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Die Feuerwiderstandsdauer von ungeschützten Stahlbauteilen lässt sich durch den Einsatz reaktiver Brandschutzsysteme (RBS) signifikant erhöhen. Durch den profilfolgenden Auftrag der Brandschutzbeschichtung und die hierfür erforderlichen geringen Trockenschichtdicken, welche in der Regel nur wenige Millimeter betragen, können neben den brandschutztechnischen Anforderungen auch die an die Stahlkonstruktion gestellten gestalterischen Ansprüche erfüllt werden. Kommt es zu einem Brand, schäumt das reaktive Brandschutzsystem auf und bildet eine thermische Schutzschicht um das Stahlbauteil aus. Dadurch wird die Erwärmung des Stahls verlangsamt und der Festigkeitsverlust infolge Temperatur wird verzögert. Die Verwendung von reaktiven Brandschutzsystemen auf Stahlbauteilen wird durch Zulassungen geregelt. In Bezug auf den durch die Zulassung geregelten Anwendungsbereich von reaktiven Brandschutzsystemen auf zugbeanspruchten Stahlbauteilen haben sich in den vergangenen Jahren verschiedene Änderungen ergeben. Der nachfolgende Beitrag gibt hierzu einen aktuellen Überblick und beschreibt die Hintergründe, welche zu den neuen Regelungen geführt haben. Ferner erfolgt in diesem Zusammenhang ein Ausblick auf noch zu untersuchende Fragestellungen, welche bisher noch nicht durch die Regelungen in den Zulassungen abgedeckt werden. Bei den nachfolgenden Ausführungen handelt es sich um einen Auszug des Beitrages für die 18. EIPOS-Sachverständigentage Brandschutz.
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.
For the first time, X-ray refraction techniques are proven for the identification of void formation in Ti-6Al-4V parts produced by selective laser melting. The topology and volume fraction of pores are measured in samples produced with different laser energy density. Unique X-ray refraction methods identify different kinds of defects, characteristic to the regions below and above the Optimum laser energy density, namely unprocessed powder (unmolten powder particles, balling effect, and Fusion defects) from empty keyhole pores. Furthermore, it is possible to detect small inhomogeneities (voids or cracks) with sizes below the spatial resolution of optical microscopy and X-ray computed tomography.
In laser machining with ultrashort laser pulses unwanted X-ray radiation in the keV range can be generated when a critical laser intensity is exceeded. Even if the emitted X-ray dose per pulse is low, high laser repetition rates can lead to an accumulation of X-ray doses beyond exposure safety limits. For 925 fs pulse duration at a center wavelength of 1030 nm, the X-ray emission was investigated up to an intensity of 2.6 × 10^14 W/cm2. The experiments were performed in air with a thin disk laser at a repetition rate of 400 kHz. X-ray spectra and doses were measured for various planar target materials covering a wide range of the periodic table from aluminum to tungsten. Without radiation shielding, the measured radiation doses at this high repetition rate clearly exceed the regulatory limits. Estimations for an adequate radiation shielding are provided.
This paper describes a wireless mobile prototype able to perform optical measurements by means of a miniatur-ized spectrometer for low light analysis, e.g. fluorescent sensors. Evaluations, calculations, calibration management and result display are performed by a computer or a standard tablet. The device was designed primarily to detect traces of oil in drinking or ground water and for the analyses of crude oils. However, it can also address a wide range of fluorescent sensors. The fast and user-friendly inspection of water quality or oil properties, as well as the adaptability and mobility, make the device attractive for a variety of users. Further application areas could be easily imple-mented by adapting the optics and the software (database, data processing and calibration plots, etc.)
An artificial digestion of silver nitrate is reported. It is shown that AgSCN nanoparticles emerge from ionic silver in saliva and remain present during the entire digestion process. The particles were characterized by infrared spectroscopy and small- and wide-angle X-ray scattering (SAXS/WAXS) regarding their composition and size distribution.
Welding residual stresses have an impact on the performance of welded structures, on their fracture resistance, their resistance against fatigue crack propagation and, most important, their fatigue strength and fatigue lifetime. The present paper provides an overview on the issue mainly from the point of view of the application of fracture mechanics to the determination of the fatigue strength as the topic of this Special issue. Besides own experimental and theoretical data a comprehensive discussion is provided in that context which includes the definition and interaction of short- and long-range (or reaction) residual stresses, the effect of cyclic mechanical loading and its treatment in fracture and fatigue analyses.
Distributed vibration sensing in optical fibers opened entirely new opportunities and penetrated various sectors from security to seismic monitoring. Here, we demonstrate a most simple and robust approach for dynamic strain measurement using wavelength-scanning coherent optical time domain reflectometry (C-OTDR). Our method is based on laser current modulation and Rayleigh backscatter shift correlation. As opposed to common single-wavelength phase demodulation techniques, also the algebraic sign of the strain change is retrieved. This is crucial for the intended applications in structural health monitoring and modal analysis. A linear strain response down to 47.5 pε and strain noise of 100 pε/√Hz is demonstrated for repetition rates in the kHz range. A field application of a vibrating bridge is presented. Our approach provides a cost-effective high-resolution method for structural vibration analysis and geophysical applications.
Im Stahlbau wird die feuerwiderstandserhöhende Wirkung reaktiver Brandschutzsysteme (RBS) bereits seit Jahrzehnten erfolgreich und mit stetig wachsender Nachfrage genutzt. Die Anwendung dieser Systeme wird durch Zulassungen geregelt. Die Ermittlung des Beitrages reaktiver Brandschutzsysteme zur Feuerwiderstandsdauer von Stahlbauteilen wird in der Regel mit Hilfe von mechanisch belasteten und unbelasteten Brandversuchen beurteilt. Ein entsprechendes Prüf- und Bewertungsverfahren war bisher für Träger und Stützen, jedoch nicht für Zugglieder vorhanden. Mehrjährige Forschungen, haben in Deutschland zur Entwicklung eines neuen Prüf- und Bewertungsverfahrens geführt, so dass der durch Zulassungen geregelte Anwendungsbereich reaktiver Brandschutzsysteme auf filigrane Stahlzugglieder, insbesondere mit Vollprofil, erweitert werden konnte. Der Beitrag beschreibt die Besonderheiten und Herausforderungen für den Einsatz von reaktiven Brandschutzsystemen auf filigranen Stahlzuggliedern, die wesentlichen Einflussparameter sowie die maßgebenden Versagensmechanismen. Ferner wird gezeigt, wie anhand von Brandversuchen, Materialuntersuchungen im Hochtemperaturbereich und numerischen Simulationen das neue Prüf- und Bewertungsverfahren entwickelt, validiert und angewendet wurde. Abschließend erfolgt ein Ausblick auf noch zu untersuchende Fragestellungen, z. B. hinsichtlich der Bauteilorientierung sowie zum Umgang mit den Anschlussbauteilen von Stahlzuggliedern.
A composite material is a combination of two or more materials with very different mechanical, thermal and electrical properties. The various forms of composite materials, due to their high material properties, are widely used as structural materials in the aviation, space, marine, automobile, and sports industries. However, some defects like voids, delamination, or inhomogeneous fiber distribution that form during the fabricating processes of composites can seriously affect the mechanical properties of the composite material. In this study, several imaging NDE techniques such as: thermography, high frequency eddy current, ultrasonic, x-ray radiography, x-ray laminography, and high resolution x-ray CT were conducted to characterize the microstructure of carbon fiber composites. Then, a 3D analysis was implemented by the destructive technique of serial sectioning for the same sample tested by the NDE methods. To better analyze the results of this work and extract a clear volume image for all features and defects contained in the composite material, an intensive comparison was conducted among hundreds of 3D-NDE and multi serial sections’ scan images showing the microstructure variation.
Fuel contamination of soils display complex and variable hydrocarbon mixtures with different volatility and toxicity characteristics. A recently suggested headspace procedure for the structure-based quantification of volatile hydrocarbons is evaluated regarding repeatability, reproducibility, and practical robustness. Three aliphatic and three aromatic fractions covering the boiling range between 69 and 216°C were defined as summation parameters by their respective equivalent carbon number ranges. A standard mixture of 35 aliphatic and aromatic hydrocarbons was used for calibration on basis of selected mass fragments specific for the aliphatics and aromatics, respectively. Two standard soils were fortified with the standard mixture or different fuels, respectively, and submitted to the analytical procedure. Limit of detection (LOD) and limit of quantification (LOQ) were for all fractions lower than 0.1 and 0.3 mg/kg, respectively. Analyte recovery was linear up to between 20 and 110 mg hydrocarbons/kg soil depending on the fraction. Hydrocarbon recovery ranged between 80% and 110% depending on the fraction and the repeatability was typically better than 10%. Finally, the impact of extraction solvent variation, column solid-phase polarity, and alternative summation of fractions were investigated. The procedure was applied to liner samples taken from a site contaminated with aviation fuel and its practicability is discussed.
Abstract While classically used to visualise the magnetic microstructure of functional materials (e.g., for magnetic applications), in this study, the Bitter technique was applied for the first time to visualise macroscopic deformation gradients in a polycrystalline low-carbon steel. Spherical indentation was chosen to produce a multiaxial elastic–plastic deformation state. After removing the residual imprint, the Bitter technique was applied, and macroscopic contrast differences were captured in optical microscopy. To verify this novel characterisation technique, characteristic “hemispherical” deformation zones evolving during indentation were identified using an analytical model from the field of contact mechanics. In addition, near-surface residual stresses were determined experimentally using synchrotron radiation diffraction. It is established that the magnetic domain distribution contrast provides deformation-related information: regions of different domain wall densities correspond to different “hemispherical” deformation zones (i.e., to hydrostatic core, plastic zone and elastic zone, respectively). Moreover, the transitions between these three zones correlate with characteristic features of the residual stress profiles (sign changes in the radial and local extrema in the hoop stress). These results indicate the potential of magnetic domain distribution imaging: visualising macroscopic deformation gradients in fine-grained ferromagnetic material with a significantly improved spatial resolution as compared to integral, mean value-based measurement methods.
Virologists. You might know a couple of them, but unless you are a virologist yourself, the probability that you have collaborated with one in the past is low. The community is relatively small, but they pack a heavy punch and are expected to play a leading role in the research into pathogens that lies ahead. You may ask why we think virologists are our future. Suffice it to say that it is not just because they have invented technologies that belong to the space age, including use of viruses as vehicles to shuttle genes into cells[1], organic nanoparticles with specific tools attached to their surfaces to get inside target cells[2], and using genetically modified viruses as therapies to fight against cancer[3]. Did you know that virologists currently only know of about 3,200 viral species but that more than 320,000 mammal-associated viruses[4] are thought to await discovery? Just think about the viruses hidden in the Arctic ice[5] or in the insects and other animals from once cut-off regions in the world, which now face ever-increasing human exposure[6]. But a heroic (as well as an apocalyptic) role for virologists may also be on the horizon, as the adoption of phage therapy may, in the future, be used to control harmful bacteria when antibiotics fail
Automatic vibration-based structural health monitoring has been recognized as a useful alternative or addition to visual inspections or local non-destructive testing performed manually. It is, in particular, suitable for mechanical and aeronautical structures as well as on civil structures, including cultural heritage sites. The main challenge is to provide a robust damage diagnosis from the recorded vibration measurements, for which statistical signal processing methods are required. In this chapter, a damage detection method is presented that compares vibration measurements from the current system to a reference state in a hypothesis test, where data9
related uncertainties are taken into account. The computation of the test statistic on new measurements is straightforward and does not require a separate modal identification. The performance of the method is firstly shown on a steel frame structure in a laboratory experiment. Secondly, the application on real measurements on S101 Bridge is shown during a progressive damage test, where damage was successfully detected for different damage scenarios.
