbing resistance, color strength and fastness to washing when compared to the commercial binders.
These judgments would provide a new competent synthesis route by introducing polyurethane acetate vinyl acrylate as the binder for use in pigment printing of cotton fabrics.
Explosion regions of propane, isopropanol, acetone, and methyl acetate/inert gas/air mixtures
(2016)
The explosion regions for propane, isopropanol, acetone, and methyl acetate with air in the presence of nitrogen, argon, helium, and carbon dioxide were determined experimentally according to EN 14756/EN1839, method T. Except for propane, all the measurements were executed at 323 K and 1 bar. Propane experiments were carried out at 293 K and 1 bar. The results show that for the same type of inert gas, propane, isopropanol, and acetone have great closeness concerning the concentration of the inert gas at the apex of the explosion envelope in a ternary diagram with air as oxidizer. This leads to consistency in the limiting oxygen concentration (LOC) and minimum required amount of inert gas (MAI) values. Concerning methyl acetate, the apex was always reached at higher percentages of inert gases compared with the other fuels. This can be attributed to the presence of two oxygen atoms inside the chemical structure. Calculation of the explosion regions was carried out based on calculated adiabatic flame temperature (CAFT) method. The flame temperatures for the experimentally determined fuel/air/N2 mixtures were calculated. Then, these temperatures were used to predict the explosion limits of similar mixtures with other inert gases than nitrogen. The modeling results show reasonable agreement with the experimental results.
The explosion regions of 1-propanol, 2-propanol, acetone and 1-butanol in air were measured in the presence of CO2, He, N2 and Ar in accordance with EN1839 method T at high temperatures and at atmospheric pressure. The experimental results show that 1-propanol, 2-propanol and acetone have very similar lower explosion limits (LELs). 1-Butanol shows a slightly wider explosion area near the LEL line. In addition, the explosion regions of all combustible/inert gas/air mixtures were calculated with the method of constant adiabatic flame temperature profiles (CAFTP), using the flame temperature profile along the explosion region boundary curve of each combustible/N2/air mixture as a reference to determine the explosion regions of combustible/inert gas/air mixtures with inert gases other than N2 at different initial temperatures. To calculate the explosion regions for systems containing He, the calculation method was modified to include the very different physical transport properties of He. Moreover, the procedure for calculating the apexes in the ternary explosion diagrams was modified. The calculation results show good agreement with the experimental results.
In this study, experimental determination and modelling investigations for the explosion regions of 1,3-dioxolane/inert gas/N2O and 1,3-dioxolane/inert gas/air mixtures were carried out and compared. The experimental measurements were carried out at 338 K and atmospheric pressure according to EN1839 method T using the inert gases N2, CO2, He and Ar. The results showed that the ratio of the lower explosion limit in N2O (LELN2O) to the lower explosion limit in air (LELair) is 0.52 and the ratio of the maximum oxygen content in air (MOCair) to the limiting oxidizer fraction in nitrous oxide (LOFN2O) is 0.36 ± 0.02 independent of the inert gas. When comparing the inert gas amount at the apex based on the pure oxidizing component, which is O2 in case of air, N2O-containing mixtures need less inert gas to reach the limiting oxidizer quantity whereas the efficiency of inert gases is in the same order. The coefficients of nitrogen equivalency however were found to differ to some extent. The explosion regions of 1,3-dioxolane/inert gas/oxidizer mixtures were modelled using the calculated adiabatic flame temperature profile (CAFTP) method as well as corrected adiabatic flame temperatures. The results indicate good agreement with experimental data for CO2, N2 and Ar- containing mixtures. The noticeable deviations that occur when He is the inert gas are due to the lacking transport data of that mixture.
Over the years, industrial and human activities and agricultural practices have caused a serious threat to human health and the environment. Indeed, it has been demonstrated that these activities are responsible for the presence of pollutants in the soil, air and water.
Water is one of the most strategic issues today, as it is associated with the living world. Therefore, water pollution is becoming a universal scourge that leads to environmental degradation, decrease of water quality and threatens public health.
Water pollution is mainly due to the discharge of certain harmful chemical compounds that are not very or not at all biodegradable (phenolic compounds, heavy metals, hydrocarbons, dyes, pesticides, etc.) by various industries: chemical, pharmaceutical, textile, food processing, etc. The impact of these industrial effluents on fauna and flora is very harmful. A sensitization of the socio-economic actors and the public, accompanied by a severe regulation in relation to the discharges, would contribute to fight against this drift, but also, by the development of effective methods allowing to remove these pollutants, not only in an analytical purpose but also of depollution.
Thus and within the framework of the preservation of an environment with regard to any anthropogenic activity, our research topic relates to the use of original biosourced polymeric phases for the extraction of the organic compounds and the heavy metals in aqueous mediums.
Therefore, we have proceeded to the synthesis and characterization of a large variety of monomers, polymers and cross-linked materials. These products, partially derived from biomass, contain various functional groups with the ability to interact with chemical components without discriminating effect.
The developed polymer phases have been successfully used for the adsorption of some organic pollutants and heavy metals in synthetic aqueous solutions.
Iron aluminides depict a sustainable and light-weight material class which could be employed in many applications requiring high strength at intermediate to high temperatures. According to first results, the alloy Fe-26Al-4Mo-0.5Ti-1B surpasses conventional materials in wet corrosion resistance and creep resistance up to 650 °C. For these reasons, the AiF research project “WAFEAL – Materials applications for iron aluminides” was initiated to transfer these findings into a standardised materials dataset and to derive best practices for processing. In the first place, a set of different microstructures adjusted by varying casting methods, wall thicknesses and heat treatments was investigated and correlated with hardness on macro and micro scale. Correlations were drawn between solidification rates and resulting grain sizes and hardness. The effect of vacancy hardening was only verified for wall thickness as low as 2.5 mm. Moreover, a common decrease of macrohardness after a heat treatment at 1000 °C for 100 h was observed irrespective of casting process or wall thickness. This effect was linked with an unexpected decrease of the complex boride phase fraction which acts as a hardening phase.
Due to the increasing scarcity of critical raw materials current high-temperature materials are sought to be replaced by alloys based on more abundant metals. One possibility within the class of intermetallics are iron aluminides, which combine sustainability and cost-efficiency with the prospect of mass savings. Iron aluminides show competitive specific strength up to 700 °C and excellent creep and wet corrosion resistance by small additions of Mo, Ti and B. Nevertheless, a Mo content of above 2 at.% which is needed for optimum corrosion resistance results in enhanced brittleness, especially at room temperature. This is why alloys with these Mo fractions were only mechanically tested under compressive loading so far. Still, testing of static and creep properties under tensile loading is required for reliable component design. Besides high standards for crack-free processing, data acquisition for tensile loads is especially complicated by environmental embrittling effects for iron aluminides. To cope with these challenges, the AiF research project “WAFEAL – Materials applications for iron aluminides” was initiated. The main goal is to collect standardised data on ambient and high-temperature tensile properties and creep properties. Samples with a nominal composition of Fe-26Al-4Mo-0.5Ti-1B [at.%] were manufactured via centrifugal casting in ceramic shell moulds followed by machining. Heat treatment for homogenisation and final polishing were carried out where appropriate. A summary of the achieved tensile and creep properties such as yield and tensile strength, maximum elongation, secondary creep rate and stress exponents will be given. Results will be also discussed regarding the influence of temperature, stress level and microstructure on the damage mechanisms. Furthermore, the effect of different alloy concentrations on the mechanical response at different temperatures will be outlined within a small experimental series.
With an increasing demand in more efficient fuel consumption to reduce CO2 emissions, weight reductions in high-temperature materials at affordable costs gain increasing attention. One potential candidate is the intermetallic material class of iron aluminides, combining the advantages in mass savings, high temperature performance and recyclability of resources. The alloy Fe-26Al-4Mo-0.5Ti-1B was selected to study the microstructural features evolving from two casting processes, five wall thicknesses and three final conditions. Conclusions are drawn upon the correlations of processing variables, grain sizes and hardness.
Iron aluminides, already reported in the late 19th century, did not cease to attract the interest of scientists and engineers ever since. Besides good oxidation resistance, low density and resource availability, potentials for hightemperature strengths that compete with high-alloy steels were unlocked by low alloy contents. Still, research on alloy design continues, as alloying usually comes at the price of brittleness in low-temperature regimes. A potential candidate is the quinary Fe–Al–Mo–Ti–B system which is strengthened by solid solution and eutectic borides. It was shown to have good strength and outstanding creep resistance under compressive loading up to elevated temperatures. Although the individual effect of alloy additions is well understood in iron aluminides, little is known about the combined effects of alloying concentrations on microstructure, phase stability and mechanical properties. Therefore a systematic study of two Ti-doped near-Fe3Al alloys with varying contents of Mo (2–4 at.%) and B (0.5–1 at.%) was conducted. In total eight different alloys were fabricated by investment casting into ceramic shell molds. Alloys were characterized and compared by grain size, phase transitions, microstructure evolution as well as elemental compositions and volume fractions of phases. For mechanical characterization, macrohardness and microhardness tests as well as tensile tests at ambient and high tempera tures were conducted. Independent of alloy additions, alloys with 24–25 at.% Al exhibit superior proof strength due to a higher matrix hardness. Decreasing B content generally decreases strength by lower secondary phase fractions which contribute via particle hardening. Reducing Mo content decreases both the solute concentration in the matrix and secondary phase fractions. Surprisingly, strength is similar or even superior to alloys with higher Mo content. Strength relations are discussed with a focus on solid-solution hardening theory and other competing strengthening mechanisms.
The increasing importance of resource availability and closed-loop material cycles are driving materials research to reduce alloying content in conventional materials or even substitute them with more sustainable alternatives. Intermetallic iron aluminide alloys (FeAl) present a potential alternative. Many alloy concepts for improved high-temperature properties or ductility have already been successfully implemented in casting technologies on a laboratory scale. However, successful testing of FeAl alloys on an industrial scale was still pending at the beginning of the project.
