Datei im Netzwerk der BAM verfügbar ("Closed Access")
Filtern
Erscheinungsjahr
- 2015 (833) (entfernen)
Dokumenttyp
- Zeitschriftenartikel (397)
- Beitrag zu einem Tagungsband (256)
- Vortrag (73)
- Posterpräsentation (43)
- Beitrag zu einem Sammelband (16)
- Forschungsbericht (16)
- Buchkapitel (14)
- Sonstiges (11)
- Tagungsband (Herausgeberschaft für den kompletten Band) (4)
- Sammelband (Herausgeberschaft für den kompletten Band) (1)
Sprache
- Englisch (612)
- Deutsch (216)
- Mehrsprachig (4)
- Französisch (1)
Schlagworte
- Corrosion (16)
- Concrete (13)
- Simulation (10)
- Monitoring (9)
- Prozessanalytik (9)
- Fluorescence (8)
- EDX (7)
- Elastomer (7)
- Fatigue (7)
- Laser beam welding (7)
Eingeladener Vortrag
- nein (73)
A surface-labeled lyophilized lymphocyte (sLL) preparation has been developed using human peripheral blood mononuclear cells prelabeled with a fluorescein isothiocyanate conjugated anti-CD4 monoclonal antibody. The sLL preparation is intended to be used as a reference material for CD4+ cell counting including the development of higher order reference measurement procedures and has been evaluated in the pilot study CCQM-P102. This study was conducted across 16 laboratories from eight countries to assess the ability of participants to quantify the CD4+ cell count of this reference material and to document cross-laboratory variability plus associated measurement uncertainties. Twelve different flow cytometer platforms were evaluated using a standard protocol that included calibration beads used to obtain quantitative measurements of CD4+ T cell counts. There was good overall cross-platform and counting method agreement with a grand mean of the laboratory calculated means of (301.7 ± 4.9) µL-1 CD4+ cells. Excluding outliers, greater than 90% of participant data agreed within ±15%. A major contribution to variation of sLL CD4+ cell counts was tube to tube variation of the calibration beads, amounting to an uncertainty of 3.6%. Variation due to preparative steps equated to an uncertainty of 2.6%. There was no reduction in variability when data files were centrally reanalyzed. Remaining variation was attributed to instrument specific differences. CD4+ cell counts obtained in CCQM-P102 are in excellent agreement and show the robustness of both the measurements and the data analysis and hence the suitability of sLL as a reference material for interlaboratory comparisons and external quality assessment.
Lightweight granules are mineral, spherical and porous particles with bulk density less than 2000 kg m . New types of lightweight granules are made from masonry -3 rubble as an alternative to the commonly used expanded clay and shale. They are produced in a multistage manufacturing process by thermal or hydrothermal treatment. Studies of the microstructure of the new lightweight granules are very important to optimise the engineering properties with regard to different applications from lightweight concrete to planting substrates and wastewater treatment. Here, the results of porosity and pore structure measurements are presented. Characteristic samples with different bulk densities of both thermally and hydrothermally hardened granules have been analysed by means of various methods.
Die Bestimmung der Haftfestigkeit von Lackierungen, Beschichtungen oder Klebeverbunden ist ein wichtiges Analyseinstrument bei der Beurteilung von entsprechenden Fertigungsabläufen. Unter Verwendung einer neuen Zentrifugentechnologie wurde in einem AiF Forschungsprojekt OKTETT die gesamte Prozesskette Vorbehandlung - Verklebung - Prüfung validiert.
Seit 1829 wird die Farbe Cadmium Gelb in der Malerei verwendet, Cadmium Rot seit 1907. Wegen ihrer Klarheit und Leuchtkraft werden diese Farben von vielen Künstlern geschätzt. Aus Schweden kommt nun der Vorstoß, die Cadmium-Farben zu verbieten, weil das Schwermetall Cadmium zur Verunreinigung landwirtschaftlicher Flächen führen könnte. Sie beraten die Europäische Chemikalienagentur ECHA, die für das Verbotsverfahren zuständig ist. Müssen Künstler in naher Zukunft auf Cadmium Gelb und Cadmium Rot verzichten?
Recently three of the authors of this paper presented analytical solutions for reference loads of plate geometries with semi-elliptical surface cracks subjected to tension, bending, combined tension-bending and biaxial tension. These solutions were shown to provide more accurate crack driving force estimates than the conventional limit load solutions available in the literature, and the method behind them allowed for a wider application range. Within the present paper a methodology for the fracture analysis of thick-wall pressurized pipes using the R6 assessment method and considering both, biaxial and combined tension-bending loading is developed and validated. The analyses are carried out analytically, and the comparison between the predicted critical loads and experimental burst test failure loads shows satisfying agreement, this way demonstrating the potential of the proposed method.
Mit dem generellen Ziel, die Anwendbarkeit und Funktionalität des Verfahrens der stochastischen subspace-basierten Schadensdetektion für Strukturen von Offshore-Windenergieanlagen nachzuweisen, wurden experimentelle und numerische Untersuchungen an einer Laborstruktur sowie anschließend numerische Untersuchungen an einer OWEA-Gründungsstruktur durchgeführt.
Das zugrundeliegende Verfahren verwendet einen Ansatz, in weder modale Kenngrößen noch andere benutzerdefinierte Eingaben erfordert, nachdem einmalig der Referenzzustand aufgenommen wurde. Dabei werden ausschließlich dem Belastungsprozess inhärente stochastische Anregungen der betrachteten Struktur genutzt.