Validation of artificial defects for non-destructive testing measurements on a reference structure
(2018)
Non-destructive testing was established over the last decades as an important tool for assessing damages, material characterization and quality assurance in civil engineering. For example, Ground Penetrating Radar (GPR) can be used to scan large areas of concrete structures to determine the spatial position of the reinforcement. With the ultrasonic echo method, the thickness of concrete structures can be easily determined even if a high density of reinforcement is given. Various methods and processes have been developed for the validation of NDT procedures aiming at ensuring the quality of measurements in practical use. The Probability of Detection (POD) for example, is an available method to compare different technical devices with each other quantitatively regarding their performance. With this method, the best suited testing device for a specific inspection task under defined boundary conditions can be selected. By using the Guide to the Expression of Uncertainty in Measurement (GUM), it is possible to quantify the measurement uncertainty of an inspection procedure for a specific task. Another important aspect to improve the acceptance of Non-destructive testing methods is the development of reference specimens.
Reference specimens serve for the calibration and further development of NDT methods under realistic conditions in different laboratories under the same conditions. A particular challenge here is the most realistic representation of a damage that can occur at building sites. Possible damages include for example horizontal and vertical cracks or honeycombs in concrete. Such a reference structure was built for the development of a new design of power plant constructions. Comparative studies on the manufacturing of realistic honeycombs and delaminations were carried out in advance on a test specimen. The results of this study are presented here.
During the energy transformation from fossil fuels to renewable energy sources, the use of hydrogen as fuel and energy storage can play a key role. This presents new challenges to industry and the scientific community alike. The storage and transport of hydrogen, which is nowadays mainly realized by austenitic stainless steels, remains problematic, which is due to the degradation of mechanical properties and the possibility of phase transformation by hydrogen diffusion and accumulation. The development of materials and technologies requires a fundamental understanding of these degradation processes. Therefore, studying the behavior of hydrogen in austenitic steel contributes to an understanding of the damage processes, which is crucial for both life assessment and safe use of components in industry and transportation. As one of the few tools that is capable of depicting the distribution of hydrogen in steels, time-of-flight secondary ion mass spectrometry was conducted after electrochemical charging. To obtain further information about the structural composition and cracking behavior, electron-backscattered diffraction and scanning electron microscopy were performed. Gathered data of chemical composition and topography were treated employing data fusion, thus creating a comprehensive portrait of hydrogen-induced effects in the austenite grade AISI 304L. Specimens were electrochemically charged with deuterium instead of hydrogen. This arises from the difficulties to distinguish between artificially charged hydrogen and traces existing in the material or the rest gas in the analysis chamber. Similar diffusion and permeation behavior, as well as solubility, allow nonetheless to draw conclusions from the experiments.
Uptake and molecular impact of aluminum-containing nanomaterials on human intestinal caco-2 cells
(2018)
Aluminum (Al) is one of the most common elements in the earth crust and increasingly used in food, consumer products and packaging. Its hazard potential for humans is still not completely understood. Besides the metallic form, Al also exists as mineral, including the insoluble oxide, and in soluble ionic forms. Representatives of these three species, namely a metallic and an oxidic species of Al-containing nanoparticles and soluble aluminum chloride, were applied to human intestinal cell lines as models for the intestinal barrier. We characterized physicochemical particle parameters, protein corona composition, ion release and cellular uptake. Different in vitro assays were performed to determine potential effects and molecular modes of Action related to the individual chemical species. For a deeper insight into signaling processes, microarray transcriptome analyses followed by bioinformatic data analysis were employed. The particulate Al species showed different solubility in biological media. Metallic Al nanoparticles released more ions than Al2O3 nanoparticles, while AlCl3 showed a mixture of dissolved and agglomerated particulate entities in biological media. The protein corona composition differed between both nanoparticle species. Cellular uptake, investigated in transwell experiments, occurred predominantly in particulate form, whereas ionic Al was not taken up by intestinal cell lines. Transcellular transport was not observed. None of the Al species showed cytotoxic effects up to 200 mg Al/mL. The transcriptome analysis indicated mainly effects on oxidative stress pathways, xenobiotic metabolism and metal homeostasis. We have shown for the first time that intestinal cellular uptake of Al occurs preferably in the particle form, while toxicological effects appear to be ion-related.
Glass-ceramics are noted for their unusual combination of properties and manifold commercialized products for consumer and specialized markets. Evolution of novel glass and ceramic processing routes, a plethora of new compositions, and unique exotic nano- and microstructures over the past 60 years led us to review the Definition of glass-ceramics. Well-established and emerging processing methods, such as co-firing, additive manufacturing, and laser patterning are analyzed concerning the core requirements of processing glass-ceramics and the Performance of the final products. In this communication, we propose a revised, updated definition of glass-ceramics, which reads “Glass-ceramics are inorganic, non-metallic materials prepared by controlled crystallization of glasses via different processing methods. They contain at least one type of functional crystalline phase and a residual glass. The volume fraction crystallized may vary from ppm to almost 100%”.
Heizöllagerbehälter aus Polyethylenformstoffen werden seit Beginn der 70-iger Jahre in Deutschland hergestellt. Die Hersteller empfehlen zur Gewährleistung der Sicherheit nach Ablauf von 30 Jahren den Ersatz dieser Behälter. Polyethylenformstoffe unterliegen im Laufe ihrer Nutzungsdauer der Alterung durch die Veränderung ihrer Eigenschaften. Das Ausmaß der Alterung und die Art des Abbauvorganges hängen im Wesentlichen vom chemischen Abbau des Polyethylens, der Wanddicke des Behälters und den Umgebungsbedingungen ab. Bisher lagen keine Untersuchungen zum Langzeitverhalten der Polyethylenformstoffe vor, insbesondere nach einer Nutzungsdauer der Tanks über 30 Jahre. Ziel der Untersu-chungen war, den tatsächlichen Schädigungsgrad der Polyethylenformstoffe im Vergleich zu den unbelasteten Formstoffen zu ermitteln. Da die BAM bis Mitte der 90-iger Jahre für die Prüfungen und Gutachten zur Zulassung dieser Behälter zuständig war, sind die Werkstoffdaten noch vorhanden.
Als Untersuchungsmethoden wurden die Bestimmung der Schmelze-Masse-Fließrate (MFR) und die Fourier-Transformation-IR-Spektroskopie (FTIR) von Tankausschnitten aus dem Bereich des Bodens, des Mantels und des Daches von 10 ausgesonderten Behältern aus den Polyethylenformstoffen A und B herangezogen. Die Messungen der MFR der Tankaus-schnitte aus diesen Bereichen zeigten Unterschiede in den Werten in Abhängigkeit vom Ge-wicht (5 kg oder 21,6 kg), welches eingesetzt wurde. Eine Abnahme der MFR-Werte wurde für die größere Anzahl der Tankwandungsausschnitte aus dem Formstoff B nach einer Lebensdauer der Tanks > 30 Jahre gemessen. Dieser Formstoff wurde hauptsächlich durch innere Alterung infolge Vernetzungen, Verzweigungen und Weichmacherverlust und weniger durch oxidativen Abbau geschädigt. Die FTIR-Messungen der Proben aus dem Bereich des Bodens und des Mantels der Tanks zeigten, dass die Intensität der asymmetrischen/symmetrischen CH2 -Streckschwingungen im Bereich: 2800 - 2900 cm-1 und der CH2 -Biegeverformungsschwingung bei 1400 cm-1 aufgrund von Kettenspaltungen zugenommen haben. Die Intensität der Carbonylstreckschwingung C=O bei 1740 cm-1 ist niedrig. Sie ist ein Maß für die Oxidation des Polymerwerkstoffes.
Unprecedented Ionization Processes in Mass SpectrometryProvide Missing Link between ESI and MALDI
(2018)
In the field of mass spectrometry,producing intact, highly-charged protein ions from surfaces is a conundrum with significant potential payoff in application areas ranging from bio-medical to clinical research. Here, we report on the ability to form intact, highly-charged protein ions on high vacuum time-of-flight mass spectrometers in the linear and reflectron modes achievable using experimental conditions that allow effective matrix removal from both the sample surfaces and from the charged clusters formed by the laser Ablation event. The charge states are the highest reported on high vacuum mass spectrometers, yet they remain at only around athird of the highest charge obtained using laser ablation with a suitable matrix at atmospheric pressure. Other than physical instrument modifications, the key to forming abundant and stable highly-charged ions appears to be the volatility of the matrix used. Cumulative results suggest mechanistic links between the ionization process reported here and traditional ionization methods of electrospray ionization and matrix-assisted laser desorp-tion/ionization.
Negatively charged flat gold nanotriangles, formed in a vesicular template phase and separated by an AOT-micelle-based depletion flocculation, were reloaded by adding a cationic polyelectrolyte, that is, a hyperbranched polyethylenimine (PEI). Heating the system to 100 °C in the presence of a gold chloride solution, the reduction process leads to the formation of gold nanoparticles inside the polymer shell surrounding the nanoplatelets. The gold nanoparticle formation is investigated by UV−vis spectroscopy, small-angle X-ray scattering, and dynamic light scattering measurements in combination with transmission electron microscopy. Spontaneously formed gold clusters in the hyperbranched PEI shell with an absorption maximum at 350 nm grow on the surface of the nanotriangles as hemispherical particles with diameters of ∼6 nm. High-resolution micrographs show that the hemispherical gold particles are crystallized onto the {111} facets on the bottom and top of the platelet as well as on the edges without a grain boundary. Undulated gold nanoplatelet superstructures with special properties become available, which show a significantly modified performance in SERS-detected photocatalysis regarding both reactivity and enhancement factor.
Two-dimensional residual stress mapping of multilayer LTT weld joints using the contour method
(2018)
Low transformation temperature (LTT) weld filler materials offer an attractive alternative to cost intensive postweld treatments as they can mitigate detrimental welding residual stresses during the welding process. Compared to conventional weld filler materials, LTT alloys are characterized by a delayed martensite transformation at low temperatures, which can result in compressive residual stresses in the weld. The high strength of these filler materials makes them potentially applicable to high-strength steels as well as for a large amount of requested repair works in steel structures. The focus of the study is on the confirmation of the LTT idea with regard to the residual stress state for multipass weld lines processed by metal active gas welding. It is demonstrated that the contour method is a well-suited technique for measuring the residual stress in the weld joint as it gives an entire two-dimensional map of the residual stress state in the weld line, heat affected zone (HAZ), and base material. The technique was applied at different LTT alloys with varying chemical compositions. Additionally, the results are compared to residual stress maps that were determined by Neutron diffraction using the Strain Analyzer for Large Scale Engineering Applications, an
instrument referred to as SALSA, at the Institut Laue-Langevin in Grenoble. For all investigated specimens, compressive residual stress distributions were determined in the area of the weld joint and the HAZ. They are balanced by tensile residual stresses in the surrounding base material. However, it is shown that the size of theregion exhibiting compressive residual stresses and the absolute values of the compressive residual stresses depend on the chemical composition of the weld filler material.
Analysis of microplastic particles (MP) in environmental samples needs sophisticated techniques and is time intensive due to sample preparation and detection. An alternative to the most common (micro ) spectroscopic techniques, FTIR or Raman spectroscopy, are the thermoanalytical methods, where specific decomposition products can be analyzed as marker compounds for different kind of plastics types and mass contents. Thermal extraction desorption gas chromatography mass spectrometry (TED-GC-MS) allows the fast identification and quantification of MP in environmental samples without sample preparation. Whereas up to now only the analysis of thermoplastic polymers was realized, this is the first time that even the analysis of tire wear (TW) content in environmental samples is possible. Various marker compounds for TW were identified. They include characteristic decomposition products of elastomers, antioxidants and vulcanization agents. Advantages and drawbacks of these marker substances were evaluated. Environmental samples from street run off were exemplarily investigated and presented.