Therefore, the aim of the project was to develop simulation-based casting concepts for industrial casting processes using the base alloy Fe-26Al-4Mo-0.5Ti-1B and to narrow down process limits by means of hot cracking tests. Findings were transferred into practice-oriented guidelines for casting of iron aluminides, which is accessible to future applicants in SMEs. The focus was placed on centrifugal casting combined with investment casting or die casting. In addition to numerous design and casting process parameters, heat treatments and alloying additions (Al, Mo, B) were varied to determine the influence of alloying elements on castability, microstructure and mechanical properties. Data from microstructure analyses (microscopic imaging, determination of grain sizes as well as phase compositions and volume fractions, fractography), mechanical tests (hardness measurements, compression tests, ambient and high-temperature tensile tests, creep tests) as well as measurements of thermophysical properties could be generated on the base alloy. Correlations of materials data with process variables allowed conclusions to be drawn on strengthening mechanisms and ductility of the alloy and how they can be controlled in terms of processing and component design. Successful casting of highly complex components with thin wall thicknesses and optimised alloy compositions points out prospects for new fields of application.
The increasing importance of resource availability and closed-loop material cycles are driving materials research to reduce alloying content in conventional materials or even substitute them with more sustainable alternatives. Intermetallic iron aluminide alloys (FeAl) present a potential alternative. Many alloy concepts for improved high-temperature properties or ductility have already been successfully implemented in casting technologies on a laboratory scale. However, successful testing of FeAl alloys on an industrial scale was still pending at the beginning of the project.
Therefore, the aim of the project was to develop simulation based casting concepts for industrial casting processes using the base alloy Fe-26Al-4Mo-0.5Ti-1B and to narrow down process limits by means of hot cracking tests. Findings were transferred into practice-oriented guidelines for casting of iron aluminides, which is accessible to future applicants in SMEs. The focus was placed on centrifugal casting combined with investment casting or die casting. In addition to numerous design and casting process parameters, heat treatments and alloying additions (Al, Mo, B) were varied to determine the influence of alloying elements on castability, microstructure and mechanical properties. Data from microstructure analyses (microscopic imaging, determination of grain sizes as well as phase compositions and volume fractions, fractography), mechanical tests (hardness measurements, compression tests, ambient and high-temperature tensile tests, creep tests) as well as measurements of thermophysical properties could be generated on the base alloy. Correlations of materials data with process variables allowed conclusions to be drawn on strengthening mechanisms and ductility of the alloy and how they can be controlled in terms of processing and component design. Successful casting of highly complex components with thin wall thicknesses and optimised alloy compositions points out prospects for new fields of application.
Ultrafast laser processing can be used to realize various morphological surface transformations, ranging from direct contour shaping to large-area-surface functionalization via the generation of “self-ordered” micro- and nanostructures as well as their hierarchical hybrids. Irradiation with high-intensity laser pulses excites materials into extreme conditions, which then return to equilibrium through these unique surface transformations. In combination with suitable top-down or bottom-up manufacturing strategies, such laser-tailored surface morphologies open up new avenues toward the control of optical, chemical, and mechanical surface properties, featuring various technical applications especially in the fields of photovoltaics, tribology, and medicine. This article reviews recent efforts in the fundamental understanding of the formation of laser-induced surface micro- and nanostructures and discusses some of their emerging capabilities.
The tetragonal crystal- structure type of chalcopyrites (chemical formula AIBIIICVI2) is a superstructure of sphalerite type. The c/a ratio differs generally from the ideal value 2, i.e., the crystal structure is pseudocubically distorted. For CuInSe2 and CuGaSe2 thin films, simulations demonstrate that it is theoretically possible to reveal the tetragonality in electron backscatter-diffraction (EBSD) patterns for CuGaSe2, whereas it may not be possible for CuInSe2. EBSD experiments on CuGaSe2 thin films using the ”Advanced Fit” band-detection method show that it is possible to extract accurate misorientation-angle distributions from the CuGaSe2 thin film. Pole figures revealing the texture of the CuGaSe2 thin film are shown, which agree well with X-ray texture measurements from the same layer.
Monodisperse iron oxide nanoparticles as reference material candidate for particle size measurements
(2020)
In order to utilize and rationally design materials at the nanoscale the reliable characterization of their physico-chemical properties is highly important, especially with respect to the assessment of their environmental or biological impact. Furthermore, the European Commission’s REACH Regulations require the registration of nanomaterials traded in quantities of at least 1 ton. Powders or dispersions where 50% (number distribution) of the constituent particles have sizes ≤ 100 nm in at least one dimension are defined as nanomaterials. This creates a need for industrial manufacturers and research or analytical service facilities to reliably characterize potential nanomaterials. Currently, BAM is developing reference nanoparticles, which shall expand the scarce list of worldwide available nano reference materials certified for particle size distribution and will also target other key parameters like shape, structure, porosity or functional properties. In this respect, materials like iron oxide or titanium dioxide are considered as candidates to complement the already available silica, Au, Ag, and polystyrene reference nanoparticles.
The thermal decomposition of iron oleate precursors in high boiling organic solvents can provide large quantities of iron oxide nanoparticles that can be varied in size and shape.[1, 2] The presence of oleic acid or other hydrophobic ligands as capping agents ensures stable dispersion in nonpolar solvents. Such monodisperse, spherical particles were synthesized at BAM and pre-characterized by electron microscopy (TEM, SEM including the transmission mode STEM-in-SEM) and dynamic light scattering comparing cumulants analysis and frequency power spectrum.
1. REACH regulations and nanosafety concerns create a strong need for nano reference materials with diverse properties.
2. Iron oxide nanoparticles are under development as new candidate reference material at BAM.
3. Narrow particle size distribution confirmed by light scattering and electron microscopy.
Iron Oxide Nanocubes as a New Certified Reference Material for Nanoparticle Size Measurements
(2023)
The rational design and increasing industrial use of nanomaterials require a reliable characterization of their physicochemical key properties like size, size distribution, shape, and surface chemistry. This calls for nanoscale reference materials (nanoRMs) for the validation and standardization of commonly used characterization methods closely matching real-world nonspherical nano-objects. This encouraged us to develop a nonspherical nanoRM of very small size consisting of 8 nm iron oxide nanocubes (BAM-N012) to complement spherical gold, silica, and polymer nanoRMs. In the following, the development and production of this nanoRM are highlighted including the characterization by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) as complementary methods for size and shape parameters, homogeneity and stability studies, and calculation of a complete uncertainty budget of the size features. The determination of the nanocubes’ edge length by TEM and SAXS allows a method comparison. In addition, SAXS measurements can also provide the mean particle number density and the mass concentration. The certified size parameters, area equivalent circular diameter and square edge length, determined by TEM with a relative expanded uncertainty below 9%, are metrologically traceable to a natural constant for length, the very precisely known (111) lattice spacing of silicon. Cubic BAM-N012 qualifies as a certified nanoRM for estimating the precision and trueness, validation, and quality assurance of particle size and shape measurements with electron microscopy and SAXS as well as other sizing methods suitable for nanomaterials. The production of this new iron oxide nanocube RM presents an important achievement for the nanomaterial community, nanomaterial manufacturers, and regulators.
Tracking waterborne microplastic (MP) in urban areas is a challenging task because of the various sources and transport pathways involved. Since MP occurs in low concentrations in most wastewater and stormwater streams, large sample volumes need to be captured, prepared, and carefully analyzed. The recent research in urban areas focused mainly on MP emissions at wastewater treatment plants (WWTPs), as obvious entry points into receiving waters. However, important transport pathways under wet-weather conditions are yet not been investigated thoroughly. In addition, the lack of comprehensive and comparable sampling strategies complicated the attempts for a deeper understanding of occurrence and sources. The goal of this paper is to (i) introduce and describe sampling strategies for MP at different locations in a municipal catchment area under dry and wet-weather conditions, (ii) quantify MP emissions from the entire catchment and two other smaller ones within the bigger catchment, and (iii) compare the emissions under dry and wet-weather conditions. WWTP has a high removal rate of MP (>96%), with an estimated emission rate of 189 kg/a or 0.94 g/[population equivalents (PEQ · a)], and polyethylene (PE) as the most abundant MP. The specific dry-weather emissions at a subcatchment were ≈30 g/(PEQ · a) higher than in the influent of WWTP with 23 g/(PEQ · a). Specific wet-weather emissions from large sub-catchment with higher traffic and population densities were 1952 g/(ha · a) higher than the emissions from smaller catchment (796 g/[ha · a]) with less population and traffic. The results suggest that wet-weather transport pathways are likely responsible for 2–4 times more MP emissions into receiving waters compared to dry-weather ones due to tire abrasion entered from streets through gullies. However, more investigations of wet-weather MP need to be carried out considering additional catchment attributes and storm event characteristics.
Im Vorhaben wurde eine forcierte Prüfmethode zur Bestimmung der Beständigkeit von metallenen Werkstoffen gegenüber Brennstoffen aus Mitteldestillaten und Gemischen aus Mitteldestillat und paraffinischen Kohlenwasserstoffen, die jeweils Fettsäuremethylester (FAME) als biogene Komponente enthalten, entwickelt. Bei der Prüfmethode werden Prüfkörper des jeweiligen Werkstoffes in speziellen Prüfmedien ausgelagert. Die Zusammensetzung von zwei Prüfmedien wurde im Vorhaben erarbeitet. Diese Prüfmedien erfassen die Effekte der Alterung des FAME, die zu erwarten sind, wenn der Brennstoff länger als 2 Jahre im Feld lagert. Sie decken den Bereich bis 20 % (V/V) FAME-Anteil ab. Die Auslagerung kann bei geringem Aufwand unter Atmosphärendruck durchgeführt werden.
Die Eignung einer Auswahl von metallenen Werkstoffen und Polymerwerkstoffen, die für Versorgungsanlagen für Mitteldestillat relevant sind, wurde durch Auslagerung in folgenden nicht gealterten Brennstoffen bestimmt: Heizöl EL schwefelarm (B0), Heizöl EL schwefelarm mit 20 % (V/V) FAME (B20), FAME (B100) und hydriertes Pflanzenöl (HVO). Die Werkstoffe wurden auch in einem 1 Jahr gealterten B20 und einem 8 Jahre gealtertem B10 ausgelagert. Die Temperatur bei der Auslagerung betrug 50 °C für die metallenen Werkstoffe und 40 °C und 70 °C für die Polymerwerkstoffe. Die Ergebnisse der Beständigkeitsbewertung wurden in Beständigkeitslisten zusammengefasst. Die mit B20 erhaltenen Bewertungen gelten generell für Gemische aus Heizöl EL schwefelarm und FAME mit einem FAME-Gehalt bis 20 % (V/V). Sie sind auch auf Gemische aus Dieselkraftstoff und FAME mit einem FAME-Gehalt bis 20 %(V/V) übertragbar.