Auf der Basis experimentell erzielter Detektionsergebnisse aus einem Ermüdungsversuch an einer Laborstruktur aus Stahl wurden numerische Modelle und Berechnungsalgorithmen entwickelt und getestet. In einem zweiten Schritt wird diese Analysemethodik auf eine fiktive OWEA-Jacketstruktur realer Größe angewendet. An den simulierten Strukturantworten im Ungeschädigten und geschädigten Zustand wird der Detektionsalgorithmus angewendet, um den Einfluss von Sensorposition und Abtastrate auf die Schadensdetektion festzustellen. Unter Berücksichtigung einzelner vereinfachender Annahmen zeigten die Ergebnisse der Anwendung der vorgestellten Detektionsmethodik an den numerisch erzeugte Antwortdatensätzen eine beachtliche Empfindlichkeit des x2-Testwert basierten Schadensindikators. Obwohl nicht unter allen Umständen in einem frühen Stadium nachweisbar, typische Ermüdungsrisse in Schweißverbindungen von aufgelösten Tragwerken haben ab einer Restbiegesteifigkeit von ca. 80% einen signifikanten und detektierbaren Einfluss auf den Schadensindikator.
Künftige Forschungsaktivitäten in diesem Bereich sollten neben der Erkennung von Schäden auch die Lokalisierung und ggf. auch die Quantifizierung zum Ziel haben. Erforderlich dazu ist die Berücksichtigung und Verarbeitung der strukturellen Parameter und ihrer Sensitivitäten im zugrunde liegenden mathematischen Modell.
Neutron radiography and tomography have been used for a time resolved in situ analysis and a 3D mapping of hydrogen diffusion in iron and steel. Samples were electrochemically charged with hydrogen and afterwards neutron transmission images were taken. Hydrogen diffusion coefficients in duplex stainless steel were determined at 623 K by measuring and comparing the sample's mean intensity with a hydrogen-free reference sample and subsequent normalisation to standards with known hydrogen content. In technical iron and in supermartensitic stainless steel the hydrogen distributions have been investigated. The radiographic images in iron show blisters, cracks and the distribution of molecular hydrogen inside cracks. The analysis of the diffusion behaviour of hydrogen out of a blister illustrates the capabilities of the method with respect to time and spatial resolution. The neutron tomography of supermartensitic tensile stressed samples illustrates the capability to visualise hydrogen distributions three-dimensionally. -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
On a utilisé la radiographie neutronique et la tomographie pour une analyse in situ à résolution temporelle et une cartographie 3D de la diffusion de l'hydrogène dans le fer et l'acier. On a chargé des échantillons par électrochimie avec de l'hydrogène et ensuite on a pris des images par émission de neutrons. On a déterminé les coefficients de diffusion de lhydrogène dans l'acier inoxydable duplex à 623 K en mesurant et en comparant l'intensité moyenne de l'échantillon avec un échantillon de référence sans hydrogène et une normalisation subséquente à des échantillons références à teneur connue en hydrogène. On a examiné la distribution d'hydrogène dans le fer technique et dans l'acier inoxydable supermartensitique. Les images radiographiques du fer montrent des soufflures, des fissures, et la distribution de l'hydrogène moléculaire à l'intérieur des fissures. L'analyse du comportement de diffusion de l'hydrogène hors d'une soufflure illustre les possibilités de la méthode par rapport à la résolution temporelle et spatiale. La tomographie neutronique des échantillons supermartensitiques chargés en traction illustre la capacité de visualiser les distributions d'hydrogène en trois dimensions.
Der Beitrag konzentriert sich auf bildgebende Messverfahren, die der dreidimensionalen Bestimmung mechanischer, geometrischer und kinematischer Parameter von Materialien und Bauteilen dienen. Das sind hier insbesondere die Mehrbildfotogrammetrie sowie die Stereomessverfahren, die auf folgenden physikalisch-optischen Grundlagen beruhen: die zeit- und raumveränderliche Projektion von Lichtstreifensystemen, die Bildkorrelation mittels Grauwertmustern und die Verfolgung kontrastreich applizierter Punkttargets. Letztendlich werden aus den gemessenen Punktkoordinaten unterschiedlicher Dichte und Belastungszustände die gewünschten 3D-Parameter abgeleitet. Hierzu gehören z. B. die Oberflächengestalt und deren Verformung, approximierte 3D-Geometrielemente, veränderliche 6DoF-Starrkörperorientierungen, Vektorverschiebungsfelder, Oberflächendehnung, Koordinaten-Zeit-Funktionen, Geschwindigkeit und Beschleunigung. Diese Kenngrößen sind beispielsweise für die Ermittlung mechanischer Werkstoffeigenschaften und -kennwerte bis hin zur Form- und Verformungsmessung von Bauteilen in gezielt quasi-statisch oder dynamisch beanspruchenden Prüfeinrichtungen wichtig. Vorteilhaft für die praktische Anwendung dieser Verfahren ist insbesondere, dass sie berührungslos arbeiten, kombiniert werden können und skalierbar sind z. B. hinsichtlich Messvolumen, Auflösung, Genauigkeit und Koordinatensystemen der zu bestimmenden 3D-Punktkoordinaten an Materialoberflächen bzw. Komponenten.
Ausgehend von der Beschreibung der messtechnischen Prinzipien dieser Verfahren sollen zwei Anwendungsbeispiele aus dem Bereich der Gefahrgutbehäl-terprüfung im Rahmen von Bauartzulassungen und der normungsbegleitenden Mate-rialforschung den Stand in der Anwendungspraxis aufzeigen und einen Eindruck hinsichtlich der flexiblen Einsatzmöglichkeiten dieser optischen 3D-Verfahren verdeutlichen.