Commercial grade-1 titanium samples (Ti, 99.6%) were treated using three alternative methods, (i) femtosecond laser processing, (ii) thermal heat treatment, and (iii) electrochemical anodization, respectively, resulting in the formation of differently conditioned superficial titanium oxide layers. The laser processing (i) was carried out by a Ti:sapphire laser (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz) in a regime of generating laser-induced periodic surface structures (LIPSS). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning setup for the processing of several square-millimeters large surface areas covered homogeneously by these nanostructures. The differently oxidized titanium surfaces were characterized by optical microscopy, micro Raman spectroscopy, variable angle spectroscopic ellipsometry, and instrumented indentation testing. The tribological performance was characterized in the regime of mixed friction by reciprocating sliding tests against a sphere of hardened steel in fully formulated engine oil as lubricant. The specific tribological performance of the differently treated surfaces is discussed with respect to possible physical and chemical mechanisms.
The water management in proton exchange membrane fuel cells (PEMFC) is strongly influenced by the design of the gas diffusion layers (GDL). Limiting current measurements in small-scale cells operating at high stoichiometries are useful to determine the oxygen transport resistance. The oxygen transport resistance increases, once water condenses inside the GDL. In this study a new electrochemical method for voltage loss estimation of GDL induced oxygen transport losses are presented. This new method, referred to as “transient limiting current” (TLC), is compared with the literature method. TLC allows a direct estimation of oxygen transport resistance at an arbitrarily conditioned state. This study also presents a case study of liquid water visualization of a PEM fuel cell with varying GDLs types.
With the help of quasi in-situ synchrotron X-ray computed tomography and time resolved radiography measurements we investigate appearance and distribution of liquid water inside the GDLs under limiting current conditions.
Thermoresponsive polymer coatings can facilitate cell sheet fabrication under mild conditions by promoting cell adhesion and proliferation at 37 1C. At lower temperatures the detachment of confluent cell sheets is triggered without enzymatic treatment. Thus, confluent cell sheets with intact extracellular matrix for regenerative medicine or tissue engineering applications become available. Herein, we applied the previously identified structural design parameters of functional, thermoresponsive poly(glycidyl ether) brushes on gold to the more application-relevant substrate glass via the self-assembly of a corresponding block copolymer (PGE-AA) with a short surface-reactive, amine-presenting anchor block. Both, physical and covalent immobilization on glass via either multivalent ionic interactions of the anchor block with bare glass or the coupling of the anchor block to a polydopamine (PDA) adhesion layer on glass resulted in stable coatings. Atomic force microscopy revealed a high degree of roughness of covalently attached coatings on the PDA adhesion layer, while physically attached coatings on bare glass were smooth and in the brush-like regime. Cell sheets of primary human dermal fibroblasts detached reliably (86%) and within 20 ± 10 min from physically tethered PGE-AA coatings on glass when prepared under cloud point grafting conditions. The presence of the laterally inhomogeneous PDA adhesion layer, however, hindered the spontaneous temperature-triggered cell detachment from covalently grafted PGE-AA, decreasing both detachment rate and reliability. Despite being only physically attached, self-assembled monolayer brushes of PGE-AA block copolymers on glass are functional and stable thermoresponsive coatings for application in cell sheet fabrication of human fibroblasts as determined by X-ray photoelectron spectroscopy.
The purpose of this study is to shed more light on the transesterification processes in alcohol-initiated and tin(II) 2-ethylhexanoate (SnOct2)-catalyzed polymerizations of lactides at low or moderate temperatures. Ethanol-initiated polymerizations are conducted in concentrated solutions at 80 °C and a strong dependence of even/odd equilibration on the alcohol/Sn ratio. Around or above 120 °C cyclization of poly(l-lactide) via “backbiting” occurs as a third mechanism. However, poly(m-lactide) shows a higher cyclization tendency and yields cyclics even at 100 °C. Combinations of ethanol and certain cyclic dibutyltin(IV) catalysts also yield cyclic oligomers of l-lactide at 80 °C. Reaction conditions allowing for a total suppression of all transesterification reactions are not found, but even-numbered poly(m-lactide)s with a purity >95% are obtained at 70 or 60 °C.
tNegatively charged ultrathin gold nanotriangles (AuNTs) were synthesized in a vesicular dioctyl sodiumsulfosuccinate (AOT)/phospholipid-based template phase. These “naked” AuNTs with localized surfaceplasmon resonances in the NIR region at about 1300 nm and special photothermal properties are ofparticular interest for imaging and hyperthermia of cancerous tissues. For these kinds of applicationsthe toxicity and the cellular uptake of the AuNTs is of outstanding importance. Therefore, this studyfocuses on the toxicity of “naked” AOT-stabilized AuNTs compared to polymer-coated AuNTs. Poly-meric coating consisted of non-modified hyperbranched poly(ethyleneimine) (PEI), maltose-modifiedpoly(ethyleneimine) (PEI-Mal) and heparin. The toxicological experiments were carried out with twodifferent cell lines (embryonic kidney carcinoma cell line HEK293T and NK-cell leukemia cell line YTS).This study revealed that the heparin-coating of AuNTs improved biocompatibility by a factor of 50 whencompared to naked AuNTs. Of note, the highest nontoxic concentration of the AuNTs coated with PEI andPEI-Mal is drastically decreased. Overall, this is mainly triggered by the different surface charges of poly-meric coatings. Therefore, AuNTs coated with heparin were selected to carry out uptake studies. Theirpromising high biocompatibility and cellular uptake may open future studies in the field of biomedicalapplications.
To keep pace with the rising number of detected mycotoxins, there is a growing need for fast and reliable toxicity tests to assess the potential threat to food safety. Toxicity tests with the bacterial-feeding nematode Caenorhabditis elegans as model organism are well established. In this study the C. elegans wildtype strain N2 (var. Bristol) was used to investigate the toxic effects of the food-relevant mycotoxins citrinin (CIT) and zearalenone-14-sulfate (ZEA-14-S) and zearalenone (ZEA) on different life cycle parameters including reproduction, thermal and oxidative stress resistance and lifespan. The metabolization of the mycotoxins by the nematodes in vivo was investigated using HPLC-MS/MS. ZEA was metabolized in vivo to the reduced isomers α-zearalenol (α-ZEL) and β-ZEL. ZEA 14-S was reduced to α-/β-ZEL 14-sulfate and CIT was metabolized to mono-hydroxylated CIT. All mycotoxins tested led to a significant decrease in the number of nematode offspring produced. ZEA and CIT displayed negative effects on stress tolerance levels and for CIT an additional shortening of the mean lifespan was observed. In the case of ZEA-14-S, however, the mean lifespan was prolonged. The presented study shows the applicability of C. elegans for toxicity testing of emerging food mycotoxins for the purpose of assigning potential health threats.
We demonstrate narrow band spectral intensity switching in dual-core photonic crystal fibers made of highly nonlinear glass under femtosecond excitation. The fibers expressed dual-core asymmetry, thus the slow and fast fiber cores were unambiguously distinguished according to their dispersion profiles. The asymmetry effect on the dual-core Propagation in anomalous dispersion region was studied both experimentally and numerically. The experimental study was carried
out using femtosecond laser amplifier system providing tunable pulses in range of 1500 nm - 1800 nm. The obtained results unveiled, that it is possible to improve nonlinearly the coupling between the two waveguides by excitation of the fast fiber core. The results were obtained in regime of high-order soliton propagation and were verified numerically by the coupled generalized nonlinear Schrödinger equations model. The spectral analysis of the radiation transferred to the non-excited core revealed the role of effects such as third order dispersion, soliton compression and spectral dependence of the coupling efficiency. The simulation results provide reasonable agreement with the experimentally observed spectral evolutions in the both fiber cores. Under 1800 nm excitation, narrow band spectral intensity switching was registered with contrast of 23 dB at 10 mm fiber length by changing the excitation pulse energy in sub-nanojoule range.
Here we demonstrate that by applying exclusively Martian resources a processing route involving suspensions of mineral particles called slurries or slips can be established for manufacturing ceramics on Mars. We developed water-based slurries without the use of additives that had a 51 wt. % solid load resembling commercial porcelain slurries in respect to the particle size distribution and rheological properties. These slurries were used to slip cast discs, rings and vases that were sintered at temperatures between 1000 and 1130 °C using different sintering schedules, the latter were set-up according the results of hot-stage microscopic characterization. The microstructure, porosity and the mechanical properties were characterized by SEM, X-ray Computer tomography and Weibull analysis. Our wet processing of minerals yields ceramics with complex shapes that show similar mechanical properties to porcelain and could serve as a technology for future Mars colonization. The best quality parts with completely vitrificated matrix supporting a few idiomorphic crystals are obtained at 1130 °C with 10 h dwell time with volume and linear shrinkage as much as ~62% and ~17% and a characteristic compressive strength of 51 MPa.
Time-resolved phase-contrast microscopy is employed to visualize spatio-temporal thermal transients induced by tight focusing of a single Ti:sapphire fs-laser pulse into a solid dielectric sample. This method relies on the coupling of the refractive index change and the sample temperature through the thermo-optic coefficient dn/dT. The thermal transients are studied on a timescale ranging from 10 ns up to 0.1 ms after laser excitation. Beyond providing direct insights into the laser–matter interaction, analyzing the results obtained also enables quantifying the local thermal diffusivity of the sample on a micrometer scale. Studies conducted in different solid dielectrics, namely amorphous fused silica (a-SiO2), a commercial borosilicate glass (BO33, Schott), and a custom alkaline earth silicate glass (NaSi66), illustrate the applicability of this approach to the investigation of various glassy materials.
THz and mid IR spectroscopy of high-molecular PE (HMW) and ultra high-molecular PE (UHMW) reveals modifications of the molecular structure. Characteristic absorption bands are changed if the two materials are exposed by γ-Co60 radiation up to 600 kGy and subsequently stored at an annealing temperature of 398 K until for 729 days.
A great amount of material properties is strongly influenced by dislocations, the carriers of plastic deformation. It is therefore paramount to have appropriate tools to quantify dislocation substructures with regard to their features, e.g., dislocation density, Burgers vectors or line direction. While the transmission electron microscope (TEM) has been the most widely-used equipment implemented to investigate dislocations, it usually is limited to the two-dimensional (2D) observation of three-dimensional (3D) structures. We reconstruct, visualize and quantify 3D dislocation substructure models from only two TEM images (stereo pairs) and assess the results. The reconstruction is based on the manual interactive tracing of filiform objects on both images of the stereo pair. The reconstruction and quantification method are demonstrated on dark field (DF) scanning (S)TEM micrographs of dislocation substructures imaged under diffraction contrast conditions. For this purpose, thick regions (> 300 nm) of TEM foils are analyzed, which are extracted from a Ni-base superalloy single crystal after high temperature creep deformation. It is shown how the method allows 3D quantification from stereo pairs in a wide range of tilt conditions, achieving line length and orientation uncertainties of 3% and 7°, respectively. Parameters that affect the quality of such reconstructions are discussed.
ABSTRACT: A collection of thioimidazolium salts were synthesized and used as a new class of nonvolatile alkylating agents. Their nonvolatility prevents exposure during use or handling and are thus drastically safer than conventional alkylating agents. We discovered that thioimidazolium Iodide salts cannot release volatile compounds in the solid state, but instead only decompose when molten. Since decomposition proceeds via alkyl iodide elimination, SN2 of iodide on the thioimidazolium cation is constrained in the solid state, and instead can occur only upon melting when ions are mobile. By smart design of these alkylators, the melting point and thus the decomposition temperature of these salts can be increased from 106 to 169 °C and release negligible volatile organic compounds prior to melting. Thioimidazolium-bis(trifluoromethanesulfonyl)imide (TFSI) ionic liquids act as a completely nonvolatile and air-stable TFSI-based alkylating agent and can be used for high-throughput Synthesis of TFSI ionic liquids without solvent. Alkyl groups from methyl to dodecyl can be transferred to a nucleophile and the product purified by sublimation of the thione byproduct, which can then be recycled. We also found that thioimidazolium salts with a dodecyl chain are bactericidal, yet can hydrolyze in water to form benign neutral products, and thus wont accumulate in the environment. These results demonstrate that thioimidazolium salts are a designable platform for the pursuit of safer and more environmentally friendly alkylating and antiseptic agents.