Die forcierte Prüfmethode kann insbesondere KMUs bei der Weiterentwicklung von bestehenden Produkten und der Entwicklung von neuen Produkten als ein kostengünstiger Schnelltest zur Überprüfung der Werkstoff- und Bauteilbeständigkeit gegenüber Mitteldestillaten mit hohem FAME-Anteil dienen. Sie kann für die Hersteller die Sicherheit erhöhen, dass Bauteile die Freigabeprüfungen der Bauaufsicht bestehen, wobei die Freigabe jedoch nur für Deutschland gültig ist.
Die Erkenntnisse des Forschungsvorhabens können in eine harmonisierte Europäische Norm für alternative Brenn- und Kraftstoffe einfließen. Diese ist für die Bauteilhersteller die Voraussetzung für die Erschließung des europäischen Marktes.
Modeling of silicon surface topographies induced by single nanosecond laser pulse induced melt-flows
(2019)
Irradiation with a single nanosecond laser pulse in the melting regime can result in a characteristic change in the surface morphology of crystalline silicon. This has been verified experimentally in a variety of situations, where dimple-shaped surface topographies are produced. In this work, the dimple height, depth, and width are modeled following and extending in a more rigorous manner the approach of Wood and Giles [Phys. Rev. B 23, 2923–2942 (1981)] and that of Schwarz-Selinger and coworkers [Phys. Rev. B 64, 155323 (2001)], upon varying the laser irradiation parameters such as peak energy density, pulse duration, and wavelength. This is achieved with numerical simulations of one-dimensional heat flow as input to the analytical fluid-flow equations.
Irradiation with a single spatially Gaussian-shaped nanosecond laser pulse in the melting regime can result in a characteristic annular change in the surface morphology of crystalline silicon. This has been verified experimentally in a variety of situations, where dimple-shaped surface topographies are produced. In a recent work we have investigated the induced changes in the surface topography upon exposure to wavelengths in the visible and near infrared spectral region. Irradiation in the UV requires a more detailed analysis due to the enhanced absorption of the material. In the present analysis, we determine under which conditions our previous model can be used and the corresponding results are presented.
In dem Projekt soll die vollständige Wiederverwertbarkeit der Schlacke und ihrer Bestandteile demonstriert werden. Dazu gehören die vollständige Rückgewinnung der metallischen Phase, die in die Edelstahlherstellung zurückgeführt werden kann, sowie die Aufwertung der mineralischen Fraktion, die ihre uneingeschränkte Verwendung als Zementzumahlstoff oder mineralischer Baustoff erlaubt. Bei geeigneter Prozessführung des elektrischen Lichtbogenofens können durch „reduzierendes Schmelzen“ die chromhaltigen Wertstoffe zusammen mit anderen Schwermetallen zu 97% in einer Metalllegierung angereichert und separiert werden. Diese kann als Rohstoff in der Metallurgie eingesetzt werden. Der Chromgehalt der mineralischen Komponte der Schlacke konnte von ca. 3% auf unter 0,1% verringert werden. Die mineralische Fraktion lässt sich durch entsprechende Zuschläge während des Schmelzbetriebes und eine anschließende Granulation der schmelzflüssigen Phase zu einem Material aufwerten, das in seiner Zusammensetzung und seinen Eigenschaften typischen Zementkomponenten entspricht und als Rohstoff in der Zementproduktion eingesetzt werden kann. Dafür müssen allerdings noch die rechtlichen Voraussetzungen geschaffen werden, da der Rohstoffeinsatz gerade im Zement strengen Auflagen unterliegt und die Zemente bestimmte Normen erfüllen müssen.
Durch die in RECARC aufgezeigte Möglichkeit der Wiederverwertung können somit Stoffkreisläufe geschlossen werden, die ansonsten zu einem Verlust wertvoller Rohstoffe führen. Vor allem die steigenden Rohstoffkosten, aber auch die immer stärker limitierten CO2-Emissionen zeigen die hohe Relevanz im Umgang mit metallurgischen Reststoffen. Eine Überführung des in RECARC demonstrierten Verfahrens in die Industrie könnte einen wichtigen Beitrag zur nachhaltigen Schonung der natürlichen Ressourcen und der Umwelt leisten.
Over the last decade there have been increasing efforts to develop three-dimensional (3D) scaffolds for bone tissue Engineering from bioactive ceramics with 3D printing emerging as a promising technology. The overall objective of the present study was to generate a tissue engineered synthetic bone graft with homogenously distributed osteoblasts and mineralizing bone Matrix in vitro, thereby mimicking the advantageous properties of autogenous bone grafts and facilitating usage for reconstructing segmental discontinuity defects in vivo . To this end, 3D scaffolds were developed from a silica-containing calcium alkali orthophosphate, using, fi rst, a replica technique – the Schwartzwalder – Somers method – and, second, 3D printing, (i.e. rapid prototyping). The mechanical and physical scaffold properties and their potential to facilitate homogenous colonization by osteogenic cells and extracellular bone matrix formation throughout the porous scaffold architecture were examined.
Osteoblastic cells were dynamically cultured for 7 days on both scaffold types with two different concentrations of 1.5 and 3 × 10⁹ cells/l. The amount of cells and bone matrix formed and osteogenic marker expression were evaluated using hard tissue histology, immunohistochemical and histomorphometric analysis. 3D-printed scaffolds (RPS) exhibited more micropores, greater compressive strength and silica release. RPS seeded with 3 × 10⁹ cells/l displayed greatest cell and extracellular Matrix formation, mineralization and osteocalcin expression. In conclusion, RPS displayed superior mechanical and biological properties and facilitated generating a tissue engineered synthetic bone graft in vitro, which mimics the advantageous properties of autogenous bone grafts, by containing homogenously distributed terminally differentiated osteoblasts and mineralizing bone matrix and therefore is suitable for subsequent in vivo implantation for regenerating segmental discontinuity bone defects.
A technical-safety evaluation of the detonation effects of pyrotechnic compositions can be performed on the basis of TNT/PETN equivalence. The equivalence determination can be carried out by characterization of the blast wave generated because of detonation in free field tests, which however can be highly resource intensive and prone to uncertainties. Here, we present underwater ‘small-scale’ experiments for the determination of such equivalents.
Underwater experiments, as described in the European standard EN 13763-15:2004, are performed to test the capability of detonators to initiate secondary explosives by determining the released energy. At BAM this test was modified to compare the energy output of the pyrotechnic mixtures (those used in air bag gas generators and firework flash compositions) and thus to determine their equivalents of high explosives like TNT or PETN. In the modified tests, small cylindrical copper containers were filled with pyrotechnic substances, which were then attached to standard detonators. This explosive charge assembly was then lowered into a water tank of about 1000 l capacity. At the same depth as the charge assembly, a piezoelectric pressure sensor was immersed in the water at a horizontal distance of about 400 mm from the charge. By recording the time-dependent pressure during the test, the shock energy as well as the energy associated with the expanding gas bubble were determined.
Solar glass in arid and semi-arid regions is exposed to sand storms which can affect the durability of PV modules. Related erosion processes have been extensively studied but the results given are difficult to compare due to being obtained by different variables like particle speed and sand mass. This study correlates the damage of solar panels to the cumulative impact energy as a global parameter.
The manufacture of sintered glasses and glass-ceramics, glass matrix composites, and glass-bounded ceramics or pastes is often affected by gas bubble formation. Against this background, we studied sintering and foaming of barium silicate glass powders used as SOFC sealants using different powder milling procedures. Sintering was measured by means of heating microscopy backed up by XPD, differential thermal analysis, vacuum hot extraction (VHE), and optical and electron microscopy. Foaming increased significantly as milling progressed. For moderately milled glass powders, subsequent storage in air could also promote foaming. Although the powder compacts were uniaxially pressed and sintered in air, the milling atmosphere significantly affected foaming. The strength of this effect increased in the order Ar ≈ N2 < air < CO2. Conformingly, VHE studies revealed that the pores of foamed samples predominantly encapsulated CO2, even for powders milled in Ar and N2. Results of this study thus indicate that foaming is caused by carbonaceous species trapped on the glass powder surface. Foaming could be substantially reduced by milling in water and 10 wt% HCl.
Surface roughness, RZ, normal transmittance, ΤN, total transmittance, ΤT, and photovoltaic (PV) module efficiency, ηS, were measured for commercial solar glass plates and PV test modules identically sandblasted with different loads of quartz sand (200–400 μm), impact inclination angles, and sand particle speed. Measured data are presented versus the specific energy uptake during sand blasting, E (J/m2). Cracks, adhering particles, and scratch-like textures probably caused by plastic flow phenomena could be observed after sand blasting. Their characteristic size was much smaller than that of sand particles. After blasting and subsequent cleaning, the glass surface was still covered with adhering glass particles. These particles, cracks, and scratch-like textures could not be removed by cleaning. For sand blasting with α = 30° inclination angle and E = 30 000 J/m2, normal transmittance, total transmittance, and relative module efficiency decreased by 29%, 2% and ∽2%, respectively. This finding indicates that diffusive transmission of light substantially contributes to PV module efficiency and that the module efficiency decrease caused by sand erosion can be better estimated from total than by normal transmittance measurements.
As an alternative shaping method to the traditionally used processes, additive manufacturing (AM) can produce economical ceramic components in small lot sizes and/or with complex geometries. Powder-based additive manufacturing processes like binder jetting are popular in the field of metal AM. One reason is the increased productivity compared to other AM technologies. For ceramic materials, powder-based AM technologies result in porous ceramic parts, provided they are not infiltrated. CerAMing GmbH unites the advantages of powder-based processes with the production of dense ceramic by means of the Layerwise Slurry Deposition. By using a suspension, a high packing density of the powder bed is achieved which leads to high green body densities. Due to this advantage the approach overcomes the problems of other powder-based AM technologies. Furthermore, a very economical debinding time allows the production of parts with high wall thicknesses.