Der vorliegende Bericht gibt einen Überblick über die Normenreihen DIN EN 16261 'Pyrotechnische Gegenstände - Feuerwerkskörper, Kategorie 4' und DIN EN 16256 'Pyrotechnische Gegenstände - Pyrotechnische Gegenstände für Bühne und Theater'. Neben der Vorstellung der jeweiligen Anwendungsbereiche werden die wesentlichen Anforderungen an Konstruktion, Funktion und Kennzeichnung aufgezeigt. Des Weiteren werden die Prüf- und Bewertungsmethoden dieser pyrotechnischen Gegenstände dargestellt und miteinander verglichen. Die Normenreihe DIN EN 16261 besteht aus 4 Teilen 'Begriffe', 'Anforderungen', 'Prüfverfahren' und 'Mindestanforderungen an die Kennzeichnung und Gebrauchsanweisung'. Die Normenreihe DIN EN 16256 ist strukturell vergleichbar aufgebaut enthält aber im Vergleich zur Normenreihe DIN EN 16261 einen weiteren Teil zur Unterscheidung der Kategorien T1 und T2.
Melamine and melamine resins are widely used as fire-retardants for polymer building materials. Cured melamine systems are used in heat-sensitive items, such as furniture and window frames and sills. In this work, differently cured methylated poly(melamine-co-formaldehyde) (cmPMF) resins were used as fire-retardant coverage for poly(styrene) (PS) and poly(ethylene) (PE) building materials. Such polymer layers should have several tenths of micrometers thickness to produce sufficient fire retardancy. These thick layers were produced by dip-coating. To promote sufficient adhesion of such thick coating to the polyolefin substrates, also in the case of high temperatures occurring at fire exposure, the polymer substrates were firstly coated with a few hundred nanometer thick adhesion-promoting plasma polymer layer. Such thin plasma polymer layers were deposited by low-pressure plasma polymerization of allyl alcohol (ppAAl). It was assumed that the hydroxyl groups of ppAAl interact with the melamine resin; therefore, ppAAl was well suited as adhesion promoter for thick melamine resin coatings. Chemical structure and composition of polymer films were investigated using infrared-attenuated total reflectance and X-ray photoelectron spectroscopy (XPS). Peel strengths of coatings were measured. After peeling, the peeled polymer surfaces were also investigated using optical microscopy and XPS the layers for identification of the locus of peel front propagation. Thermal properties were analyzed using TGA (thermo-gravimetric analyses). Finally, the fire-retardant properties of such thick coated polymers were evaluated by exposure to flames.
The fluorine content of polymer particles labelled with 2,2,2-trifluoroethylamine was reliably quantified with overlapping sensitivity ranges by XPS and solid-state NMR. This provides a first step towards reference materials for the metrological traceability of surface group quantifications. The extension of this concept to fluorescence spectroscopy is illustrated.
Pyrotechnische Gegenstände in Form von Treibladungskartuschen für den Einsatz in der Sprengtechnik
(2015)
Anforderungen, Prüfverfahren und praktische Erprobung von Treibladungskartuschen für den Einsatz in der Sprengtechnik werden erläutert. Nach der europäischen Rechtslage und den europäischen Normen handelt es sich bei derartigen Gegenständen um so genannte steinbrechende Kartuschen, die der EU-Richtlinie 2007/23/EG unterliegen und somit als pyrotechnische Gegenstände behandelt werden.
Ultraschall-Transmissionsmessungen werden seit Jahrzehnten bei der Qualitätssicherung von Betonkonstruktionen eingesetzt. Aus den Wellengeschwindigkeiten lassen sich dynamische Elastizitätsmoduln und – nach lokaler Kalibrierung – auch Druckfestigkeiten ermitteln. Zudem ergeben sich Hinweise auf Risse und andere Materialschwächungen. Der Einsatz erfolgt vor allem im Labor oder an der Bauwerksoberfläche. Neuerdings werden auch Monitoringsysteme mit eingebetteten Sensoren auf Ultraschallbasis erfolgreich getestet. Die Talsperre Eibenstock dient als größte Sperre in Sachsen der Trinkwasserversorgung und dem Hochwasserschutz. Hier wurden während der Bauphase im Jahr 1979 im Fußbereich des Mauerkörpers Ultraschallsensoren eingebracht, die in Verbindung mit einem Messoszilloskop eine Überwachung der Erhärtung des Mauerbetons ermöglichten.
Der für die Sensorauswahl eingesetzte Messstellenumschalter wurde im September 2011 grundlegend instand gesetzt. Danach zeigte sich, dass die eingebetteten Sensoren selbst sowie die Verkabelung auch nach über fünfunddreißig Jahren in einwandfreiem Zustand sind. Eine nunmehr aufgelegte Messserie mit modernem Gerät von über einem Jahr mit ein- bis zweimonatigen Intervallen zeigte, dass die Wellengeschwindigkeit seit der Bauphase noch einmal um gut 10 % zugenommen hat, was für eine erhöhte Druckfestigkeit spricht. Innerhalb des Jahres zeigten sich auch bei Einsatz neuer, sehr sensibler Auswertemethoden (sog. Codawelleninterferometrie) nur geringfügige Schwankungen. Diese waren auch nicht zu erwarten, da sich die Füllhöhe zu den Messzeitpunkten nur gering unterschied, die Temperatur im Bauwerksinneren nur wenig schwankte und der Bauwerkszustand sehr gut ist.