In this work, two novel donor/acceptor (D/A) complexes, namely, diindenoperylene (DIP)/1,3,4,5,7,8-hexafluoro-tetracyanonaphthoquinodimethane (F6TCNNQ) and alpha-sexithiophene (6T)/F6TCNNQ, are studied. The D/A complexes segregate in form of π−π stacked D/A cocrystals and can be observed by X-ray scattering. The different conformational degrees of freedom of the donor molecules, respectively, seem to affect the thin-film crystalline texture and composition of the D/A mixtures significantly. In equimolar mixtures, for DIP/F6TCNNQ, the crystallites are mostly uniaxially oriented and homogeneous, whereas for 6T/F6TCNNQ, a mostly 3D (isotropic) orientation of the crystallites and coexistence of domains of pristine compounds and D/A complex, respectively, are observed. Using optical absorption spectroscopy, we observe for each of the two mixed systems a set of new, strong transitions located in the near-IR range below the gap of the pristine compounds: such transitions are related to charge-transfer (CT) interactions between donor and acceptor. The optical anisotropy of domains of the D/A complexes with associated new electronic states is studied by ellipsometry. We infer that the
CT-related transition dipole moment is perpendicular to the respective π-conjugated planes in the D/A complex.
Thin Sol-Gel Alumina Coating as Protection of a 9% Cr Steel Against Flue Gas Corrosion at 650 °C
(2018)
Samples of sol-gel alumina coated and uncoated P92 steel were exposed to flue gas at 650 °C for 300 h. As result of this treatment a 50 µm thick bi-layered oxide scale had formed on the surface of the uncoated sample. Below the scale a 40 µm thick inner oxidation zone was detected. In contrast, the porous, micron thick alumina coating enabled the formation of a chromium oxide scale with a thickness of some nanometers at the interface between steel substrate and coating. In this case high temperature corrosion of the steel was prevented so far.
The main goal of the study was to evaluate the catalytic activity of two hybrid nanocatalysts consisting in Fe3O4 nanoparticles modified with either chitosan (CS) or polyethylene glycol (PEG)/ferrous oxalate (FO), and further deposited on solid substrate as thin films. X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and scanning electron microscopy (SEM) were employed for the structural and morphological characterizations of the heterogeneous catalysts. The Degradation kinetic studies of two reactive azo dye (Reactive Black 5 (RB5) and Reactive Yellow 84 (RY84)) as well as Bisphenol A (BPA) solutions were carried out using Fenton-like oxidation, in the presence of different concentrations of H2O2, at initial near-neutral pH and room temperature. The results indicated that a low amount of catalytic material (0.15 g/L), deposited as thin film, was able to efficiently trigger dye degradation in solution in the presence of 6.5mmol/LH2O2 for RB5 and of only 1.6mmol/LH2O2 in the case of BPA and RY84. In the presence of complex matrices such asWWTP waters, the removal of BPAwas low (only 24% for effluent samples). Our findings recommend the studied immobilized nanocatalysts as promising economical tools for the pretreatment of wastewaters using advanced oxidation processes (AOPs).
The age hardening response of a high-purity Al–4Cu–1Li–0.25Mn alloy (wt. %) during isothermal aging without and with an applied external load was investigated. Plate shaped nanometer size T1 (Al2CuLi) and θ′ (Al2Cu) hardening phases were formed. The precipitates were analyzed with respect to the development of their structure, size, number density, volume fraction and associated transformation strains by conducting transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) studies in combination with geometrical Phase analysis (GPA). Special attention was paid to the thickening of T1 phase. Two elementary types of single-layer T1 precipitate, one with a Li-rich (Type 1) and another with an Al-rich (Defect Type 1) central layer, were identified. The results show that the Defect Type 1 structure can act as a precursor for the Type 1 structure. The thickening of T1 precipitates occurs by alternative stacking of These two elementary structures. The thickening mechanism was analyzed based on the magnitude of strain associated with the precipitation transformation normal to its habit plane. Long-term aging and aging under load resulted in thicker and structurally defected T1 precipitates. Several types of defected precipitates were characterized and discussed. For θ′ precipitates, a ledge mechanism of
thickening was observed. Compared to the normal aging, an external load applied to the peak aged state leads to small variations in the average sizes and volume fractions of the precipitates.
The knowledge of the temperature-induced changes of the superconductor volume and of the thermomechanical behavior of the different coil and tooling materials is required for predicting the coil geometry and the stress distribution in the coil after the Nb3Sn reaction heat treatment. In this paper, we have measured the Young’s and shear moduli of the HL-LHC 11 T Nb3Sn dipole magnet coil and reaction tool constituents during in situ heat cycles with the dynamic resonance method. The thermal expansion behaviors of the coil components and of a free standing Nb3Sn wire were compared based on dilation experiments.
In the field of optically excited thermography, flash lamps (impulse shaped planar heating) and halogen lamps (modulated planar heating) have become established for the specific regimes of impulse and lock-in thermography. Flying-spot laser thermography is implemented by means of a rasterized focused laser, e. g. for crack detection (continuous wave operation) and photothermal material characterization (high-frequency modulated). The availability of novel technologies, i. e. fast and high-resolution IR cameras, brilliant innovative light sources and high-performance data acquisition and processing technology will enable a paradigm shift from stand-alone photothermal and thermographic techniques to uniform quantitative measurement and testing technology that is faster and more precise. Similar to an LED array, but with irradiance two orders of magnitude higher, a new type of brilliant laser source, i. e. the VCSEL array (vertical-cavity surface-emitting laser), is now available. This novel optical energy source eliminates the strong limitation to the temporal dynamics of established light sources and at the same time is spectrally clearly separated from the detection wavelength. It combines the fast temporal behavior of a diode laser with the high optical irradiance and the wide illumination area of flash lamps. In addition, heating can also be carried out in a structured manner, because individual areas of the VCSEL array can be controlled independently of each other. This new degree of freedom enables the development of completely new thermographic NDT methods.
The synthesis route and thermoelectric characterization of n-type Fe2-xTi1+xO5 (0 ≤ x ≤ 0.5) and Fe1.75(Ti1-yNby)1.25O5 (0 ≤ y ≤ 0.05) are presented. Their electrical conductivity obeys the small polaron model and their Seebeck coefficient is weakly dependent on temperature. The carrier concentration is increased with increasing Ti content in Fe2-xTi1+xO5, thus improving the electrical conductivity and decreasing the absolute values of the Seebeck coefficient. The composition with x = 0.5 shows reduced electrical conductivity contradicting the change in the carrier concentration, as it contains more microcracks than the other compositions. Fe2-xTi1+xO5 exhibits extremely low thermal conductivity. Fe2-xTi1+xO5 with x = 0.25 exhibits the highest ZT, ~ 0.014 at 1000 K. Therefore, a limited extent microcracks are beneficial to thermoelectric properties; however, when they are too extended they can be detrimental. On the contrary to Fe2TiO5, Nb substitution into Fe1.75Ti1.25O5 does not obviously improve its thermoelectric properties.
Among the photothermal methods, full-field thermal imaging is used to characterize materials, to determine thicknesses of layers, or to find inhomogeneities such as voids or cracks. The use of classical light sources such as flash lamps (impulse heating) or halogen lamps (modulated heating) led to a variety of nondestructive testing methods, in particular, lock-in and flash-thermography. In vertical-cavity surface-emitting lasers (VCSELs), laser light is emitted perpendicularly to the surface with a symmetrical beam profile. Due to the vertical structure, they can be arranged in large arrays of many thousands of individual lasers, which allows power scaling into the kilowatt range. Recently, a high-power yet very compact version of such a VCSEL-array became available that offers both the fast timing behavior of a laser as well as the large illumination area of a lamp. Moreover, it allows a spatial and temporal control of the heating because individual parts of the array can be controlled arbitrarily in frequency, amplitude, and phase. In conjunction with a fast infrared camera, such structured heating opens up a field of novel thermal imaging and testing methods. As a first demonstration of this approach, we chose a testing problem very challenging to conventional thermal infrared testing: The detection of very thin subsurface defects perpendicularly oriented to the surface of metallic samples. First, we generate destructively interfering thermal wave fields, which are then affected by the presence of defects within their reach. It turned out that this technique allows highly sensitive detection of subsurface defects down to depths in excess of the usual thermographic rule of thumb, with no need for a reference or surface preparation.
The thermal radiation impact of organic peroxide fireballs is experimentally assessed using an infrared camera. Fireballs are generated while liquid peroxide filled steel drums are subjected to gas burner fire at different heating rates. Three large burning clouds are observed with varying flame characteristics. Thermal radiation properties are assessed by infrared images with the presented methods. Despite of the two-dimensional temperature fields, the flames are treated and characterized as three-dimensional objects. Fireball diameters and heights are calculated based on a representing radiating sphere with the same cloud volume. By the use of the solid flame model and assumptions for emissivity and transmissivity, heat fluxes and thermal radiation doses against distance are predicted. Thermal safety distances are presented based on the maximum irradiance and the allowed exposure time. The validation of the maximum and time-dependent radiation fields is achieved through heat flux sensors in varying distances to the fireball. The results prove the use of an infrared camera and a volume based size calculation to fully assess the thermal radiation hazards of fireballs.
Pure and Al-doped ZnO powders have been sintered by Spark Plasma Sintering. Al doping allows the ceramics to reach a relative density greater than 90% at a sintering temperature of 500°C. The morphology of powder nanoparticles impacts the final grain size of the sintered bulk compounds. A ceramic sintered from isotropic nanoparticles of 30 nm in diameter can reach an average grain size of 110 nm, whereas a ceramic sintered from platelets and isotropic nanoparticles exhibits an average grain size in the submicrometric range. The influence of ceramic grain size on the thermal conductivity has been investigated. It shows that substantial decrease of the grain size from several microns down to 100 nm reduces the thermal conductivity from 29.5 to 7.8 W/m K at 100°C. The stability of nanostructured ceramic has also been checked. After SPS, an annealing at 500°C in air also leads to grain growth.
A combination of different complementary methods is employed to investigate scaling of the molecular dynamics of two different liquid crystals. Each method is sensitive to different kind of fluctuations and provides therefore a different window to look at the molecular dynamics. In detail, broadband dielectric spectroscopy is combined with specific heat spectroscopy and neutron scattering. As systems the nematic liquid crystal E7 and a discotic liquid crystalline pyrene are considered. First of all it was proven that both systems show all peculiarities which are characteristic for glassy dynamics and the glassy state. Especially for the nematic liquid crystal E7 it could be unambiguously shown by a combination of dielectric and specific heat spectroscopy that the tumbling mode is the underlying motional process responsible for glassy dynamics. Dielectric investigations on the discotic liquid crystalline pyrene reveal that at the phase transition from the plastic crystalline to the hexagonal columnar liquid crystalline phase the molecular dynamics changes from a more strong to fragile temperature dependence of the relaxation rates. Moreover a combination of results obtained by specific heat spectroscopy with structural methods allows an estimation of the length scale relevant for the glass transition.