Experimental study on M23C6 nucleation and growth mechanisms in Ni-base superalloy single crystals
(2017)
The addition of carbon to Ni-base superalloy single crystals has been increasingly carried out to improve low angle grain boundary (LAGB) resistance and castability. Consequently, the precipitation of carbides is highly probable during long-term application of components subjected to higher temperatures (> 1000 °C). While the view on the role of carbides as strengthening or detrimental is polemical, their inevitable increased presence in carbon-doped alloys must be addressed. In the present work, the evolution of M23C6 carbides forming in the commercial grade Ni-base superalloy LEK 94 during high-temperature and low-stress creep exposure is assessed. Although carbon is not intentionally added to the LEK 94 alloy, it admits up to 0.1 at. %, which together with the high content of M23C6-forming transition metals, leads to their precipitation. The precipitation is induced here during creep experiments at 1020 °C and a nominal applied stress of 160 MPa along [001]. The correlation of precipitation and external load is carried out by evaluating the carbides in the gage section of parallel and circularly notched cylindrical samples, as well as in their heads. Characterization is made by transmission electron microscopy (TEM). Although primary MC carbides form mostly in interdendritic regions during casting, high temperature exposure induces M23C6 carbide nucleation especially in the γ phase of dendritic regions, where a stronger partitioning of refractory elements is present. The carbides have a needle shape with their main axis on 〈100〉 and a cube-on-cube orientation relationship. They present incoherent {100} facets along their elongated region and semi-coherent {111} facets at their ends. Their nucleation and growth mechanisms are discussed based on microstructural observation under different experimental conditions.
The presentation shows how the three-dimensional quantification of dislocations and their characteristic features, e.g. Burgers vector, line direction, dislocation density, is carried out at the transmission electron microscope in scanning mode (STEM) at Division 5.1 at BAM. Exemplarily, the methods are shown for Ni-base superalloy single crystals, for which a short introduction is given using further TEM techniques. Additional examples on low angle grain boundaries, nucleation of oxides at dislocations and interaction of dislocations and carbides are shown.
The content of the presentation was addapted, aiming at scientists who work within the DFG Priority Programme 1713 "Strong coupling of thermo-chemical and thermo-mechanical states in applied materials".
The LEK94 is a Ni-base superalloy single crystal (SX) of the second generation, a materials class which is important for its high temperature creep resistance (>1000°C) in first stage blades of low-to-medium pressure gas turbines. Monocrystalline Ni-base superalloy SXs have a two-phase microstructure consisting of small cubes (' phase with the ordered L12 crystal structure, cube edge length: 500 nm), separated by thin channels (γ phase with fcc solid solution structure, channel width: 20 nm). The microstructural evolution during high temperature and low stress tensile creep has been thoroughly investigated previously, mainly for [001] loading, both in terms of dislocation activity (filling of γ channels, formation of dislocation networks, cutting of the γ’ phase) as well as phase coarsening (rafting, topological inversion). Other loading geometries have received less attention.
The present work studies high temperature and low stress creep deformation of the superalloy LEK 94 at temperatures around 1000°C, where rafting occurs. Differences between loading under different uniaxial, biaxial and triaxial stress states are discussed. Stereo-microscopy and g∙b analysis in the scanning transmission electron microscopy mode (STEM) are combined for microstructural analysis. The focus is set on the role of dislocation interactions with the aging microstructure. Both development in STEM characterization methods, as well as the roles of phase coarsening, γ channel filling, microstructural heterogeneity and γ’ phase cutting are discussed.
The demand for improved castability and low angle grain boundary (LAGB) resistance has led to the addition of low contents of e.g., B, Hf, Zr or C, into large industrial gas turbine components made of Ni-base superalloy single crystals (SXs). Due to the long-term application of Ni-base superalloy SX components in the temperature regime > 1000 °C, the formation of carbides is highly probable, which could jeopardize mechanical properties, such as high cycle fatigue. In the present contribution, the effect of internal and external stresses on the nucleation and growth characteristics of M23C6 carbides is investigated. Creep experiments are performed on the Ni-base superalloy SX LEK 94, which shows a low C concentration (= 0.1 at. %), at 1020 °C under parallel and circularly notched tensile specimens at a nominal stress of 160 MPa in the crystallographic direction [001]. The carbides are then characterized via scanning (S) and transmission (T) electron microscopy (EM). Nucleation is enhanced in the dendritic cores, often as coalesced colonies, extending over micrometers within M-rich (M: Cr, Re, W, Mo) γ channels. Lath shapes with facets on {100} (parallel to growth direction) and {111} are common. These facets exist since early stages (Fig.1a) and later develop misfit dislocations (Fig.1b), preserving the orientation relationship {100}γ || {100}M23C6. Fig. 1c shows a region from the creep gage, where carbides interact with superdislocations in the γ’ phase. Possible mechanisms are discussed.
Oxidation of a Fe-13Cr alloy under water vapor at 600 °C produced a zone of nano-sized precipitation underneath the outside scale formed by iron oxides and Fe‒Cr spinel. The majority of the spinel layer shows a mixed orientation relationship to the ferritic matrix {100}α || {100}sp & <011>α || <001>sp. However, also the discovered precipitated particles are characterized by the same crystallographic orientation relationship to the respective ferritic parent grain. The habit of the precipitates is best described by a lath morphology with their main axis parallel to <100> of ferrite.
Energy dispersive X-ray spectroscopy (EDX) and electron backscatter diffraction (EBSD) in an scanning electron microscope (SEM) have been applied to characterize the oxide layer in the micrometer scale. The clearly smaller precipitates were subsequently investigated by transmission electron microscopy (TEM). Specimens have been prepared by focused ion-beam (FIB) milling at an area previously characterized by EBSD. They cover the ferritic base material, but mainly the precipitation zone and the Fe‒Cr spinel layer. Energy filtered selected area diffraction (SAD) in the conventional (C)TEM and high-angle annular darkfield (HAADF) imaging in the scanning (S)TEM mode were employed in the characterization of the specimens.
The field of materials science is defined as “the study of the properties of solid materials and how those properties are determined by a material’s composition and structure.”. Many –if not most– of the materials that are produced nowadays owe their properties to structures engineered down to the nanoscopic level. This need has been partly realized thanks to the understanding of materials’ building blocks via characterization techniques that reach this level of resolution. Transmission electron microscopy, since its first implementation in the early 1930s (in Berlin), has been implemented to achieve imaging –and spectral– analysis at lateral resolutions down to the atomic level.
In this contribution, a series of practical examples will be presented, where applied materials are characterized by a range of transmission electron microscopy techniques to understand structural and functional properties of a wide range of materials. Among these materials examples will be presented on structural conventionally and additively manufactured metallic alloys, high entropy alloys, dissimilar aluminum-to-steel welds, magnetic nanoparticles, ceramic coatings, high temperature oxidation products. Addressed will be either the effect of processing route or that of the exposure to experimental conditions similar to those found in the respective intended applications.
Additive manufacturing (AM) of metallic alloys has gained momentum in the past decade for industrial applications. The microstructures of AM metallic alloys are complex and hierarchical from the macroscopic to the nanometer scale. When using laser-based powder bed fusion (L-PBF) process, two main microstructural features emerge at the nanoscale: the melt pool boundaries (MPB) and the solidification cellular substructure.
Here, details of the MPB are revealed to clearly show the three-dimensional nature of MPBs with changes of cell growth of direction and their relation to their surrounding cellular substructure, as investigated by transmission electron microscopy (TEM) for L-PBF 316L austenitic stainless steel (cf. Figure 1). A hitherto unknown modulated substructure with a period of 21 nm is further discovered within cells as the result of a partial Ga+-focused ion beam-induced ferritic transformation of the austenite. Cell cores and cell boundaries differ notably regarding the modulated substructure.
Ni-base superalloy single crystals have been used in turbine blades for hot sections of gas turbines for over four decades. In order to increase the efficiency of the turbines, a continuous increase in the inlet temperature of combustion gases into the turbine has driven the design of turbine blades to complicated shapes and the presence of a complex pattern of cooling channels. These three-dimensional shapes, together with the inhomogeneous distribution of stresses along the blade, induce an also complicated triaxial stress state, which does not compare to uniaxial tests that are performed to characterize high temperature properties such as creep. A round notch on a test piece represents a simple configuration that generates a quasi-isostatic stress state across the notch. In the present contribution, the effect of a sharp round notch on the microstructural micromechanisms within the notched region cylindrical bars, loaded along [001] at 1020 °C and 160 MPa net stress, is studied. To this end, a series of interrupted creep tests is conducted on plain and notched bars and the microstructure is compared. Results are discussed in terms of degree microstructural coarsening, and dislocation activity. The effect of notch generation via grinding is also discussed in these terms. The presence of carbides evolving in from residual carbon is also shown and discussed. .Funding by the German Research Association (DFG) [grant number AG 191/1] is acknowledge
Unlike conventional alloys, which typically consist of one main element, high-entropy alloys (HEAs) contain five or more principal elements, which broaden chemical complexity and with it a realm of synergistic mechanisms. The AlMo0.5NbTa0.5TiZr HEA initiated a subclass of Al-containing refractory (r)HEAs that has recently drawn attention [2]. The alloy has a superalloy-resembling B2/bcc nanostructure, which inspired its name refractory high entropy superalloy (RSA). With high-temperature (HT) compressive strengths beyond conventional Ni-based superalloys, this nanostructure could be used for improved HT structural applications. However, in the application-relevant HT regime the Al-Zr-rich B2 phase decomposes to form a hexagonal Al-Zr-based intermetallic (Al4-xZr5; x: 0..1) [3,4]. This work explores the fascinating yet fatal micromechanisms associated to this phase transformation, in the context of creep, annealing and oxidation experiments performed between 800 and 1200 °C.
The material was produced by arc-melting and heat treatment in argon, which lead to grain boundaries decorated with up to 7%. Interrupted constant-load creep tests were performed under vacuum (at 10-4 Pa), at 900–1100 °C with external tensile stresses of 30–120 MPa. Oxidation experiments were separately conducted for 24 hours at 800 and 1000 °C in both dry (21% O2 + 79% N2) and humid (8% O2 + 74% N2 + 18% H2O) air. After the experiments, the samples were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy to reveal degradation mechanisms. Crystallographic texture, orientation relationships and stabilization of an oxygen-containing iso structure (Al4-xZr5(Ox-y); y: 0..x) of the Al-Zr-rich intermetallic are found and discussed.
The present work describes the shear creep behavior of the superalloy LEK 94 at temperatures between 980 and 1050 °C and shear stresses between 50 and 140 MPa for loading on the macroscopic crystallographic shear system (MCSS) (011)[01-1]. The strain rate versus strain curves show short primary and extended secondary creep regimes. We find an apparent activation energy for creep of Qapp = 466 kJ/mol and a Norton-law stress exponent of n = 6. With scanning transmission electron microscopy, we characterize three material states that differ in temperature, applied stress, and accumulated strain/time. Rafting develops perpendicular to the maximum principal stress direction, gamma channels fill with dislocations, superdislocations cut gamma' particles, and dislocation networks form at gamma/gamma' interfaces. Our findings are in agreement with previous results for high-temperature and low-stress [001] and [110] tensile creep testing, and for shear creep testing of the superalloys CMSX-4 and CMSX-6 on the MCSSs (111)[01-1] and (001)[100]. The parameters that characterize the evolving gamma/gamma' microstructure and the evolving dislocation substructures depend on creep temperature, stress, strain, and time.