Die Aussagen zur Betongüte sind direkt vergleichbar mit den früheren Mess- und Untersuchungsergebnissen an der Talsperre Gottleuba, die im gleichen Zeitraum errichtet wurde und ebenfalls mit einem Ultraschallsystem ausgerüstet war. Die Experimente zeigten, dass ein Einsatz von Ultraschallsystemen für die Bauwerksüberwachung auch über Jahrzehnte möglich ist. Dies war im vorliegenden Fall nie geplant, aber durch den Einsatz der Mitarbeiter vor Ort und der Herstellerfirma möglich. Bei zukünftigen Systemen ist eine langfristige Planung unter Einbeziehung aller Beteiligten sowie eine Einbindung in Überwachungs- und Wartungspläne notwendig, damit die qualitätsgesichert gewonnen Daten gewinnbringend genutzt werden können.
The investigation of physical properties and chemical composition generates important data for answering cultural-history questions that cannot be solved by historical and philological methods alone. In its individual materiality, each manuscript is the result of a wide variety of influences. The ‘life’ of a manuscript starts with its production, followed by the use and storage of the manuscript, and is finally characterized by its treatment during restoration. Some of these characteristics are still in existence and may provide insights into the production process and history of a manuscript.
Geothermal sources are found to be the most aggressive natural environments for construction materials in terms of corrosion. This study was focused on investigating the suitability of stainless steel UNS S31603 in volcanic areas of geothermal sites Sibayak and Lahendong (Indonesia). Influence of different factors (temperatures up to 175 °C, chloride content up to 1500 mg/L and pH down to 2) was assessed to determine a 'safe operating window' of a power plant and assure the system integrity. Investigations were performed by means of electrochemical methods and long-term exposure tests.
The surfaces of polymeric dialyzer membranes consisting of polysulfone and polyvinylpyrrolidone were investigated regarding the lateral distribution and quantitative surface composition using time-of-flight secondary-ion-mass-spectrometry and x-ray photoelectron spectroscopy. Knowledge of the distribution and composition on the outer surface region is of utmost importance for understanding the biocompatibility of such dialyzer membranes. Both flat membranes and hollow fiber membranes were studied.
Aufgrund von Änderungen des Technischen Regelwerks im Bereich der Betriebssicherheitsverordnung und in den relevanten Normen wurde von der Kommission für Anlagensicherheit (KAS) eine Überarbeitung der Technischen Regel für Anlagensicherheit TRAS 110 in der Fassung von 10. November 2008 für erforderlich gehalten. Nach Beteiligung der Öffentlichkeit und der Bundesländer ist die Neufassung am 6. Januar 2015 im Bundesanzeiger veröffentlicht worden.
The materials in oxyfuel power plant will be subjected to CO2– and SO2–rich gases on the fireside. The oxidation behaviour of two 9–12 % Cr steels T92 and VM12 was studied under dry oxyfuel environment in the temperature range of 580–650 °C for up to 1,000 h. The oxide structure and morphology were analyzed using various experimental techniques. A complex temperature dependence of oxidation rate is observed for both T92 and VM12 whereby the oxidation rate decreased with increasing temperature. This is attributed to increased Cr-enrichment in the inner scale with increasing temperature. T92 and VM12 alloys are also susceptible to carburization in an oxyfuel environment.
The use of open GIS standards offers a broad variety of potential, particularly in the field of data exchange, data storage, and interoperability. GML and CityGML are excellent examples for the ontological description of real world objects by means of an open standard whereas SensorML serves to describe measurements, sensors and measuring platforms. The use of such standards offers not only the possibility of using a common standardised language, but also the use of open service standards. The combination of spatial data and sensor standards in services and service-oriented architectures goes far beyond previous existing solutions on the market and provides a novel platform for monitoring structures. That in fact is far more than a simple data storage model. The methods and models presented in this contribution allow a direct integration of sensor data and its provision through an open standard language. In this case, all the intermediate steps at any time through an open service interface are addressed and may be made available and provided to different actors and stakeholders participating in a construction scenario. The great potential and the added value of such an information system is the permanent availability of measurement and object data and an associated integrated analysis of sensor data in combination with a finite element model (FEM). The automatic derivation of a finite element model from the 3D structure model, the visualisation of FEM, the provision of raw (measurement) data and sensor information for each time of measurement transform the platform into a universal tool in the field of structural monitoring. This contribution introduces the individual components, the standards used and the interaction between the components to an overall system.
Antibodies armed with photosensitizers: from chemical synthesis to photobiological applications
(2015)
Targeting photosensitizers to cancer cells by conjugating them with specific antibodies, able to recognize and bind to tumor-associated antigens, is today one of the most attractive strategies in photodynamic therapy (PDT). This comprehensive review updates on chemical routes available for the preparation of photo-immunoconjugates (PICs), which show dual chemical and biological functionalities: photo-properties of the photosensitizer and the immunoreactivity of the antibody. Moreover, photobiological results obtained with such photo-immunoconjugates using in vitro and in vivo cancer models are also discussed.
In diesem Beitrag präsentieren wir innovative Methoden für die breitbandige und resonanzfreie Messung und Anregung von Ultraschall. Das Messverfahren verwendet eine Kunststofffolie und ein Laser-Vibrometer als breitbandigen und resonanzfreien Empfänger. Im Allgemeinen ermöglicht dieses Verfahren eine präzise Messung der Schallschnelle und des Schalldruckes in beliebigen, für das Laserlicht transparenten Flüssigkeiten und Gasen mit bekannter Dichte und Schallgeschwindigkeit. Das resonanzfreie Senden von Ultraschall basiert auf einem elektro-thermo-akustischen Wandlerprinzip und ermöglicht, im Gegensatz zu herkömmlichen Ultraschallwandlern, die Erzeugung von beliebig geformten akustischen Signalen ohne Resonanzen und ohne Nachschwingen.