It is widely accepted that the magnetic state of a ferromagnetic material may be irreversibly altered by mechanical loading due to magnetoelastic effects. A novel standardized nondestructive testing (NDT) technique uses weak magnetic stray fields, which are assumed to arise from inhomogeneous deformation, for structural health monitoring (i.e., for detection and assessment of damage). However, the mechanical and microstructural complexity of damage has hitherto only been insufficiently considered. The aim of this study is to discuss the phenomenon of inhomogeneous “self-magnetization” of a polycrystalline ferromagnetic material under inhomogeneous deformation experimentally and with stronger material-mechanical focus. To this end, notched specimens were elastically and plastically deformed. Surface magnetic states were measured by a three-axis giant magnetoresistant (GMR) sensor and were compared with strain field (digital image correlation) and optical topography measurements. It is demonstrated that the stray fields do not solely form due to magnetoelastic effects. Instead, inhomogeneous plastic deformation causes topography, which is one of the main origins for the magnetic stray field formation. Additionally, if not considered, topography may falsify the magnetic signals due to variable lift-off values. The correlation of magnetic vector components with mechanical tensors, particularly for multiaxial stress/strain states and inhomogeneous elastic-plastic deformations remains an issue.
Load partitioning between phases in a cast AlSi12CuMgNi alloy was investigated by in-situ compression test during neutron diffraction experiments. Computed tomography (CT) was used to determine volume fractions of eutectic Si and intermetallic (IM) phases, and to assess internal damage after ex-situ compression tests. The CT reconstructed volumes showed the interconnectivity of IM phases, which build a 3D network together with eutectic Si. Large stresses were found in IMs, revealing their significant role as a reinforcement for the alloy. An existing micromechanical model based on Maxwell scheme was extended to the present case, assuming the alloy as a three-phase composite (Al matrix, eutectic Si, IM phases). The model agrees well with the experimental data.
Moreover, it allows predicting the principal stresses in each phase, while experiments can only determine stress differences between the axial and radial sample directions. Finally, we showed that the addition of alloying elements not only allowed developing a 3D interconnected network, but also improved the strength of the Al matrix, and the ability of the alloy constituents to bear mechanical load.
Amyloid fibrils are polymers formed by proteins under specific conditions and in many cases they are related to pathogenesis, such as Parkinson’s and Alzheimer’s diseases. Their hallmark is the presence of a β-sheet structure. High resolution structural data on these systems as well as information gathered from multiple complementary analytical techniques is needed, from both a fundamental and a pharmaceutical perspective. Here, a previously reported de novo designed, pH-switchable coiled coil-based peptide that undergoes structural transitions resulting in fibril formation under physiological conditions has been exhaustively characterized by transmission electron microscopy (TEM), cryo-TEM, atomic force microscopy (AFM), wide-angle X-ray scattering (WAXS) and solid-state NMR (ssNMR). Overall, a unique 2-dimensional carpet-like assembly composed of large coexisiting ribbon-like, tubular and funnel-like structures with a clearly resolved protofilament substructure is observed. Whereas electron microscopy and scattering data point somewhat more to a hairpin model of β-fibrils, ssNMR data obtained from samples with selectively labelled peptides are in agreement with both, hairpin structures and linear arrangements.
The physico-chemical basis of DNA radiosensitization: Implications for cancer radiation therapy
(2018)
High-energy radiation is used in combination with radiosensitizing therapeutics to treat cancer. The most common radiosensitizers are halogenatednucleo-sides and cisplatin derivatives, and recently also metal nanoparticles have been suggested as potentialradiosensitizing agents. The radiosensitizingaction of these compounds can at least partly be ascribed to an enhancedreactivity towards secondary low-energy electrons generated along the radiation track of the high-energyprimary radiation, or to an additional emission of secondary reactive electrons close to the tumor tissue. This is referred to as physico-chem ical radiosensitization. In this Conceptarticle we presentcurrent experimental methodsused to study fundamentalprocesses of physico-chemical radiosensitization and discuss the most relevant classes of radiosensitizers. Open questions in the current discussions are identified and future directions outlined, which can lead to optimized treatment protocols or even novel therapeuticconcepts.
In this study, a nonlinear three-dimensional finite element (FE) model was developed and validated to investigate the response of concrete filled tube (CFT) columns subjected to post-earthquake fires. Three steps were considered successively in the modelling, namely, cyclic, thermal and structural analyses. Outputs from the cyclic loading including residual deformationswere imposed as an initial condition to the thermal-stress model, imitating the seismic response of the column. Subsequently, a nonlinear sequentially thermal-stress analysis was conducted to simulate the fire response of column after the earthquake. The proposed FE model was validated by comparing the simulation resultswith the observations of full-scale fire and cyclic tests available in the literature.
The validated numericalmodelwas then used to study the behavior of CFT columns under the combined action of earthquake and fire as a multi-hazard event. Three probable seismic damage scenarios were considered in the column, namely, middle length, bottom and top end region damages. The level of damage was assumed as a high damage level, presuming that the column reached 50% of its lateral resistance while still maintaining ist overall stability after the earthquake. The results showed that the top and bottom end region damages have not significantly influence the fire response of the damaged column. Besides, the column with the middle span damage performed a lesser fire resistance time owing to the coincidence of damage location to that of onset of global buckling.
The evolutionary success of termites has been driven largely by a complex communication system operated by a rich set of exocrine glands. As many as 20 different exocrine organs are known in termites. While some of these organs are relatively well known, only anecdotal observations exist for others. One of the exocrine organs that has received negligible attention so far is the labral gland. In this study, we examined the structure and ultrastructure of the Labrum in soldiers of 28 termite species. We confirm that the labral gland is present in all termite species, and comprises two secretory regions located on the ventral side of the labrum and the dorso-apical part of the hypopharynx. The Labrum of Neoisoptera has a hyaline tip, which was secondarily lost in Nasutitermitinae, Microcerotermes and species with snapping soldiers. The epithelium of the gland generally consists of class 1 secretory cells, with an addition of class 3 secretory cells in some species. A common feature of the secretory cells is the abundance of smooth endoplasmic reticulum, an organelle known to produce lipidic and often volatile secretions. Our observations suggest that the labral gland is involved in communication rather than defence as previously suggested. Our study is the first to provide a comprehensive picture of the structure of the labral gland in soldiers across all Termite taxa.
The influence of the support structure on residual stress and distortion in SLM Inconel 718 parts
(2018)
The effect of support structure and of removal from the base plate on the residual stress state in selective laser melted IN718 parts was studied by means of synchrotron X-ray diffraction. The residual stresses in subsurface region of two elongated prisms in as-built condition and after removal from the base plate were determined. One sample was directly built on a base plate and another one on a support structure. Also, the distortion on the top surface due to stress release was measured by contact profilometry. High tensile residual stress values were found, with pronounced stress gradient along the hatching direction. In the sample on support, stress redistribution took place after removal from the base plate, as opposed to simple stress relaxation for the sample without support. The sample on support structure showed larger distortion compared to sample without support. We conclude that the use of a support decreases stress values but stress-relieving heat treatments are still needed.
Comprehensive insights into the early stages of corrosion mechanisms provide fundamental knowledge to further understand and model long time material behaviour. The present work studies the early stages of combined oxidation and sulphidation of ferritic model alloys for time scales up to 250 h at 650 °C to observe the influence of chromium during the corrosion under SO2. Model alloys were used to focus on the reaction of the intended elements: Fe, Cr, S, and O. Pure iron simultaneously forms magnetite and iron sulphide in an early stage of corrosion, covered by a pure oxide layer after 100 h. Iron with 13 wt% Cr shows hematite and mixed Fe-Cr-oxides first, before sulphides nucleate in the inner corrosion zone. With increasing ageing time a magnetite layer is observed below the hematite layer. Quantitative phase fractions of all corrosion products observed were determined from cross section images. Characterization of the Fe13Cr corrosion scale by FIB revealed a highly porous structure in the inner corrosion zone where Cr-rich (Fe, Cr)-sulphides are present, and caused the scale to spall easily.
The work presents the procedure developed within the German research project IBESS, which allows for the fracture mechanics-based prediction of the fatigue strength of welded joints under constant amplitude loading. Based on the experimental observations of the crucial failure mechanisms, the approach focuses on the short crack propagation, where elastic-plastic fracture mechanics and the build-up of closure effects must be considered as well as the variability of the local geometry at the weld toe and the modelling of multiple crack interaction. Analytical solutions are provided for the approximation of the through-thickness stress profiles at the weld toe and for the determination of the crack driving force in the form of a plasticity-corrected stress intensity factor range ∆K_p. Proposals for the determination of the initial crack size and the crack closure factor are also included.
The approach is validated against a large number of experimental data, which comprises fatigue tests on individual cracks monitored by heat tinting and beach-marking techniques, as well as stress life curves. Three kinds of welded joints, two steels of significant different strengths and three stress ratios are considered. The results show that the procedure provides good estimations of the statistical distribution of the fatigue strength of welded joints both for the finite and infinite life regime. Furthermore, the predictions are compared with available benchmark data for structural steels.
BACKGROUND CONTEXT: Targeted delivery of osteoinductive bone morphogenetic Proteins (eg, GDF5) in bioresorbable calcium phosphate cement (CPC), potentially suitable for vertebroplasty and kyphoplasty of osteoporotic vertebral fractures, may be required to counteract augmented local bone catabolism and to support complete bone regeneration. The biologically optimized GDF5 Mutant BB-1 may represent an attractive drug candidate for this purpose.
PURPOSE: The aim of the current study was to test an injectable, poly (l-lactide-co-glycolide) acid (PLGA) fiber-reinforced, brushite-forming CPC containing low-dose BB-1 in a sheep lumbar osteopenia model.
STUDY DESIGN/ SETTING: This is a prospective experimental animal study.
METHODS: Bone defects (diameter 5 mm) were generated in aged, osteopenic female sheep and were filled with fiber-reinforced CPC alone (L4; CPC+fibers) or with CPC containing different dosages.
To save weight and resources lightweight tanks with complex geometries made of glass-fibre reinforced plastics (GFRP) are a promising innovation for the transportation of dangerous goods. To realise the use of polymer tanks for such applications, their fire safety must be guaranteed. This paper presents solutions to protect fibre-reinforced plastic tanks from fire. The fire resistance of six GFRP tanks with different fire protection systems was tested in an outdoor full-scale fire test facility according to the regulation stipulated in the ADR (European agreement concerning the national carriage of dangerous goods by road). All tanks feature a complex geometry and a holding capacity of 1100 litres. The fire protection systems are composed of specialised resins as well as two intumescent coatings. All systems had a protective impact. The best results were achieved by the epoxy based intumescent coating, which was able to prolong the time needed to reach 150 °C inside the tank by 20 min. The emergence of a temperature holding point inside the tank due to condensation effects was observed at temperatures around 100 °C.
Slags from the nonferrous metals industry have great potential to be used as feedstocks for the production of alkali-activated materials. Until now, however, only very limited information has been available about the structural characteristics of these materials. In the work presented herein, synthetic slags in the CaO–FeOx–SiO2 system, representing typical compositions of Fe-rich slags, and inorganic polymers (IPs) produced from the synthetic slags by activation with alkali Silicate solutions have been studied by means of X-ray absorption near-edge structure (XANES) spectroscopy at the Fe K-edge. The iron in the slags was largely Fe2+, with an average coordination number of approximately 5 for the iron in the amorphous fraction. The increase in average oxidation number after alkali-activation was conceptualized as the consequence of slag dissolution and IP precipitation, and employed to calculate the degrees of reaction of the slags. The degree of reaction of the slags increased with increasing amorphous fraction. The iron in the IPs had an average coordination number of approximately 5; thus, IPs produced from the Fe-rich slags studied here are not Fe-analogs of aluminosilicate geopolymers, but differ significantly in terms of structure from the latter.