Photon upconversion upon 1550 nm excitation is of high relevance for applications in the third biological excitation window, for photovoltaics beyond current limitations, and enables appealing options in the field of glass Fiber telecommunications. Trivalent doped erbium ions (Er3+) are the material of choice for 1550 nm excited upconversion, however, they suffer from a low absorption cross-section and a low brightness. Therefore, the ability of Silicon metasurfaces to provide greatly enhanced electrical near-fields is employed to enable efficient photon upconversion even at low external Illumination conditions. Hexagonally shaped β-NaYF4:Er3+ nanoparticles are placed on large-area silicon metasurfaces designed to convert near-infrared (1550 nm) to visible light. More than 2400-fold enhanced photon upconversion luminescence is achieved by using this metasurface instead of a planar substrate.
With the aid of optical simulations based on the finite-element method, this result is attributed to the coupling of the excitation source with metasurface resonances at appropriate incident angles. Analysis of the excitation power density dependence of upconversion luminescence and red-to-green-emission ratios enables the estimation of nanoscale near-field enhancement on the metasurface. The findings permit the significant reduction of required external excitation intensities for photon upconversion of 1550 nm light, opening perspectives in biophotonics, telecommunication, and photovoltaics.
Enhanced photon upconversion using erbium-doped nanoparticles interacting with silicon metasurfaces
(2021)
Photon upconversion (UC) using trivalent erbium (Er+3) doped crystals is a promising concept to harness near infrared photons of the solar spectrum which cannot be directly absorbed by silicon solar cells. However, their UC efficiency at low-intensity 1 sun illumination is not relevant on device level so far. Exploiting giant near-field enhancement effects on metasurfaces is an appealing approach to enable efficient UC at low irradiance conditions. Here, we report on more than 1000-fold enhanced photon UC of NaYF4:Er+3 nanoparticles interacting with the near-fields supported by a silicon metasurface under 1550 nm excitation.
The embrittlement of metallic alloys by liquid metals leads to catastrophic material failure and severely impacts their structural integrity. The weakening of grain boundaries by the ingress of liquid metal and preceding segregation in the solid are thought to promote early fracture. However, the potential of balancing between the segregation of cohesion-enhancing interstitial solutes and embrittling elements inducing grain boundary decohesion is not understood. Here, we unveil the mechanisms of how boron segregation mitigates the detrimental effects of the prime embrittler, zinc, in a Σ5 [0 0 1] tilt grain boundary in α −Fe (4 at.% Al). Zinc forms nanoscale segregation patterns inducing structurally and compositionally complex grain boundary states. Ab-initio simulations reveal that boron hinders zinc segregation and compensates for the zinc induced loss in grain boundary cohesion. Our work sheds new light on how interstitial solutes intimately modify grain boundaries, thereby opening pathways to use them as dopants for preventing disastrous material failure.
Aiming at the overall negative surface charge of bacteria, a new strategy of antibacterial agents based on large polymer-modified graphene oxide (GO) sheets is assessed. The presented flexible, polycationic Sheets match the size and charge density of the Escherichia coli surface charge density (2 × 1014 cm−2). These matching parameters create an unspecific but very strong bacteria adsorber by multivalent, electrostatic attraction.
Their interaction with bacteria is visualized via atomic force and confocal microscopy and shows that they effectively bind and wrap around E. coli cells, and thereby immobilize them. The incubation of Gram-negative and -positive bacteria (E. coli and methicillin-resistant Staphylococcus aureus, MRSA) with these polycationic sheets leads to the inhibition of proliferation and a reduction of the colony forming bacteria over time.
This new type of antibacterial agent acts in a different mode of Action than classical biocides and could potentially be employed in medicinal, technical, or agriculture applications. The presented microsheets and their unspecific binding of cell interfaces could further be employed as adsorber material for bacterial filtration or immobilization for imaging, analysis, or sensor technologies.
We analyzed the results of high-energy X-ray CT scans for three 20×16×16 in. block samples of Indiana limestone from our recent radial acidizing experiments with HCl. CT scans were done for complete samples, and 3D images of internal dissolution patterns were built. Each 3D image consists of submillimeter-size voxels to capture fine details of individual wormholes.
The obtained 3D images of acidized blocks allow us to observe from various angles the details of the wormholes obtained in the three experiments, which demonstrated wide pore-volume-to-breakthrough (PVBT) range with three different injection rates. Also, variation of the CT number reveals the presence of depositional layers in all block samples, and the obtained CT images were used to interpret the effect that rock layers might have on wormhole penetration at different injection rates.
Further, the built voxel models were used to calculate the radial distributions of dissolved rock volume, which otherwise are not obvious for such complex branched structures as wormholes. We observed how varied experimental conditions affected those distributions. The radial distributions were found very similar across the samples, which suggested the way to detect the effective wormhole penetration depth.
The crystallization behavior of sodium ion conductive Na2MnP2O7 glass was examined to clarify the crystallization mechanism. The formation of thermodynamically metastable phase, layered Na2MnP2O7, at the surface of the glass occurred. Heat treatment at 430 °C for 3 h lead to surface crystals of Na2MnP2O7 oriented with the (101) direction perpendicular to the sample surface. As the heat treatment temperature increased, the glass-ceramic samples deformed, and the presence numerous micro bubbles due to dissolved water was detected.
We report on the in situ investigation of mechanochemical syntheses of metal phosphonates. The metal phosphonates are formed in milling reactions starting from a metal acetate and a phosphonic acid. The conversions are observed by synchrotron PXRD and Raman spectroscopy to shed light on the reaction mechanisms including possible intermediates.
The exploration of metal phosphonates chemistry has gained great interest during the last decades, because of their structural diversity. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reactions (OER).
Here, we present the in situ investigation of mechanochemical syntheses of different manganese phosphonates by synchrotron X-ray diffraction. Nitrilotri(methylenephosphonic acid) and N,N-Bis(phosphonomethyl)glycine were chosen as ligands. The liquid-assisted milling process can be divided into three steps, including an amorphous stage. One of the products has not been obtained by classical solution chemistry before.
These metal phosphonates and/or their derivatives are considered to be active in electrochemical energy conversion. The verification of their applicability is one of the topics of our resent research.
Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. By milling the reactants, various organic, inorganic, and metal-organic compounds can be obtained in high yields. Although mechanochemistry is widely used, the underlying mechanisms are not fully understood making mechanochemical reactions difficult to predict. Metal phosphonates are metal-organic compounds accessible by grinding. Because of their structural diversity, the exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reaction (OER). Here, we present the in situ investigation of the mechanochemical synthesis of a manganese(II)-phosphonate by synchrotron X-ray diffraction and thermography. The product has not been obtained by classical solution chemistry before and its crystal structure was determined from PXRD data. The milling process can be divided into different steps, with the product crystallization corresponding with the highest temperature rise. The activity of this metal phosphonate towards OER was measured and is presented here.
Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. The exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades due to their structural diversity. We synthesized manganese phosphonates in milling reactions. The mechanochemical reactions were investigated in situ to reveal the underlying mechanisms.
Two divalent manganese aminophosphonates, manganese mono (nitrilotrimethylphosphonate) (MnNP3) and manganese bis N-(carboxymethyl)iminodi(methylphosphonate)) (Mn(NP2AH)2), have been prepared by mechanochemical synthesis and characterized by powder X-ray diffraction (PXRD). The structure of the novel compound Mn(NP2AH)2 was determined from PXRD data. MnNP3 as well as Mn(NP2AH)2 exhibits a chain-like structure.
In both cases, the manganese atom is coordinated by six oxygen atoms in a distorted octahedron. The local coordination around Mn was further characterized by extended X-ray absorption fine structure. The synthesis process was followed in situ by synchrotron X-ray diffraction revealing a three-step reaction mechanism. The asprepared manganese(II) phosphonates were calcined on air.
All samples were successfully tested for their suitability as catalyst material in the oxygen evolution reaction.
Ca-, Sr-, and Ba-Based coordination polymers (CPs) were prepared mechanochemically by milling metal-hydroxide samples with anthranilic acid (oABAH). {[Ca(oABA)2(H2O)3]}n consists of one-dimensional polymeric chains that are further connected by a hydrogen-bonding network. {[Sr(oABA)2(H2O)2]·H2O}n is a one-dimensional CP in which water molecules bridge Sr2+ ions and increase the dimensionality by building an extended network. {[Ba(oABA)2(H2O)]}n crystallizes as a two-dimensional CP comprising one bridging water molecule. The cation radii influence the inorganic connectivity and dimensionality of the resulting crystal structures. The crystal structures were refined from powder X-ray diffraction data using the Rietveld method. The local coordination environments were studied via extended X-ray absorption fine structure (EXAFS) measurements. The compounds were further characterized using comprehensive analytical methods such as elemental analysis, thermal analysis, MAS NMR, imaging, and dynamic vapor sorption (DVS) measurements. Compounds 1, 2, and 3 exhibit small surface areas which decrease further after thermal annealing experiments. All compounds exhibit a phase transformation upon heating, which is only reversible in 3.
New fluorinated coordination polymers were prepared mechanochemically by milling the alkaline earth metal hydroxides MII(OH)2·xH2O (MII: Ca, Sr) with tetrafluoroisophthalic acid (H2mBDC-F4). The structures of [{Ca(mBDC-F4)(H2O)2}·H2O] and [{Sr(mBDC-F4)(H2O)2}·H2O] were determined based on ab initio calculations and their powder X-ray diffraction (PXRD) data. The compounds are isomorphous and crystallize in the orthorhombic space group P212121. The determined structures were validated by using extended X-ray absorption (EXAFS) data. The new materials were thoroughly characterized using elemental analysis, thermal analysis, magic angle spinning NMR, and attenuated total reflection-infrared spectroscopy. Further characterization methods such as BET, dynamic vapor sorption, and scanning electron microscopy imaging were also used. Our investigations indicate that mechanochemistry is an efficient method for preparing such materials.