Thin poly(acrylic acid) PAA films were deposited by pulsed plasma polymerization on different organic and inorganic substrates. The structureproperty relationships of the deposited acrylic acid polymers were studied in dependence on the monomer pressure by various techniques and probes. The surface and bulk properties of the plasma deposited films were investigated by X-ray photoelectron spectroscopy, attenuated total reflection infrared, and broad band dielectric spectroscopy. The experimental infrared frequencies of PAA films are compared with those predicted from quantum mechanical calculation. The concentration of the COOH groups in the film (stored in ambient air) decreased by about 15 % compared to the as-prepared sample. The plasma deposited PAA probably form a highly branched product. However, the dielectric measurements show that in addition to the hydrogen bonds, self condensation process was able to hinder the localized fluctuation as well. These processes lead to form a cross-linked network polymer film. Nevertheless, a low energy is sufficient to break these processes during heating at atmospheric pressure. Therefore, homogenized samples with free branches (functional group) were obtained after a first heating with structures close to conventional polymerized acrylic acid. Thus, a thermally stable product was obtained.
Revealing the inner secrets of intumescent chars by advanced small scale tests combined with µ-CT
(2015)
Testing of intumescent coatings for Steel is usually done in intermediate scale or even full scale experiments and is hence quite expensive. We developed two complementary small scale tests, simulating fully developed Tire. First is a strongly modified electrical muffle furnace, which is now able to follow the Standard temperature-time curve (according EN 1363-1) for 90 min in a very accurate manner. Düring the experiment backside temperatures are recorded and the growth of the char is observed with a custom made high temperature endoscope. Second is a testing apparatus based on a propane-oxygen-bumer for direct severe flame impingement of coated samples, reaching temperatures far above 1500 °C.
Our small scale samples are coated Steel plates of a size of 75 x 75 x 2 mm3. The structure-propertyrelation between additives, thermal properties and morphology of the char were examined using a well determined series of samples consisting of basic composition mixed with different additives. With the burner-testing-apparatus we studied the behavior of a high performance coating, which shows a transformation of the carbonaceous char into a ceramic foam at temperatures as high as 1600 °C. Nondestructive micro-computed tomography was used to characterize the morphology of the char. According to the structure of the foams we used different analytic methods like cell-detection or wallthickness-analysis. Additional scanning electron and optical microscopy were performed. The combination of the CT-data with the measured backside temperatures of the different samples provides us a deep understanding of the interaction between isolating properties and morphology of intumescent chars.
Microstructure, mechanical properties and corrosion behaviour of WZ21 (%wt.) alloy prepared by a powder metallurgy route from rapidly solidified powders have been studied. Results were compared to those of the same alloy prepared through a conventional route of casting and extrusion. The microstructure of the extruded ingot consisted of α-Mg grains and Mg3Zn3Y2 (W-phase) and LPSO-phase particles located at grain boundaries. Moreover, stacking faults were also observed within α-Mg grains. The alloy processed by the powder metallurgy route exhibited a more homogeneous and finer microstructure, with a grain size of 2 µm. In this case W-phase and Mg24Y5 phase were identified, but not the LPSO-phase. The microstructural refinement induced by the use of rapidly solidified powders strengthened the alloy at room temperature and promoted superplasticity at higher strain rates. Corrosion behaviour in PBS medium evidenced certain physical barrier effect of the almost continuous arrangements of second phases aligned along the extrusion direction in conventionally processed WZ21 alloy, with a stable tendency around 7 mm/year. On the other hand, powder metallurgy processing promoted significant pitting corrosion, inducing accelerated corrosion rate during prolonged immersion times.
Gas cylinders made from composite materials receive growing popularity in applications where light weight is of advantage. At the same time manufacturers are interested in cutting cost and weight through material reduction for better acceptance of a product, e.g. H2-vehicles. This requires a better understanding of safety relevant properties.
The safety determination of current standards is mainly based on the minimum burst pressure of a few specimens. Various research projects were conducted aiming at reducing minimum burst pressure requirements without compromising safety. No satisfying results were found. While looking at reliability aspects it could be concluded, that the minimum burst pressure of unused specimens is not a satisfying criterion for safety during service life.
This paper introduces first ideas for a method to determine one aspect of reliability of composite gas cylinders, employing probabilistic analysis of burst pressures of a sample of specimens. This can create potential for saving material cost while granting a higher safety level than the current method. Additionally, degradation over service time can be assessed.