This paper addresses the effects of the deterioration on the value of damage detection information. The quan-tification of the value of damage detection information for deteriorated structures is based on Bayesian pre-posterior decision analysis, comprising structural system performance models, consequence, benefit and costs models and damage detection information models throughout the service life of a structural system. The value of damage detection information accounts for the relevance and precision of the information to ensure the structural integrity and to reduce the potential structural system risks and expected costs throughout the ser-vice life before implementing damage detection system. With the developed approach, the value of damage detection information for a statically determinate Pratt truss bridge girder subjected to different deterioration models is calculated. The analysis shows the impact of the deterioration model parameters on the value of damage detection information. The results can be used to develop optimal maintenance strategies before im-plementation of the damage detection system.
The paper provides an application of the IBESS approach to the investigation of the influence of various parameters of the global and local weld geometry as well as material defects on the fatigue strength of weldments. For this purpose, the global weld parameters, such as the weld toe radius, the flank angle, the excess weld metal, local secondary notches (in the present study as a measure of surface imperfections) and inclusions sizes have been determined as statistical distributions for different joint types and geometries and two steels of different strengths. The results are in line with literature data and reveal the potential of the theoretical approach to predict the correct trends. The combination with an advanced weld quality system has been demonstrated to be possible.
Microplastics are increasingly entering marine, limnic and terrestrial ecosystems worldwide, where they sorb hydrophobic organic contaminants. Here, the sorption behavior of the fuel-related water contaminants benzene, toluene, ethyl benzene and xylene (BTEX) and four tertiary butyl ethers to virgin and via UV radiation aged polypropylene (PP) and polystyrene (PS) pellets was investigated. Changes in material properties due to aging were recorded using appropriate polymer characterization methods, such as differential scanning calorimetry, Fourier transform infrared spectroscopy, gel permeation chromatography, X-ray photoelectron spectroscopy, and microscopy.
Pellets were exposed to water containing BTEX and the ethers at 130-190 mg/L for up to two weeks.
Aqueous sorbate concentrations were determined by headspace gas chromatography. Sorption to the polymers was correlated with the sorbate's Kow and was significant for BTEX and marginal for the ethers.
Due to substantially lower glass transition temperatures, PP showed higher sorption than PS. Aging had no effect on the sorption behavior of PP. PS sorbed less BTEX after aging due to an oxidized surface layer.
In this paper, a nonlinear three-dimensional finite element (FE) model was developed and validated to study the effect of seismic damage location on the response of concrete filled tube (CFT) columns at fire after earthquakes. Three analyses were conducted consecutively in the modelling, namely, cyclic, thermal and structural. Results of the cyclic loading analysis comprising residual deformations were applied as the Initial condition to the thermal-stress model, replicating the seismic performance of column.
Following, a nonlinear sequentially coupled-thermal stress Analysis was carried out to investigate the fire response of CFT columns after the seismic event. Three damage scenarios were contemplated, considering any possible potential damages that could be generated by the earthquake loading on CFT columns. The accuracy of the proposed FE model was examined by comparing the numerical results with that of available tests on fire and cyclic loading. By means of the validated model, the performance of damaged CFT columns was then investigated under fire after earthquakes. The level of damage was assumed as a high damage level, presuming that the column reached 50% of ist lateral resistance while still maintaining its overall stability after the earthquake. The results were presented broadly, including the axial deformation history as well as the fire resistance time for CFT columns. To have a comprehensive insight on the influence of damage location in columns, the fire response of damaged specimens was compared with that of an intact one.
The increasing request for hair ethyl glucuronide (HEtG) in alcohol consumption monitoring according to cut-off levels set by the Society of Hair Testing (SoHT) has triggered a proficiency testing program based on interlaboratory comparisons (ILC). Here, the outcome of nine consecutive ILC rounds organised by the SoHT on the determination of HEtG between 2011 and 2017 is summarised regarding interlaboratory reproducibility and the influence of procedural variants. Test samples prepared from cut hair (1 mm) with authentic (in-vivo incorporated) and soaked (in-vitro incorporated) HEtG concentrations up to 80 pg/mg were provided for 27–35 participating laboratories. Laboratory results were evaluated according to ISO 5725-5 and provided robust averages and relative reproducibility standard deviations typically between 20 and 35% in reasonable accordance with the prediction of the Horwitz model. Evaluation of results regarding the analytical techniques revealed no significant differences between gas and liquid chromatographic methods In contrast, a detailed evaluation of different sample preparations revealed significantly higher average values in case when pulverised hair is tested compared to cut hair. This observation was reinforced over the different ILC rounds and can be attributed to the increased acceptance and routine of hair pulverisation among laboratories. Further, the reproducibility standard deviations among laboratories performing pulverisation were on average in very good agreement with the prediction of the Horwitz model. Use of sonication showed no effect on the HEtG extraction yield.
The so-called cyclic R curve, i.e. the crack size dependence of the fatigue crack propagation threshold in the physically short crack regime, is a key parameter for bringing together fatigue strength and fracture mechanics concepts. Its adequate determination is of paramount importance. However, notwithstanding this relevance, no test guideline is available by now and only very few institutions have spent research effort on cyclic R curves so far. The aim of the present paper is to give an overview on the state-of-the-art. Besides an introduction into the basic principles, the discussion will concentrate on the experimental determination on the one hand and questions of its application on the other hand.
The occurrence of small particles consisting of organic polymers, so-called microplastic (MP), in aquatic Environments attracts increasing interest in both public and science. Recent sampling campaigns in surface Waters revealed substantial numbers of particles in the size range from a few micrometers to a few millimeters. In order to validate sample preparation, identification and quantification and to investigate the behavior of MP particles and potential toxic effects on organisms, defined MP model particles are needed. Many studies use spherical compounds that probably behave differently compared to irregularly shaped MP found in environmental samples.
However, preparation and handling of MP particles are challenging tasks and have been systematically investigated in the present study. Polystyrene (PS) as a commonly found polymer with a density slightly above that of water was selected as polymer type for milling and fractionation studies. A cryogenic ball mill proved to be practical and effective to produce particles in the size range from 1 to 200 μm. The yield of small particles increased with increasing pre-cooling and milling durations. Depending on the concentration and the size, PS particles do not completely disperse in water and particles partly creep vertically up along glass walls. Stabilized MP suspensions without use of surfactants that might harm organisms are needed for toxicological studies. The stabilization of PS particle suspensions with ozone treatment reduced the wall effect and increased the number of dispersed PS particles but increased the dissolved organic carbon concentration and changed the size Distribution of the particles.
Severe fires at the Friedrichshain flak bunker in May 1945 destroyed or severely damaged an important part of the collection of the Kaiser-Friedrich-Museum, Berlin, today’s Bode Museum. Fragments of two marble sculptures by Tullio Lombardo, sculptor of the Italian renaissance, have survived and are now stored in the Bode Museum. In preparation for restoration, the condition of the sculptures has been documented in detail in 2010. The study revealed that the fragments are not stable enough to exhibit them in a horizontal nor in an upright position. The intention of a further study in 2012 was to find a correlation between ultrasonic velocity and mechanical properties of burned Carrara marble as a basis for stabilization measures. The results and numerous supplementary experiments show that the current condition of the sculptural fragments can not only be explained by the exposure to fire.
Contrast-variation small-angle neutron scattering (CV-SANS), small-angle X-ray scattering (SAXS), nuclear magnetic resonance (NMR) measurements of diffusion and isothermal titration calorimetry (ITC) are used to gain insight into the aggregation of an alkyl–C60 derivative, molecule 1, in n-hexane, n-decane and toluene as a function of concentration and temperature. Results point to an associative mechanism of aggregation similar to other commonly associating molecules, including non-ionic surfactants or asphaltenes in non-aqueous solvents. Little aggregation is detected in toluene, but small micelle-like structures form in n-alkane solvents, which have a C60-rich core and alkyl-rich shell. The greatest aggregation extent is found in n-hexane, and at 0.1 M the micelles of 1 comprise around 6 molecules at 25 °C. These micelles become smaller when the concentration is lowered, or if the solvent is changed to n-decane. The solution structure is also affected by temperature, with a slightly larger aggregation extent at 10 °C than at 25 °C. At higher concentrations, for example in solutions of 1 above 0.3 M in n-decane, a bicontinuous network becomes apparent. Overall, these findings aid our understanding of the factors driving the assembly of alkyl–π-conjugated hydrophobic amphiphiles such as 1 in solution and thereby represent a step towards the ultimate goal of exploiting this phenomenon to form materials with well-defined order.
Territories of rock-inhabiting fungi: Survival on and alteration of solid air-exposed surfaces
(2018)
Subaerial biofilms that are omnipresent at the interface between all solid substrates and the atmosphere are composed of a unique and widespread group of ascomycetes called rock-inhabiting fungi or microcolonial fungi (MCF), typically in communities with other microorganisms. While subaerial biofilms in toto have important roles in mineral weathering and biodeterioration of materials, methodological approaches to subaerial biofilm communities are diverse and frequently focussed on MCF. Here, we review the historical development of the research methods applied in the field and consider perspectives to increase our understanding of the biofilm-induced changes of solid substrate surfaces.
Repair is an indispensable part of the maintenance of structures over their lifetimes. Structural grouting is a widely used remediation technique for concrete components, trenches, mine subsidence, dam joints, restoration of masonry structures, and geological stabilizations. A structural grout system should be injectable in narrow spaces and hence include ingredients with finer particles. Ultrafine cements are ideal for these type of demanding grouts due to their superior properties compared to that of the less expensive, but coarser ordinary Portland cement (OPC). Supplementary cementitious materials (SCMs) are often used to replace OPC clinker based binder in order to modify certain properties and to reduce costs. The most commonly used SCMs are fly ash (FA), and ground granulated blast furnace slag (GGBS). For various special applications microsilica (MS), and metakaolin (MK) are also used. Identifying the optimum replacement contents of OPC by SCMs are a challenge during the design of such grouts. The aim of this experimental study is to investigate the effect of the selected SCMs (FA, MS and MK) on the slump flow, time of efflux, viscosity, shrinkage, and compressive and flexural strength of ultrafine cement based grouts with constant water-binder ratio and superplasticizer content. The test program was formulated using Box-Behnken design principles. Maximum percentages of replacement with ultrafine cement was 6% by volume of cement for MS and 16% for FA, and MK. The results suggest that most investigated grouts have the potential to be used for structural applications. The appropriate quadratic models are then formulated through statistical tools and presented as response surfaces. The trends indicate that fly ash improves the rheological properties, whereas microsilica and metakaolin positively affect shrinkage and mechanical properties to some extent. Based on the influence of SCMs and priorities among the properties, Decision Matrix Analysis (DMA) is carried out to select the most suitable ones among the SCMs. The analysis suggests that microsilica and fly ash are more suitable as SCMs than metakaolin without affecting the properties.
Social insects employ a range of behaviours to protect their colonies against disease, but little is known about how such collective behaviours are orchestrated. This is especially true for the social Blattodea (termites). We developed an experimental approach that allowed us to explore how the social response to disease is co-ordinated by multistep host-pathogen interactions. We infected the eastern subterranean termite Reticulitermes flavipes with the entomopathogenic fungus Metarhizium anisopliae, and then, at different stages of infection, reintroduced them to healthy nestmates and recorded behavioural responses. As expected, termites groomed pathogen-exposed individuals significantly more than controls; however, grooming was significantly elevated after fungal germination than before, demonstrating the importance of fungal status to hygienic behaviour. Significantly, we found that cannibalism became prevalent only after exposed termites became visibly ill, highlighting the importance of host condition as a cue for social hygienic behaviour. Our study reveals the presence of a coordinated social response to disease that depends on stage of infection. Specifically, we show how the host may play a key role in triggering its own sacrifice. Sacrificial self-flagging has been observed in other social insects: our results demonstrate that termites have independently evolved to both recognize and destructively respond to sickness.
The importance of soldiers to termite Society defence has long been recognized, but the contribution of soldiers to other societal functions, such as colony immunity, is less well understood.