New fluorinated alkaline earth metal−organic frameworks were successfully synthesized by milling of metal hydroxides M(OH)2 with tetrafluoroterephthalic acid H2 pBDC-F4. Both calcium- and strontium-tetrafluoroterephthalates are tetrahydrated, while the barium tetrafluoroterephthalate is free of coordinating water molecules. The two isomorphic structures Ca(pBDC-F4)·4H2O and Sr(pBDC-F4)·4H2O were solved from the powder diffraction data by ab initio structure determination and subsequent Rietveld refinement. The products were thoroughly characterized by elemental analysis, thermal analysis, magicangle spinning NMR, Fourier transform infrared spectroscopy, scanning electron microscopy imaging, and Brunauer−Emmett−Teller measurements. Our findings suggest that the mechanochemical synthesis route is a promising approach for the preparation of new fluorinated alkaline earth metal−organic frameworks.
Two strontium-based dicarboxylate systems [Sr(oBDC-F4)(H2O)2] (1) and [{Sr(oBDC)(H2O)2)·H2O] (2) were synthesized mechanochemically via milling of Sr(OH)2·8H2O with tetrafluorophthalic acid (H2oBDC-F4) or phthalic acid (H2oBDC), respectively. The new structures were determined ab initio from the powder X-ray diffraction (PXRD) data. Both compounds 1 and 2 crystallize in the monoclinic space group P21 /c as two-dimensional coordination polymers (2D-CPs). The determined structures were validated by extended X-ray absorption (EXAFS) data. Compounds 1 and 2 show different thermal stabilities. The fluorinated CP 1 is decomposed at 300 °C while the nonfluorinated CP 2 transforms into a new phase after thermal treatment at 400 °C. The two hydrated CPs exhibit small surface areas which increase after the thermal posttreatment for 1 but remains unchanged for the dehydrated sample of 2. Dynamic vapor sorption (DVS) experiments indicate that both the dehydrated and hydrated samples of 2 depict no significant differences in their adsorption isotherms. The DVS of water indicates that the phase transition after thermal posttreatment of 2 is irreversible.
A series of Ca-based coordination polymers were prepared mechanochemically by milling Ca(OH)2 with phthalic acid (H2oBDC), isophthalic acid (H2mBDC), and terephthalic acid (H2pBDC). The hydrated compounds [Ca(oBDC)(H2O)], [Ca(mBDC)(H2O)3.4], and [Ca(pBDC)(H2O)3] were prepared for the first time via mechanochemical routes. The refined structures were validated by extended X-ray absorption data. The new dehydrated compound [Ca(oBDC)] (1-H2O), obtained after the thermal post-treatment of 1 in a reversible phase transition process, was determined ab initio based on the powder X-ray diffraction (PXRD) data. The materials were thoroughly characterized using elemental analysis, thermal analysis, and spectroscopic methods: magic-angle spinning NMR and attenuated total reflection-infrared spectroscopy. The specific surface areas and sorption properties of the hydrated and dehydrated samples were determined using the isotherms of gas sorption and dynamic vapor sorption measurements.
Eu2+ is used to replace toxic Pb2+ in metal halide perovskite nanocrystals (NCs). The synthesis implies injection of cesium oleate into a solution of europium (II) bromide at an experimentally determined optimum temperature of 130 ○C and a reaction time of 60 s. Structural analysis indicates the formation of spherical CsEuBr3 nanoparticles with a mean size of 43 ± 7 nm. Using EuI2 instead of EuBr2 leads to the formation of 18-nm CsI nanoparticles, while EuCl2 does not show any reaction with cesium oleate forming 80-nm EuCl2 nanoparticles.
The obtained CsEuBr3 NCs exhibit bright blue emission at 413 nm (FWHM 30 nm) with a room temperature photoluminescence quantum yield of 39%. The emission originates from the Laporte-allowed 4f7–4f65d1 transition of Eu2+ and shows a PL decay time of 263 ns.
The long-term stability of the optical properties is observed, making inorganic lead-free CsEuBr3 NCs promising deep blue emitters for optoelectronics.
Over the last few years, the Federal Institute for material research (BAM, Berlin) together with the Centre for the Study of Manuscript Cultures (CSMC, University of Hamburg) have initiated a systematic material investigation of black inks produced from Late Antiquity to the Middle Ages (ca. fourth century CE–fourteenth/fifteenth centuries CE), aimed primarily at extending and complementing findings from previous sporadic studies. Part of this systematic investigation has focused on Egyptian Coptic manuscripts, and the present preliminary study is one of its outputs. It centres on a corpus of 45 Coptic manuscripts—43 papyri and 2 ostraca—preserved at the Palau-Ribes and Roca-Puig collections in Barcelona. The manuscripts come from the Monastery of Apa Apollo at Bawit, one of the largest monastic settlements in Egypt between the Late Antiquity and the Early Islamic Period (sixth–eighth centuries CE). The composition of their black inks was investigated in situ using near-infrared reflectography (NIRR) and X-ray fluorescence (XRF). The analyses determined that the manuscripts were written using different types of ink: pure carbon ink; carbon ink containing iron; mixed inks containing carbon, polyphenols and metallic elements; and iron-gall ink. The variety of inks used for the documentary texts seems to reflect the articulate administrative system of the monastery of Bawit. This study reveals that, in contrast to the documents, written mostly with carbon-based inks, literary biblical texts were written with iron-gall ink. The frequent reuse of papyrus paper for certain categories of documents may suggest that carbon-based inks were used for ephemeral manuscripts, since they were easy to erase by abrasion.
In this paper, we present a study aimed at characterizing the optimal fiber optic components for Brillouin sensing in multimode fibers. For this purpose the use of single-mode and multimode circulators as well as couplers typically used in the Brillouin measurement setups was investigated. On the one hand the undesired coupling losses between conventional fiber optic measurement system components and a multimode sensor fiber can be overcome by replacing the singlemode components with their own multimode equivalents. On the other hand the use of multimode fiber optic circulators and multimode couplers affects the mode distribution of laser light which can impair the measurement signal backscattered in the multimode sensor fibers. In view of an increasing interest in high strain measurements using polymer optical fibers (POFs) as Brillouin-distributed sensors the investigation on Brillouin scattering effects in multimode fibers (MMFs) was performed on a low-loss perfluorinated graded-index polymer optical fiber (PFGI-POF). The obtained results were compared with those of a standard graded-index multimode (GI-MMF) silica glass optical fiber (GOF).
This study confirms the relevance of the adaptation of the measurement system components to the use of the multimode sensor fibers. In addition, due to mode coupling effects occurring in the tested POF itself, the results show differences in the yield of the components adaptation in the sensory implementation of the two kinds of the tested optical fibers.
A new algorithm for detection of longitudinal crack-like indications in radiographic images is developed in this work. Conventional local detection techniques give unsatisfactory results for this task due to the low signal to noise ratio (SNR ~ 1) of crack-like indications in radiographic images. The usage of global features of crack-like indications provides the necessary noise resistance, but this is connected with prohibitive computational complexities of detection and difficulties in a formal description of the indication shape. Conventionally, the excessive computational complexity of the solution is reduced by usage of heuristics. The heuristics to be used, are selected on a trial and error basis, are problem dependent and do not guarantee the optimal solution. Not following this way is a distinctive feature of the algorithm developed here. Instead, a global characteristic of crack-like indication (the estimation function) is used, whose maximum in the space of all possible positions, lengths and shapes can be found exactly, i.e. without any heuristics. The proposed estimation function is defined as a sum of a posteriori information gains about hypothesis of indication presence in each point along the whole hypothetical indication. The gain in the information about hypothesis of indication presence results from the analysis of the underlying image in the local area. Such an estimation function is theoretically justified and exhibits a desirable behaviour on changing signals. The developed algorithm is implemented in the C++ programming language and testet on synthetic as well as on real images. It delivers good results (high correct detection rate by given false alarm rate) which are comparable to the performance of trained human inspectors.
CsCoO2, featuring a two-dimensional layered architecture of edge- and vertex-linked CoO4tetrahedra, is subjected to a temperature-driven reversible second-order phase transformation at 100 K, which corresponds to a structuralrelaxation with concurrent tilting and breathing modes of edge-sharing CoO4tetrahedra. In the present investigation, it was found that pressure induces a phase transition, which encompasses a dramatic change in the connectivity ofthe tetrahedra. At 923 K and 2 GPa, beta-CsCoO2 undergoes a first-order phasetransition to a new quenchable high-pressure polymorph,alpha-CsCoO2. It is built up of a three-dimensional cristobalite-type network of vertex-sharing CoO4 tetrahedra. According to a Rietveld refinement of high-resolution powderdiffraction data, the new high-pressure polymorph gamma-CsCoO2 crystallizes in the tetragonal space groupI41/amd:2 (Z= 4) with the lattice constants a= 5.8711 (1) and c= 8.3214 (2) A, corresponding to a shrinkage in volume by 5.7% compared with the ambient-temperature and atmospheric pressure-CsCoO2polymorph.The pressure-induced transition (beta>gamma) is reversible;-CsCoO2 stays metastable under ambient conditions, but transforms back to the-CsCoO2structure upon heating to 573 K. The transformation pathway revealed isremarkable in that it is topotactic, as is demonstrated through a clean displacive transformation track between the two phases that employs the symmetry oftheir common subgroupPb21a(alternative setting of space group No. 29 that matches the conventional-phase cell).
Das langsame Risswachstum (slow crack growth, SCG) sowie der umgebungsbedingte Spannungsriss (environmental stress cracking, ESC) sind relevante Schädigungsmechanismen für teilkristalline Werkstoffe auf Basis von Polyethylen hoher Dichte (PE-HD).
Der Vortrag gibt einerseits einen Überblick über die grundlegenden Struktur-Eigenschafts-Beziehungen in diesem Kontext, andererseits werden auch verschiedene praxisorientierte Prüfverfahren vorgestellt. Letztere wurden in gemeinsamen Forschungsprojekten von BAM und LBF mit dem Schwerpunkt Gefahrgutbehälter bzw. Pflanzenschutzmittel vergleichend untersucht und durch weitergehende Analytik ergänzt.
The complex nature of liquid water saturation of polymer electrolyte fuel cell (PEFC) catalyst layers (CLs) greatly affects the device performance. To investigate this problem, we present a method to quantify the presence of liquid water in a PEFC CL using small-angle X-ray scattering (SAXS). This method leverages the differences in electron densities between the solid catalyst matrix and the liquid water filled pores of the CL under both dry and wet conditions. This approach is validated using ex situ wetting experiments, which aid the study of the transient saturation of a CL in a flow cell configuration in situ. The azimuthally integrated scattering data are fitted using 3D morphology models of the CL under dry conditions. Different wetting scenarios are realized in silico, and the corresponding SAXS data are numerically simulated by a direct 3D Fourier transformation. The simulated SAXS profiles of the different wetting scenarios are used to interpret the measured SAXS data which allows the derivation of the most probable wetting mechanism within a flow cell electrode.