In Europe the maximum allowable concentration for tributyltin (TBT) compounds in surface water has been regulated by the water framework directive (WFD) and daughter directive that impose a limit of 0.2 ng L-1 in whole water (as tributyltin cation). Despite the large number of different methodologies for the quantification of organotin species developed in the last two decades, standardised analytical methods at required concentration level do not exist. TBT quantification at picogram level requires efficient and accurate sample preparation and preconcentration, and maximum care to avoid blank contamination. To meet the WFD requirement, a method for the quantification of TBT in mineral water at environmental quality standard (EQS) level, based on solid phase extraction (SPE), was developed and optimised. The quantification was done using species-specific isotope dilution (SSID) followed by gas chromatography (GC) coupled to inductively coupled plasma mass spectrometry (ICP–MS). The analytical process was optimised using a design of experiment (DOE) based on a factorial fractionary plan. The DOE allowed to evaluate 3 qualitative factors (type of stationary phase and eluent, phase mass and eluent volume, pH and analyte ethylation procedure) for a total of 13 levels studied, and a sample volume in the range of 250–1000 mL. Four different models fitting the results were defined and evaluated with statistic tools: one of them was selected and optimised to find the best procedural conditions. C18 phase was found to be the best stationary phase for SPE experiments. The 4 solvents tested with C18, the pH and ethylation conditions, the mass of the phases, the volume of the eluents and the sample volume can all be optimal, but depending on their respective combination. For that reason, the equation of the model conceived in this work is a useful decisional tool for the planning of experiments, because it can be applied to predict the TBT mass fraction recovery when the experimental conditions are drawn. This work shows that SPE is a convenient technique for TBT pre-concentration at pico-trace levels and a robust approach: in fact (i) number of different experimental conditions led to satisfactory results and (ii) the participation of two institutes to the experimental work did not impact the developed model.
Im ersten Teil dieses Aufsatzes wurde gezeigt, dass nur ein Teil der für den Deponiebau wesentlichen technischen Eigenschaften in den europäisch harmonisierten Bauproduktnormen DIN EN 13252 und DIN EN 13257, die der CE-Kennzeichnung der Geotextilien (GTX) und geotextilverwandten Produkte (GTP) zugrunde liegen, erfasst werden. Um eine im Wesentlichen vorhandene Gleichwertigkeit der Produkteigenschaften überhaupt abwägen zu können, müssen aber sämtliche relevanten Eigenschaften bekannt sein. Dies erfordert für CE-gekennzeichnete Produkte zusätzliche Prüfungen auf der Grundlage der DepV-Liste der Kriterien und Einwirkmechanismen (Anhang 1, Nummer 2.1.1, DepV). In diesem Teil werden die Tabellen C1 und C2 sowie die Tabelle D aus dem ersten Teil, in denen die Eigenschaften der harmonisierten europäischen Normen (hEN) den Anforderungen der DepV gegenübergestellt wurden, in technischer Hinsicht näher erläutert.
Several fires involving external thermal insulating (ETIC) systems with polystyrene in Germany started an extensive discussion about fire safety of such systems. The Frankfurt fire service started to collect reports about real fire cases which involved ETICS with polystyrene two years ago. This collection shows that especially fires, which started in front of the buildings led to more severe fires of the facades than fires inside the buildings. In several fires the ignition sources were burning waste containers. Three of the real cases are discussed in more detail: a serious fire in Frankfurt on a building site and two fires of apartment buildings, which developed quite differently. Additionally the plastic waste containers, which started several fires are investigated regarding ignitability and heat release rates. The investigation shows that plastic waste containers are very effective as ignition source and that the usual placement directly in front of combustible facades can be a problem for fire safety. Moving these containers and unintentional contact with the facade can lead to damage of the facade coating. These damages were investigated qualitatively and quantitative on a wide collection of buildings. After classifying the damage intermediate scale tests were performed in a modified Single Burning Item (SBI) Test. The damage of the coating was varied as well as the power of the sand bed burner of the SBI apparatus. The damage significantly influenced the fire development on the specimen. In some tests the damaged rendering of the ETIC system collapsed and resulted in a sudden fire growth: after the collapse of the rendering the whole specimen was suddenly on fire. Several effects, which could be seen in the intermediate scale tests correspond to observations which were made in the real cases. As a consequence of the investigations challenges and possible measures to enhance fire safety of ETIC systems are discussed.
Multicomponent flame retardant systems containing aluminum diethylphosphinate in thermoplastic styrene–ethylene–butylene–styrene elastomers are investigated (oxygen index, UL 94, cone calorimeter, and mechanical testing). Solid-state nuclear magnetic resonance, scanning electron microscopy, and elemental analysis illuminate the interactions in the condensed phase. Thermoplastic styrene–ethylene–butylene–styrene elastomers are a challenge for flame retardancy (peak heat release rate at 50 kW m-2 > 2000 kW m-2, oxygen index = 17.2 vol%, no UL-94 horizontal burn rating) since it burns without residue and with a very high effective heat of combustion. Adding aluminum diethylphosphinate results in efficient flame inhibition and improves the reaction to small flame, but it is less effective in the cone calorimeter. Its efficacy levels off for amounts >~25 wt%. As the most promising synergistic system, aluminum diethylphosphinate/melamine polyphosphate was identified, combining the main gas action of aluminum diethylphosphinate with condensed phase mechanisms. The protection layer was further improved with several adjuvants. Keeping the overall flame retardant content at 30 wt%, aluminum diethylphosphinate/melamine polyphosphate/titanium dioxide and aluminum diethylphosphinate/melamine polyphosphate/boehmite were the best approaches. An oxygen index of up to 27 vol% was achieved and a horizontal burn rating in UL 94 with immediate self-extinction; peak heat release rate decreased by up to 85% compared to thermoplastic styrene–ethylene–butylene–styrene elastomers, to <300 kW m-2.
We demonstrate polarity-sensitive orientation mapping of non-centrosymmetric phases by Electron Backscatter Diffraction (EBSD). The method overcomes the restrictions of kinematic orientation determination by EBSD, which is limited to the centro-symmetric Laue-groups according to Friedel's rule. Using polycrystalline GaP as an example, we apply a quantitative pattern matching approach based on simulations using the dynamical theory of electron diffraction. This procedure results in a distinct assignment of the local orientation according to the non-centrosymmetric point group of the crystal structure under investigation.