We explore this issue by examining the role of soldiers in protecting nestmates against pathogen infection. Even though they are unable to engage in grooming behaviour, we find that the presence of soldiers of the Darwin termite, Mastotermes darwiniensis, significantly improves the survival of nestmates following entomopathogenic infection.
We also show that the copious exocrine oral secretions produced by Darwin termite soldiers contain a high concentration of Proteins involved in digestion, chemical biosynthesis, and immunity. The oral secretions produced by soldiers are sufficient to protect nestmates against infection, and they have potent inhibitory activity against a broad spectrum of microbes. Our findings support the view that soldiers may play an important role in colony immunity, and broaden our understanding of the possible function of soldiers during the origin of soldier-first societies.
The quality of research antibodies is an issue for decades. Although several papers have been published to improve the situation, their impact seems to be limited. This publication makes the effort to simplify the description of validation criteria in a way that the occasional antibody user is able to assess the validation level of an immunochemical reagent. A simple, 1-page checklist is supplied for the practical application of these criteria.
Temperature-induced, stress-induced martensitic phase transitions and martensite reorientation process in Ni rich (50.9 at.%) NiTi pseudoelastic NiTi wires with ultra-fine grained (UFG) microstructure were studied by electrical resistance measurements. Measurements of the electrical resistance as a function of temperature at different constant mechanical loads accompanied by complementary experiments with variable loads at constant temperature were performed. Results show that the transformation mechanisms in UFG microstructures exhibit a higher level of complexity when compared with those characterizing the behavior of other microstructures (e.g., recrystallized or larger grains size). It was found that a threshold stress level below 150 MPa delimits the transition from a homogeneous (low stress) to localized but reversible Lüders type transformation (high stress) when the transformations are induced under constant applied stress and that reorientation processes require stresses of 100 MPa in the present UFG wires. Even though the strain evolutions do not always show two distinct yielding events during cooling or heating, electrical resistance measurements proved that a two-step transformation involving R-phase and B19' martensite was always present in the extended range of temperatures and stresses investigated here.
Recent DNA-based studies have shown that the built environment is surprisingly rich in fungi. These indoor fungi – whether transient visitors or more persistent residents – may hold clues to the rising levels of human allergies and other medical and building-related health problems observed globally. The taxo¬nomic identity of these fungi is crucial in such pursuits. Molecular identification of the built mycobiome is no trivial undertaking, however, given the large number of unidentified, misidentified, and technically compromised fungal sequences in public sequence databases. In addition, the sequence metadata required to make informed taxonomic decisions – such as country and host/substrate of collection – are often lacking even from reference and ex-type sequences. Here we report on a taxonomic annotation workshop (April 10–11, 2017) organized at the James Hutton Institute/University of Aberdeen (UK) to facilitate reproducible studies of the built mycobiome. The 32 participants went through public fungal ITS bar¬code sequences related to the built mycobiome for taxonomic and nomenclatural correctness, technical quality, and metadata availability. A total of 19,508 changes – including 4,783 name changes, 14,121 metadata annotations, and the removal of 99 technically compromised sequences – were implemented in the UNITE database for molecular identification of fungi (https://unite.ut.ee/) and shared with a range of other databases and downstream resources. Among the genera that saw the largest number of changes were Penicillium, Talaromyces, Cladosporium, Acremonium, and Alternaria, all of them of significant importance in both culture-based and culture-independent surveys of the built environment.
The present work provides a comparative study on the interface and adhesion properties of surface modified single glass fibers embedded in an acrylate matrix. To facilitate a covalent bonding at the fibermatrix interface, the fibers are functionalized with selected organosilanes that comprise either passive (unsaturated C¼C bonds of methacrylate moieties) or photoactive functionalities (photocleavable bis(acyl)phosphane oxide groups). Immobilization of the functional silanes is carried out by a classic silanization reaction involving a condensation reaction across the surface hydroxyl groups of the inorganic glass fibers. The change of the physico-chemical properties of the fibers due to desizing and subsequent surface modification is monitored by X-ray photoelectron spectroscopy and zeta potential measurements. In addition, scanning electron microscopy is used to follow the changes in surface morphology. After the modification step, the desized and modified single fibers are embedded in a photocurable acrylate resin formulation. By performing single fiber pull-out tests, maximum pull-out force, friction strength and apparent interfacial shear strength are determined as a function of the coupled silanes. The results reveal that the attached organosilanes lead to a significant increase in adhesion strength, whilst the performance of the photo-cleavable organosilane is superior to the passive methacryl-functional derivative.
Systematic errors in the evaluation of uncorrected data from thermographic lock-in measurements
(2018)
Lock-in thermography (LT) is based on the correct evaluation of phase differences between the temperature oscillations at different surface regions of the object under test during periodic heating. Since the usual heating procedures contain a DC component, the actual heating pattern achieved is not harmonic. This causes systematic deviations when phase differences are determined by means of harmonic analysis, e.g. with FFT analysis. The resulting errors depend clearly on the ratio between DC and AC amplitude, which is demonstrated at simulated and experimentally recorded temperature transients. Further experimental LT data obtained by different oscillating energy inputs showed a variety of possible shapes of transients with different DC components.
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.
Tris(3,5-dimethylpyrazolyl)arsane (1) is introduced as a low-cost and convenient to handle arsenic precursor for the straight Forward synthesis of InAs Quantum dots (QDs). Transamination of 1 with the solvent oleylamine (OLAH) gives trioleylarsane (As(OLA)3) which in the presence of the reducing agents diisobutylaluminum hydride (DIBAL-H) or trioleylphosphane (P(OLA)3) yields InAs QDs via a typical hot injection approach. The size of the obtained InAs core QDs are tuned by varying the reaction time, the amount of the applied reducing agent, or even more effectively by changing the Indium and/or zinc halide precursors, InX3, and ZnX2 (Cl, Br, or I). Passivation of the resulting InAs particles with a
protective ZnS or ZnSe shell results in improved photoluminescence of the core/shell QDs covering a spectral range between 600 and 1150 nm.
A new dimer of the food-relevant mycotoxin zearalenone was isolated after electrochemical and chemical oxidation. The structure was determined as a 16-O-15'-biaryl ether-linked dimer based on spectroscopic analyses (1H- and 13C-NMR, COSY, HMBC, and HSQCAD) and high-Resolution mass spectrometry analysis (Q-TOF).
Modern advanced high-strength steel sheets for automotive applications are mostly zinc coated for corrosion resistance. However, the presence of zinc can—besides its positive effects—increase the material’s susceptibility to liquid metal embrittlement (LME) during resistance spot welding (RSW). Zinc and its eutectics are, due to their low melting point, present in liquid state during the welding process. This fact can, in combination with other factors like tensile strains or stresses, lead to the formation of brittle, intergranular cracks in the weld, and heat-affected zone. This phenomenon is commonly called liquid metal embrittlement. In order to understand the process from a practical perspective, one must learn what factors facilitate it. In this study, industry-relevant parameters are investigated regarding their influence on the occurrence of LME, embodied by the formation of surface cracks. It was found that electrode wear has less of an influence on the cracking susceptibility than welding current or tensile stresses. Finite element analysis is believed to provide a powerful tool in order to gain insights on the formation process. Modeling of the process shows promising initial results, revealing the underlying local stress and strain fields, unmeasurable with common techniques.
Biomedical applications, including functional biomaterials, carbohydrate-arrays, and glycan-based biosensors.
The chemistry of glycan immobilization plays an essential role in the bioavailability and function of surface bound carbohydrate moieties. For biomedical applications the stability over time (shelf life) of glycan arrays is a crucial factor. Herein we report on approaches for surface and interface characterization relevant to the needs of production of glycan microarrays which were tested using model carbohydrate surfaces. For detailed characterization of glycan model surfaces we used a combination of X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and ToF SIMS which are complementary techniques of surface chemical analysis. Links to fluorescence spectroscopy often used for characterization in the microarray community were established as well. In detail, amine-reactive silicon oxide and glass surfaces were used for anchoring oligosaccharides with an amino linker. The amount of surface bound carbohydrates was estimated by X-ray photoelectron spectroscopy (XPS). Glycan immobilization was investigated using lectins, which are glycan-binding molecules. A shelf life study of model glycan microarrays on epoxy-coated glass surfaces was done over a period of 160 days under different storage conditions utilizing fluorescence, ToF-SIMS and XPS analysis. It was shown that glycan activity of the models used can be maintained at least for half a year of storage at 4 °C.
Surface characterisation of Escherichia coli under various conditions by near-ambient pressure XPS
(2018)
Bacteria are inherently in a hydrated state and therefore not compatible to ultra-high vacuum techniques such as XPS without prior sample preparation involving freeze drying or fast freezing.
This has changed with the development of near-ambient pressure (NAP)-XPS, which makes it possible to characterise the bacterial surface with minimal sample preparation. This paper presents NAP-XPS measurements of Escherichia coli under various NAP conditions: at 11 mbar in a humid environment, at 2 mbar after drying in the chamber, pre-dried at 4 mbar, and at 1 mbar after overnight pumping at 10^−4 mbar. The high-resolution spectra of carbon, nitrogen, and oxygen are presented and found to be in general agreement with XPS measurements from freeze-dried and fast-frozen bacteria. However, it was found that the amount of carbon components associated with polysaccharides increases relative to aliphatic carbon during drying and increases further after overnight pumping. This implies that drying has an impact on the bacterial surface.
Many ambient desorption/ionization mass spectrometry (ADI-MS) techniques rely critically on thermal desorption. Meanwhile, the analyte classes that are successfully studied by any particular ADI-MS methods are strongly dependent on the type of ionization source. Generally, spraybased ionization sources favor polar analytes, whereas plasmabased sources can be used for more hydrophobic analytes and are more suitable for molecules with small molar masses. In the present work, classic atmospheric-pressure chemical ionization (APCI) is used. To provide improved desorption performance for APCI, a surface acoustic wave nebulization (SAWN) device was implemented to convert liquid analytes into fine airborne particles. Compared to conventional SAWN that is used solely as an ionization source for liquid samples, the coupling of SAWN and APCI significantly improves ion signal by up to 4 orders of magnitude, reaching comparable ion abundances to those of electrospray ionization (ESI). Additionally, this coupling also extends the applicable mass range of an APCI source, conventionally known for the ionization of small molecules <500 Da. Herein, we discuss cursory evidence of this applicability to a variety of analytes including both polar and nonpolar small molecules and novel peptides that mimic biomolecules upward of 1000 Da. Observed species are similar to ESI-derived ions including doubly charged analyte ions despite presumably different charging mechanisms. SAWN−APCI coupling may thus involve more nuanced ionization pathways in comparison to other ADI approaches.
Recently, we suggested an unconventional approach (the so-called Internal-Field-Guarded-Active-Region Design “IFGARD”) for the elimination of the quantum-confined Stark effect in polar semiconductor heterostructures. The IFGARD-based suppression of the Stark redshift on the order of electronvolt and spatial charge carrier separation is independent of the specific polar semiconductor material or the related growth procedures. In this work, we demonstrate by means of micro-photoluminescence techniques the successful tuning as well as the elimination of the quantum-confined Stark effect in strongly polar [000-1] wurtzite GaN/AlN nanodiscs as evidenced by a reduction of the exciton lifetimes by up to four orders of magnitude. Furthermore, the tapered geometry of the utilized nanowires (which embed the investigated IFGARD nanodiscs) facilitates the experimental differentiation between quantum confinement and Stark emission energy shifts. Due to the IFGARD, both effects become independently adaptable.