The aim of this study is to develop nanometer-thin epoxy-based films on aluminium alloy AA2024-T3 as a model coating system for high resolution corrosion studies. Spin coating was used for the layer-by-layer (LbL) deposition of poly-(ethylenimine) (PEI) and poly([o-cresyl glycidyl ether]-co-formaldehyde) (CNER) bilayers. The film chemistry and the cross-linking process were characterized by means of Fourier-transform infrared spectroscopy (FTIR).
Ellipsometric data confirmed the linear increase of film thickness. The potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) results indicate the improvement of the film barrier properties with increasing film thickness. Mapping of the topography and the volta potential was performed by means of scanning Kelvin probe force microscopy (SKPFM).
The results indicate the presence of a homogeneous film structure, while the intermetallic phases can still be identified below the coating. The SKPFM Analysis confirmed that the model films are suitable for investigation of corrosion processes at the coating/metal interface.
The application of characterization methods with high spatial resolution to the analysis of buried coating/metal interfaces requires the design and use of model systems. Herein, an epoxy-like thin film is used as a model coating resembling the epoxy-based coatings and adhesives widely used in technical applications. Spin coating is used for the deposition of a 30 nm-thin bilayer (BL) composed of poly-(ethylenimine) (PEI) and poly[(o-cresyl glycidyl ether)-co-formaldehyde] (CNER). Fourier-transform infrared spectroscopy (FTIR) results confirm that the exposure of coated AA2024-T3 (AA) samples to the corrosive electrolyte solution does not cause the degradation of the polymer layer. In situ atomic force microscopy (AFM) studies are performed to monitor local corrosion processes at the buried interface of the epoxy-like film and the AA2024-T3 aluminum alloy surface in an aqueous electrolyte solution. Hydrogen evolution due to the reduction of water as the cathodic corrosion reaction leads to local blister formation. Based on the results of the complementary energy-dispersive X-ray spectroscopy (EDX) analysis performed at the same region of interest, most of the hydrogen evolved originates at the vicinity of Mg-containing intermetallic particles.
The industrial use of additive manufacturing for the production of metallic parts with high geometrical complexity and lot sizes close to one is rapidly increasing as a result of mass individualisation and applied safety relevant constructions. However, due to the high complexity of the production process, it is not yet fully understood and controlled, especially for changing (lot size one) part geometries.
Due to the thermal nature of the Laser-powder bed fusion (L-PBF) process – where parts are built up layer-wise by melting metal powder via laser - the properties of the produced part are strongly governed by its thermal history. Thus, a promising route for process monitoring is the use of thermography. However, the reconstruction of temperature information from thermographic data relies on the knowledge of the surface emissivity at each position on the part. Since the emissivity is strongly changing during the process due to phase changes, great temperature gradients, possible oxidation, and other potential influencing factors, the extraction of real temperature data from thermographic images is challenging. While the temperature development in and around the melt pool, where melting and solidification occur is most important for the development of the part properties. Also, the emissivity changes are most severe in this area, rendering the temperature deduction most challenging.
A possible route to overcome the entanglement of temperature and emissivity in the thermal radiation is the use of hyperspectral imaging in combination with temperature emissivity separation (TES) algorithms. As a first step towards the combined temperature and emissivity determination in the L-PBF process, here, we use a hyperspectral line camera system operating in the short-wave infrared region (0.9 µm to 1.7 µm) to measure the spectral radiance emitted. In this setup, the melt pool of the L-PBF process migrates through the camera’s 1D field of view, so that the radiation intensities are recorded simultaneously for multiple different wavelength ranges in a spatially resolved manner. At sufficiently high acquisition frame rate, an effective melt pool image can be reconstructed. Using the grey body approximation (emissivity is independent of the wavelength), a first, simple TES is performed, and the resulting emissivity and temperature values are compared to literature values. Subsequent work will include reference measurements of the spectral emissivity in different states allowing its analytical parametrisation as well as the adaption and optimisation of the TES algorithms. An illustration of the proposed method is shown in Fig.1.
The investigated method will allow to gain a deeper understanding of the L-PBF process, e.g., by quantitative validation of simulation results. Additionally, the results will provide a data basis for the development of less complex and cheaper sensor technologies for L-PBF in-process monitoring (or for related process), e.g., by using machine learning.
Results of the project ProMoAM (Process monitoring in additive manufacturing) presented. Results from in-situ eddy current testing, optical emission spectroscopy, thermography, optical tomography as well as particle and gas emission spectroscopy are summarized and correlated to results from computed tomography for future in-situ defect detection.
Additive manufacturing of metals gains increasing relevance in the industrial field for part production. However, especially for safety relevant applications, a suitable quality assurance is needed. A time and cost efficient route to achieve this goal is in-situ monitoring of the build process. Here, the BAM project ProMoAM (Process monitoring in additive manufacturing) is briefly introduced and recent advances of BAM in the field of in-situ monitoring of the L-PBF and the LMD process using thermography are presented.
Additive manufacturing (AM) offers a range of novel applications. However, the manufacturing process is complex and the production of defect-free parts with a high reliability is still a challenge. Thermography is a valuable tool for process surveillance, especially in metal AM processes. The high process temperatures allow one to use cameras usually operating in the visible spectral range. Here, we compare the results of first measurements during the manufacturing process of a commercial laser metal deposition (LMD) setup using a MWIR camera with those from a VIS high-speed camera with band pass filter in the NIR range.
Additive manufacturing (AM) opens the route to a range of novel applications.However, the complexity of the manufacturing process poses a challenge for the production of defect-free parts with a high reliability. Since process dynamics and resulting microstructures of AM parts are strongly influenced by the involved temperature fields, thermography is a valuable tool for process surveillance. The high process temperatures in metal AM processes allow one to use cameras usually operating in the visible spectral range to detect the thermally emitted radiation from the process. In our work, we compare the results of first measurements during the manufacturing processes of a commercial laser metal deposition (LMD) setup and a laser beam melting (LBM) setup using a MWIR camera with those from a VIS high-speed camera with band pass filter in the NIR range.
For metal-based additive manufacturing, sensors and measuring systems for monitoring of the energy source, the build volume, the melt pool and the component geometry are already commercially available. Further methods of optics, spectroscopy and non-destructive testing are described in the literature as suitable for in-situ application, but there are only a few reports on practical implementations.
Therefore, a new BAM project aims to develop process monitoring methods for the in-situ evaluation of the quality of additively manufactured metal components. In addition to passive and active thermography, this includes optical tomography, optical emission and absorption spectroscopy, eddy current testing, laminography, X-ray backscattering and photoacoustic methods. These methods are used in additive manufacturing systems for selective laser melting, laser metal deposition and wire arc additive manufacturing. To handle the sometimes huge amounts of data, algorithms for efficient preprocessing are developed and characteristics of the in-situ data are extracted and correlated to defects and inhomogeneities, which are determined using reference methods such as computer tomography and metallography. This process monitoring and fusion of data of different measurement techniques should result in a significant reduction of costly and time-consuming, destructive or non-destructive tests after the production of the component and at the same time reduce the production of scrap.
Here, first results of simultaneous measurements of optical emission spectroscopy and thermography during the laser metal deposition process using 316L as building material are presented. Temperature values are extracted from spectroscopic data by fitting of blackbody emission spectra to the experimental data and compared with results from a thermographic camera. Measurements with and without powder flow reveal significant differences between welding at a pristine metal surface and previously melted positions on the build plate, illustrating the significant influence of the partial oxidation of the surface during the first welding process on subsequent welding. The measurement equipment can either be mounted stationary or following the laser path. While first results were obtained in the stationary mode, future applications for online monitoring of the build of whole parts in the mobile mode are planned.
This research was funded by BAM within the focus area Material.
Thermography is one on the most promising techniques for in-situ monitoring for metal additive manufacturing processes. The high process dynamics and the strong focus of the laser beam cause a very complex thermal history within the produced specimens, such as multiple heating cycles within single layer expositions. This complicates data interpretation, e.g., in terms of cooling rates. A quantity that is easily calculated is the time a specific area of the specimen is at a temperature above a chosen threshold value (TOT). Here, we discuss variations occurring in time-over-threshold-maps during manufacturing of a defect free cuboid specimen.
In-situ Prozessüberwachung in der additiven Fertigung von Metallen mittels optischer Verfahren
(2020)
Einer der aussichtsreichsten Ansätze, die Qualität und Sicherheit der gefertigten Teile in der metallbasierten additiven Fertigung (AM) zu erhöhen und die Notwendigkeit aufwändiger und zeitintensiver, zerstörender oder zerstörungsfreier Prüfungen (ZfP) nach der Fertigung zu verringern, liegt in dem Einsatz von in-situ Prozessüberwachungstechniken. Bereits jetzt werden erste Messsysteme zur Kontrolle der Energiequelle, des Bauraums, des Schmelzbades und der Bauteilgeometrie kommerziell angeboten. Weitere ZfP Verfahren, wie z.B. die aktive und passive Thermografie, werden in der Literatur als geeignet für die in-situ Anwendung angesehen, allerdings gibt es noch wenig konkrete praktische Umsetzungen, da die Möglichkeiten und individuellen Grenzen dieser Methoden, angewendet auf AM, noch nicht ausreichend erforscht sind. Aus diesem Grund verfolgt die BAM mit dem Projekt „Process Monitoring of AM“ (ProMoAM) im Themenfeld Material das Ziel, Verfahren des Prozessmonitorings zur in-situ Bewertung der Qualität additiv gefertigter Metallbauteile weiterzuentwickeln.
Im Beitrag wird zunächst das Projekt vorgestellt und anschließend der Fokus auf eine Messserie gelegt, in der Probekörper aus dem austenitischen Edelstahl 316L mit lokal variierenden Prozessparametern mittels selektiven Laserschmelzen (L-PBF) aufgebaut wurden. Der Bauprozess wurde hierbei durch das maschineneigene, koaxial arbeitende Photodiodensystem (Melt-Pool-Monitoring), einer Mittelwellen-Infrarotkamera und einer optischen Tomografiekamera im sichtbaren Wellenlängenbereich (Langzeitbelichtung für die Dauer eines Lagenaufbaus mit einer CMOS-Kamera mit hoher Ortsauflösung) simultan überwacht. Als Referenz für diese Methoden wurden die Probekörper mittels Computertomografie untersucht. Für die dabei anfallenden teils großen Datenmengen wurden Algorithmen für ein effizientes Preprocessing entwickelt. Es wurden Merkmale der Messdaten in Korrelation zu Fehlern und Inhomogenitäten extrahiert, welche für die einzelnen Methoden vergleichend vorgestellt und diskutiert werden.