The approaching CO2 targets have now enforced automotive OEMs to engage R&D efforts also in powertrain to reduce friction, increase lifetime properties, and load carrying capacities of running systems. Martensitic steels such as 36NiCrMoV1-5-7 have a great potential to be used in automotive powertrain applications due to its favorable mechanical properties. In order to realize lightweight strategies, it is essential that steels with improved fracture toughness values and higher annealing temperatures with regard to higher contact pressures and possible thin film coating application be considered. State-of-the-art steels, like 16MnCr5, 21NiCrMo, 30CrMoV9, and 100Cr6 are not able to sustain a further increase in torque or load during operating time as well as annealing effects under higher oil or deposition temperatures. Therefore, the recent research on the slip-rolling resistance, frictional, and wear behavior of steels such as 36NiCrMoV1-5-7, Cronidur 30 (AMS 5898), 20MnCr5 (SAE 4820 or 5120), and 100Cr6H (SAE E52100) showed that possible lean alloying concept alternatives with promising performance characteristics are already available.
The elastic anisotropy caused by the texture in the Nb3Sn filaments of PIT and RRP wires has been calculated by averaging the estimates of Voigt and Reuss, using published Nb3Sn single crystal elastic constants and the Nb3Sn grain orientation distribution determined in both wire types by Electron Backscatter Diffraction. At ambient temperature the calculated Nb3Sn E-moduli in axial direction in the PIT and the RRP wire are 130 GPa and 140 GPa, respectively. The calculated E-moduli are compared with tensile test results obtained for the corresponding wires and extracted filament bundles.
Die beiden in dieser Arbeit dargestellten Beispiele zeigen, dass sich die Low-strain-Pfahlintegritätsprüfung noch über den bisherigen, schon sehr erfolgreichen Stand hinaus entwickeln kann. Der Einsatz von Vibratortechnik und passender mathematischer Methoden bietet das Potential, Prüfungen auch unter bisher nicht lösbaren Randbedingungen durchzuführen. Dazu gehören sehr schlanke Pfähle und Messungen bei hohem Störpegel. Der erhöhte Mess- und Auswerteaufwand ist jedoch im Einzelfall gegenüber dem erzielbaren Erfolg abzugleichen. Apparativ müssen noch Entwicklungsarbeiten geleistet werden, um einen einfachen und zuverlässigen Einsatz in der Praxis zu ermöglichen. Die Messung mit mehreren Sensoren entlang des Pfahls kann schon heute in der Praxis eingesetzt werden. In vielen Fällen lassen sich damit auch Messungen an Pfählen im Bestand durchführen, bei denen die konventionelle Pfahlprüfung aufgrund von überlagernden Signalen aus der aufgehenden Struktur versagt.
Partial discharge in polymeric insulation of high voltage equipment causes cumulative damage that progressively deteriorates the insulation, leading to eventual failure. The electrical detection of related discharge current pulses may be challenged by electromagnetic interference from the environment. In such situations the detection of acoustic emission from partial discharge can greatly enhance its detectability, especially when electromagnetically immune fiber-optic acoustic sensors are used. During experiments involving such fiber-optic sensors that were specifically designed for the detection of partial discharge in elastomeric insulation, an unexpected type of acoustic emission was observed in silicone elastomer specimens with tip–plate electrode configurations and under DC electrical stress. We present and discuss experimental results that indicate space charge injection and subsequent spontaneous dynamical processes as the source of the detected acoustic emission. We use sensitive conventional partial discharge measurement instrumentation to show that the apparent acoustic efficiency of the processes leading to the observed acoustic emission is very high. Acoustic emission triggered by discharge events with individual apparent charge values of only a few femtocoulombs could be detected.
Ober die europäischen Produktnormen für Geokunststoffe (hEN) wird gestritten: Dienen sie nur einem einheitlichen Verfahren der CE-Kennzeichnung oder werden darin alle relevanten geotechnischen Eigenschaften so verbindlich festgelegt, dass darüber hinausgehende nationale Vorschriften ungültig werden? Der Streit wurde durch ein Urteil des Europäischen Gerichtshofs weiter angefacht. Davon noch nicht betroffen ist der Deponiebau. Die Deponie ist ein besonderes Bauwerk, bei dem vor allem abfallrechtliche Regelungen beachtet werden müssen. In der deutschen Deponieverordnung wurde daher eine mit der Europäischen Kommission abgestimmte Gleichwertigkeitsklausel für CE-gekennzeichnete Bauprodukte verankert, die diese Besonderheit berücksichtigt. Wir zeigen, dass das in den hEN festgelegte Eigenschaftsspektrum der Bauprodukte im Wesentlichen nicht gleichwertig zu dem Spektrum ist, das sich aus den Anforderungen der Deponieverordnung ergibt. Die Qualitätssicherung der hEN, die nur eine zertifizierte werkseigene Produktionskontrolle jedoch keine Fremdüberwachung vorsieht, entspricht ebenfalls nicht den Anforderungen der Deponieverordnung. Eine CE-Kennzeichnung kann daher eine BAM-Zulassung nicht gleichwertig ersetzen. Auch für andere geotechnische Anwendungsgebiete gilt, dass die geltenden hEN die Geokunststoffe nicht ausreichend charakterisieren. Die Antwort auf die Frage, wie verbindlich diese mangelhaften hEN werden könnten, ist daher von weitreichender Bedeutung für die gesamte Geotechnik.