ISO/TR 19693:2018—Surface chemical analysis—Characterization of functional glass substrates for biosensing applications gives an overview of methods, strategies, and guidance to identify possible sources of problems related to substrates, device production steps (cleaning, activation, and chemical modification), and shelf life (storage conditions and aging). It is particularly relevant for surface chemical analysts characterizing glass‐based biosensors, and developers or quality managers in the biosensing device production community. Based on quantitative and qualitative surface chemical analysis, strategies for identifying the cause of poor Performance during device manufacturing can be developed and implemented. A review of measurement capabilities of surface analytical methods is given to assist readers from the biosensing community.
One-part alkali-activated (geopolymer) mortars based on three different silica-rich starting materials and sodium aluminate, with and without ground granulated blast furnace slag (GGBFS) addition, were tested regarding sulfuric acid resistance according to DIN 19573:2016-03 (70 days at pH = 1). Corresponding pastes were characterized by XRD, SEM, chemical analysis, 29Si MAS NMR and 1H-29Si CPMAS NMR after water storage and after acid exposure. The mortars exhibited a high resistance against sulfuric acid attack, with the best ones conforming to the requirements of DIN 19573:2016-03. The analytical results showed that this was due to precipitation of silica gel at the acid-mortar interface, which formed a mechanically stable layer that protected the subjacent mortar and thus inhibited further degradation. The addition of GGBFS decreased the acid resistance via formation of expansive calcium sulfate phases.
Subsurface characterization of high-strength high-interstitial austenitic steels after impact wear
(2018)
The microstructure of the subsurface after impact wear of three high-strength high interstitial austenitic steels has been analysed using transmission electron microscopy (TEM) in alloys with C and N as interstitial elements. In all cases, a nanocrystalline region followed by a transition zone and a cold-worked area are present. Additionally, microhardness and nano-scratching tests were conducted to study the wear-related properties of the impact subsurface and the base material. The results of the microstructural analysis reveal that the following mechanisms are involved during impact wear: abrasion (ploughing), microcrack formation associated with contact fatigue, entrapment and adhesion of SiO2 particles. The analysis of the wear-related properties indicates that the subsurface acts as a self-protective layer that prevents the deterioration of the substrate.
Populations of genetically identical cells can display marked variation in phenotypic traits; such variation is termed phenotypic heterogeneity. Here, we investigate the effect of substrate and electron donor limitation on phenotypic heterogeneity in N2 and CO2 fixation in the green sulphur bacterium Chlorobium phaeobacteroides. We grew populations in chemostats and batch cultures and used stable isotope labelling combined with nanometer‐scale secondary ion mass spectrometry (NanoSIMS) to quantify phenotypic heterogeneity. Experiments in H2S (i.e. electron donor) limited chemostats show that varying levels of NH4+ limitation induce heterogeneity in N2 fixation. Comparison of phenotypic heterogeneity between chemostats and batch (unlimited for H2S) populations indicates that electron donor limitation drives heterogeneity in N2 and CO2 fixation. Our results demonstrate that phenotypic heterogeneity in a certain metabolic activity can be driven by different modes of limitation and that heterogeneity can emerge in different metabolic processes upon the same mode of limitation. In conclusion, our data suggest that limitation is a general driver of phenotypic heterogeneity in microbial populations.
Partial penetration welding with fiber laser on 20mm thick plates was carried out in horizontal position to study the role of secondary heating in modeling of high power fiber laser welding. Experiments were carried out using 18.8kW laser with 1.5 m/min welding speed at Ar assist gas flow rates of 0, 17, 29, and 40 l/min, all four cases show similar bead shape with bright emission of vapor plume. Numerical simulations were performed using volume of fluid method by considering three different models as models A–C. Model A considers only Fresnel reflection inside the keyhole using real time tracking of free surface. Model B considers vapor recondensation flux inside keyhole along with model A. Finally, model C is used, which considers vapor plume heating at 4100K temperature along with models A B. Secondary heating by recondensation and vapor plume is vital in modeling of high power fiber laser welding; especially, the upper part of the bead is more influenced due to secondary heating. Tungsten particles are also used to visualize the flow pattern of melt pool.
Studies on the mechanochemical Knoevenagel condensation of fluorinated benzaldehyde derivates
(2018)
The mechanochemical Knoevenagel condensation of three fluorinated benzaldehyde derivates and malononitrile was investigated. The reactions were performed under solvent- and catalyst-free conditions and resulted in highly crystalline products after crystallization from a viscous phase in the milling jar.
The quality of the obtained crystals was sufficient for single-crystal X-ray diffraction circumventing a recrystallization step. To gain more information on the reaction, progress was investigated in situ using time-resolved Raman spectroscopy. The results show a direct conversion of the reactants.
Studies on the development of antibodies for the highly hydrophobic plasticizers DINCH and DEHT
(2018)
Diisononylcyclohexane-1,2-dicarboxylate (DINCH) and di-2-ethylhexyl terephthalate (DEHT), two of the most important substitutes for phthalate plasticizers, are used for a wide range of applications. Consequently, an increasing occurrence in urine and environmental samples is reported. Reliable and fast analytical methods for the quantification of these plasticizers are needed. So far, mainly GC-MS or LC-MS methods are used. We aimed to develop the first antibodies and immunoassays allowing for high-throughput analysis of samples. We designed two DINCH hapten structures and one DEHT hapten structure and employed hapten-protein conjugates for the immunization of rabbits. Sensitive competitive enzyme-linked immunosorbent assays (ELISAs) against each hapten using the produced polyclonal antibodies were established. Yet, binding of DINCH to the respective antibodies was not observed in neither direct nor indirect assay formats, even when using protein conjugates with the heterologous haptens and different carrier proteins in the indirect format. The use of surfactants and solvents in the sample buffer did not result in recognition of the plasticizers. Also, no binding of DEHT in ELISA employing the respective antibodies was detected. We speculate that the production of antibodies against these highly hydrophobic molecules is not possible via our route, however a different hapten design could overcome this obstacle.
Die Grundidee einer Schwingungsminderung ist es eine tiefe Eigenfrequenz der Struktur zu erreichen, so dass höhere Frequenzen abgemindert werden. Das gilt für die Minderung an der Quelle, zum Beispiel einem Eisenbahngleis, und für die Minderung am Empfänger, dem Gebäude. Die Eigenfrequenz ermittelt man aus dem Verhältnis der Auflagersteifigkeit und der Masse. Wie ist die Masse bei einem Gebäude zu wählen? Und wie ist die Untergrundsteifigkeit zu berücksichtigen? Als Referenzsituation ohne Minderungsmaßnahme? Der Beitrag bringt Rechenergebnisse zu abgefederten Gebäuden mit einfachen und komplexen (FE-) Modellen, Mess- und Rechenergebnisse zur Schwingungsübertragung von unabgefederten Gebäuden. Es wird der Einfluss der Abstimmfrequenz, der Bodensteifigkeit und der „starren“ Gebäudemasse untersucht. Die komplexen Gebäudemodelle erlauben, neben der Berechnung einer elastischen Gebäudelagerung, auch die Variation von Gebäudeparametern zur Reduktion der Deckenschwingungen. Den Ergebnissen bei der Erschütterungs-übertragung in Gebäude werden zwei ähnliche Beispiele zur elastischen Maschinenlagerung und zur elastischen Gleislagerung gegenübergestellt.
Measuring means knowing. The structural engineer’s Knowledge about structures is vitally important for the assessment of their structural safety. This contribution shows, how non-destructive testing methods can be used to collect valuable Information about existing structures. This value is expressed in this paper by the usability in probabilistic assessments and thus by the reliability of the information. The development of non-destructive testing methods in civil-engineering allows the realistic measurement and visualization of inner constructions of concrete components with a minimum of destructive interventions.
The evaluation of the quality of measurement data is of fundamental importance for quantitative measurements in order to ensure the objectivity of testing and evaluation and to assess the reliability of the knowledge acquired. Both systematic and random deviations must be identified, quantified and taken into account to obtain statistically sound data. The Focus of this contribution is on the methodical path, how displayed measurement data can be processed into reliable knowledge.
It is not about developing assessment methods but about providing
necessary knowledge to increase their operational usability.
Borosilicate glasses (16Na2O–10B2O3–74SiO2, NBS) with water contents up to 22 mol% H2O were prepared to study the effect of water on structural relaxation using DTA, viscometry and internal friction measurements. The results show that the glass transition temperature Tg of DTA and the isokom temperature T12, of viscometry are in excellent agreement, confirming the equivalence of enthalpy and viscous relaxation for NBS glass. Combining Tg data with water speciation data demonstrates that OH groups are mainly responsible for the decrease of Tg with increasing hydration, while molecular water plays only a minor role. Internal friction spectra at 7.125 Hz confirm the decisive influence of water on mechanical relaxation. The temperature range of α-relaxation (glass transition) strongly decreases while two β-relaxation peaks (sub-Tg) progressively appear with increasing water content. A high temperature β-relaxation peak, attributed to the presence of OH groups, shifts from 670 to 450 K as total water content increases from 0.01 to 5 wt%. A low temperature β-relaxation peak, attributed to molecular water, appears at 380 K and 330 K in glasses containing 3 and 5 wt% H2O, respectively. These findings suggest that relaxation mechanism of different hydrous species at low temperature may contribute to fatigue of stressed glasses.
Composite pressure vessels are important components in the storage of gases under high pressure. Among others, a common type of pressure vessel is made of a metal liner overwrapped with a fibre-reinforced plastic material. Conventional hydrostatic tests, used to assess the integrity of pressure vessels, may overstress the material and thus reduce the remaining lifetime of the tested component. Therefore, a truly non-destructive structural health monitoring (SHM) system would not only ensure a safer usage and extended lifetime, but also remove the necessity for periodic inspection and the testing of pressure vessels. The authors propose the use of guided ultrasonic waves, which have the potential to detect the main damage types, such as cracking in the metal liner, fibre breaks and composite matrix delamination. For the design of such an SHM system, multimodal ultrasonic wave propagation and defect-mode interaction must be fully understood. In this paper, simulation results obtained by means of finite element modelling (FEM) are presented. Based on the findings, suggestions are made regarding appropriate wave modes and their interaction with different flaw types, as well as the necessary excitation and suitable sensor configurations. Finally, a first approach for a reliable SHM system for composite pressure vessels is suggested.
This work describes a vibration-based structural health monitoring of a prestressed-concrete box girder bridge on the A100 Highway in Berlin by applying statistical pattern recognition technique to a huge amount of data continuously collected by an integrated monitoring system during the period from 2000 to 2013. Firstly, the general condition and potential damage of the bridge is described. Then, the dynamic properties are extracted from 20 velocity sensors. Environmental variability captured by five thermal transducers and traffic intensity approximately estimated by strain measurements are also reported. Nonlinear influences of temperature on natural frequencies are observed. Subsequently, the measurements during the first year are used to build a baseline health index. The multiple linear regression (MLR) method is used to characterize the nonlinear relationship between natural frequencies and temperatures. The Euclidean distance of the residual errors is calculated to build a statistical health index. Finally, the indices extracted from the following years gradually deviate; which may indicate structural deterioration due to loss of prestress in the prestressed tendons.
The aim of this study was to identify specific chemical bonds and characteristic structures in melanoidins formed from D-glucose and L-alanine between 130 and 200 °C. The results might be used to control the type and amount of melanoidin produced during food processing. For this purpose, complementary techniques, such as FTIR, NMR, EPR, and MALDI-ToF, were employed. At 160 °C color, solubility and UV/Vis absorption change characteristically and consequently, structural transformations could be observed in FTIR and NMR spectra. For example, sharp signals of N-H, C-N, and C-H oscillations in the L-alanine spectrum are prone to inhomogeneous broadening in melanoidins prepared above 150 °C. These changes are caused due to formation of heterogeneous macromolecular structures and occur during condensation reactions that lead to an increasing loss of water from the melanoidins with increasing temperatures. Additionally, MALDI-ToF-MS indicates the polymerization of glyoxal/glyoxylic acid and EPR shows the formation of radical structures.