Introduction to ProMoAM
(2021)
Additive manufacturing of metals offers the opportunity to build parts with a high degree of complexity without additional costs, opening a new space for design optimization. However, the processes are highly complex and due to the rapid thermal cycles involved, high internal stresses and peculiar microstructures occur, which influence the parts mechanical properties. To systematically examine the formation of internal stresses and the microstructure, in-process spatially resolved measurements of the part temperature are needed. If the emissivity of the inspected part is known, its thermodynamic temperature can be reconstructed by a suited radiometric model. However, in additive manufacturing of metals, the emissivity of the part surface is strongly inhomogeneous and rapidly changing due to variations of, e.g., the degree of oxidation, the material state and temperature. Thus, here, the applicability of thermography in the determination of thermodynamic temperatures is limited. However, measuring the process thermal radiation at different wavelengths simultaneously enables one to separate temperature and emissivity spatially resolved to obtain further insight into the process. Here, we present results of an initial study using multispectral thermography to obtain real temperatures and emissivities in the powderfree LMD process.
Due to the rapid thermal cycles involved in additive manufacturing of metals, high internal stresses and peculiar microstructures occur, which influence the parts mechanical properties. To systematically examine their formation, in-process measurements of the temperature are needed. Since the part emissivity is strongly inhomogeneous and rapidly changing in the process, the applicability of thermography for the determination of thermodynamic temperatures is limited. Measuring the thermal radiation in different wavelengths simultaneously, temperature and emissivity can be separated. Here, we present results of a preliminary study using multispectral thermography to obtain real temperatures and emissivities in directed energy deposition (DED) processes.
Aktuell werden Prozessmonitoringsysteme in der additiven Fertigung (AM) zur Überwachung der Energiequelle, des Bauraums, des Schmelzbades und der Bauteilgeometrie zumindest im metallbasierten AM schon kommerziell angeboten. Weitere Verfahren aus den Bereichen der Optik, Spektroskopie und zerstörungsfreien Prüfung werden in der Literatur als geeignet für die in-situ Anwendung bezeichnet, es finden sich aber nur wenige Berichte über konkrete Umsetzungen in die Praxis.
Die Bundesanstalt für Materialforschung und -prüfung hat ein neues Projekt gestartet, dessen Ziel die Entwicklung von Verfahren des Prozessmonitorings zur in-situ Bewertung der Qualität additiv gefertigter Bauteile in AM-Prozessen mit Laser- bzw. Lichtbogenquellen ist. Verschiedene Verfahren der zerstörungsfreien Prüfung, wie Thermografie, optische Tomografie, optische Emissionsspektroskopie, Wirbelstromprüfung und Laminografie werden in verschiedenen AM-Prozessen zum Einsatz gebracht und die Ergebnisse fusioniert. Die evaluierten Ergebnisse werden mit Referenzverfahren wie Computertomografie und Ultraschall-Tauchtechnik verglichen. Ziel ist eine deutliche Reduzierung aufwändiger und zeitintensiver, zerstörender oder zerstörungsfreier Prüfungen nach der Fertigung des Bauteiles und zugleich eine Verringerung von Ausschussproduktion.
Hier wird das Projekt als Ganzes vorgestellt und der Fokus auf verschiedene Methoden der Temperaturmessung mit Hilfe der Thermografie gelegt. Anforderungen an die Messtechnik für verschiedene AM-Systeme werden diskutiert und erste experimentelle Ergebnisse werden präsentiert.
Additive manufacturing (AM) opens the route to a range of novel applications. However, the complexity of the manufacturing process poses a challenge to produce defect-free parts with a high reliability. Since process dynamics and resulting microstructures of AM parts are strongly influenced by the involved temperature fields and cooling rates, thermography is a valuable tool for process monitoring. Another approach to monitor the energy input into the part during process is the use of optical tomography.
Common visual camera systems reach much higher spatial resolution than infrared thermography cameras, whereas infrared thermography provides a much higher temperature dynamic. Therefore, the combined application increases the depth of information. Here, we present first measurement results using a laser beam melting setup that allows simultaneous acquisition of thermography and optical tomography from the same point of view using a beam splitter. A high-resolution CMOS camera operating in the visible spectral range is equipped with a near infrared bandpass filter and images of the build plate are recorded with long-term exposure during the whole layer exposing time. Thus, areas that reach higher maximum temperature or are at elevated temperature for an extended period of time appear brighter in the images. The used thermography camera is sensitive to the mid wavelength infrared range and records thermal videos of each layer exposure at an acquisition rate close to 1 kHz.
As a next step, we will use computer tomographic data of the built part as a reference for defect detection.
This research was funded by BAM within the focus area Materials.
Aktuell werden Prozessmonitoringsysteme in der additiven Fertigung (AM) zur Überwachung der Energiequelle, des Bauraums, des Schmelzbades und der Bauteilgeometrie zumindest im metallbasierten AM schon kommerziell angeboten. Weitere Verfahren aus den Bereichen der Optik, Spektroskopie und zerstörungsfreien Prüfung werden in der Literatur als geeignet für die in-situ Anwendung bezeichnet, es finden sich aber nur wenige Berichte über konkrete Umsetzungen in die Praxis.
Die Bundesanstalt für Materialforschung und -prüfung hat ein neues Projekt gestartet, dessen Ziel die Entwicklung von Verfahren des Prozessmonitorings zur in-situ Bewertung der Qualität additiv gefertigter Bauteile in AM-Prozessen mit Laser- bzw. Lichtbogenquellen ist. Verschiedene Verfahren der zerstörungsfreien Prüfung, wie Thermografie, optische Tomografie, optische Emissionsspektroskopie, Wirbelstromprüfung und Laminografie werden in verschiedenen AM-Prozessen zum Einsatz gebracht und die Ergebnisse fusioniert. Die evaluierten Ergebnisse werden mit Referenzverfahren wie Computertomografie und Ultraschall-Tauchtechnik verglichen. Ziel ist eine deutliche Reduzierung aufwändiger und zeitintensiver, zerstörender oder zerstörungsfreier Prüfungen nach der Fertigung des Bauteiles und zugleich eine Verringerung von Ausschussproduktion.
Hier wird das Projekt als Ganzes vorgestellt und der Fokus auf verschiedene Methoden der Temperaturmessung mit Hilfe der Thermografie gelegt. Anforderungen an die Messtechnik für verschiedene AM-Systeme werden diskutiert und erste experimentelle Ergebnisse werden präsentiert.
The project ProMoAM is presented. The goal of the project is to evaluate which NDT techniques or combination of techniques is suited for in-situ quality assurance in additive manufacturing of metals. To this end, also 3d-data fusion and visualization techniques are applied. Additional ex-situ NDT-techniques are used as references for defect detection and quantification. Feasability studies for NDT-techniques that are presently not applicable for in-situ use are performed as well.
The presentation gives a brief overview of the whole project and the different involved NDT-techniques.
Additive manufacturing (AM) offers a range of novel applications. However, the manufacturing process is complex and the production of defect-free parts with high reliability and durability is still a challenge. Thermography is a valuable tool for process surveillance, especially in metal AM processes. The high process temperatures allow one to use cameras usually operating in the visible spectral range. Here, we compare the results of measurements during the manufacturing process of a commercial laser metal deposition setup using a mid-wavelength-IR camera with those from a visual spectrum high-speed camera with band pass filter in the near-IR range.
Due to the rapid thermal cycles involved in additive manufacturing of metals, high internal stresses and peculiar microstructures occur, which influence the parts mechanical properties. To systematically examine their formation, in-process measurements of the temperature are needed. Since the part emissivity is strongly inhomogeneous and rapidly changing in the process, the applicability of thermography for the determination of thermodynamic temperatures is limited. Measuring the thermal radiation in different wavelengths simultaneously, temperature and emissivity can be separated. Here, we present results of a preliminary study using multispectral thermography to obtain real temperatures and emissivities in directed energy deposition (DED) processes.
Additive manufacturing offers a range of novel applications. However, the manufacturing process is complex and the production of almost defect-free parts with high reliability and durability is still a challenge. Thermography is a valuable tool for process surveillance, especially in metal additive manufacturing processes. The high process temperatures allow one to use cameras usually operating in the visible spectral range. Here, we compare the results of measurements during the manufacturing process of a commercial laser metal deposition setup using a mid wavelength infrared camera with those from a short wavelength infrared camera and those from a visual spectrum high-speed camera with band pass filter in the near infrared range.
Materials
(2022)
This presentation summarizes outcomes of the CUSP projects POLYRISK and PlasticsFatE according to thermoanalytical methods.It highlights the importants of analytical methods to measure physical and chemical properties of the test materials. These informations are neccessary for interpretation of the toxicological test results.
Der Vortrag wurde im Rahmen der Abschlusskonferenz des Forschungsschwerpunktes "Plastik in der Umwelt" des BMBF gehalten. Er fasst die Ergebnisse des Verbundprojektes RUSEKU zusammen. Es wurde die Herstellung verschiedener Testmaterialien für die Mikroplastik (MP) Analytik beschrieben. Im weiteren geht es um verschiedene Ansätze MP kostengünstig und schnell zu detektieren, z.B. mit Nahinfrarotspektroskopie. Nanoplastik konnte mit der Transmissionselektronenmikroskopie sichtbar gemacht werden. Für die praxisnahe Beprobung von Gewässern wurde die Fraktionierte Filtration entwickelt. Integrale Beprobungen können mit dem Sedimentationskasten erfolgen. Als Beispiele für die Beprobung realer Gewässer wurde das urbane Abwassersystem Kaiserslautern, Getränkewasser und Waschmaschinenwasser gezeigt.
Mikroplastik findet sich in Ozeanen, Seen, Flüssen und Bächen. Es kann in unserem Boden, in der Luft und sogar in Organismen nachgewiesen werden. Jedes Jahr werden weltweit Millionen Tonnen freigesetzt. Doch wo und wie landet Mikroplastik in der Umwelt? Und wie können wir diese winzigen Partikel nachweisen?