The analysis of physical and chemical properties of artefacts provides important data for answering questions that cannot be solved by historical and philological methods alone. In its individual materiality, each manuscript is the result of various influences (e.g. production, storage, restoration, preservation). Given the recent technological developments (e.g. miniaturization of structural units, enlargement of memory capacity), technical diagnostics of art and cultural objects are becoming increasingly sought after in trans-disciplinary research. In this review we present a multi-instrumental approach to the investigation of manuscripts. Several case studies will illuminate our methodology.
Using plastic jerrycans or plastic containers, dangerous goods are transported as air freight in commercial aircrafts. Liquids or gases can escape by leakage or permeation effects from these plastic containers. The German Federal Institute for Materials Research and Testing (BAM) conducted prior research which showed that the lower explosion limit can be reached when transporting dangerous goods in sea-freight containers under normal transportation situations. The presented study is motivated based on these findings. The research objective of this study is to analyze the transportation situation of dangerous goods in cargo compartments of commercial airplanes. The scope of this paper is to present the experimental method used for validating a numerical model for CFD (Computational Fluid Dynamics) simulations and to present some simulation results of the mass transport of dangerous goods in the cargo compartment.
The velocity profiles and the mass transport is calculated using numerical simulations and measured by Laser-Doppler-Anemometry (LDA) experiments. The mock-up is a generic model of a wide-body aircraft lower deck cargo compartment in a 1: 10 scale. Geometry, air exchange rates and inlet as well as outlet flow conditions in the cargo compartment are modeled using realistic boundary conditions. The commercial CFD (Computational Fluid Dynamics) code ANSYS CFX 14 is used for numerical flow simulations applying RANS (Reynolds-Averaged-Navier-Stokes) equations and turbulence models. The turbulence models studied are the renormalization group k-e-model (RNG), the BSL-Reynolds-Stress model (BSL) and the SST-k-co-model by Menter (SST).
The flow measurement with LDA in the mock-up of a cargo compartment proves to be a feasible method for producing data to validate CFD simulations. Qualitative evaluation of the results shows a good overall agreement between numerical and experimental results. The experimental validation indicates that the implemented CFD model is capable of reproducing the flow situation in the model mock-up
In this work the determination of Cd, Cu, Cr, Fe and Sb as organic and inorganic additives in in-house plastic materials (ABS, LDPE) using electrothermal vaporization combined with inductively coupled plasma optical emission spectroscopy is described. The influence of CCl2F2 as gaseous halogenation modifier was investigated. Especially for the carbide forming elements the sensitivity was improved and the memory effects were significantly reduced. Calibration was performed by external calibration and standard addition with aqueous standard solutions added directly into the sample boats. Absolute limits of detection (3s-criterion) range between 0.1 ng (Cd) and 9 ng (Fe) which corresponds to relative values of 0.1 mg kg-1 and 1.6 mg kg-1, respectively, taking 5 mg as typical sample mass. The detection limits are sufficient to monitor the element contents of plastic materials according to European directives such as European directive on the safety of toys. The developed ETV-ICP-OES method allows a fast analysis with a high sample throughput (3 minutes per analysis), low sample consumption and good trueness and precision for the analyzed elements. Sample preparation is reduced to ashing the samples in a muffle furnace. Furthermore, measurements are possible regardless of the chemical form in the additives. For verification the results obtained with the developed method were compared with measurement results of independent methods ICP-MS/OES after digestion. In addition Cd, Cr and Pb were determined in a solid plastic reference material BAM-H010 to confirm the applicability and accuracy of the method.
Commercial platforms consisting of ready-to-use microarrays printed with target-specific DNA probes, a microarray scanner, and software for data analysis are available for different applications in medical diagnostics and food analysis, detecting, e.g., viral and bacteriological DNA sequences. The transfer of these tools from basic research to routine analysis, their broad acceptance in regulated areas, and their use in medical practice requires suitable calibration tools for regular control of instrument performance in addition to internal assay controls. Here, we present the development of a novel assay-adapted calibration slide for a commercialized DNA-based assay platform, consisting of precisely arranged fluorescent areas of various intensities obtained by incorporating different concentrations of a 'green' dye and a 'red' dye in a polymer matrix. These dyes present 'Cy3' and 'Cy5' analogues with improved photostability, chosen based upon their spectroscopic properties closely matching those of common labels for the green and red channel of microarray scanners. This simple tool allows to efficiently and regularly assess and control the performance of the microarray scanner provided with the biochip platform and to compare different scanners. It will be eventually used as fluorescence intensity scale for referencing of assays results and to enhance the overall comparability of diagnostic tests.
Die grundsätzliche Eignung des Verfahrens zur Beurteilung der Passivschichtstabilität konnte mit den vorliegenden Untersuchungen nachgewiesen werden und Grenzen der Anwendbarkeit aufgezeigt werden. Es sind verschiedene Einflüsse in Parameterstudien gezielt untersucht und mit bekannten Methoden zur Beschreibung der Korrosionsbeständigkeit verifiziert worden. Das KorroPad-Prüfverfahren wirkt vorrangig oberflächenspezifisch und eignet sich zur vergleichenden Prüfung von nichtrostenden Stahloberflächen hinsichtlich ihrer Korrosionsbeständigkeit. Der Feuchtlagerung frisch bearbeiteter Oberflächen vor einer KorroPad-Prüfung kommt dabei eine große Bedeutung zu, um eine sichere Differenzierung von korrosionsanfälligen und -beständigen Oberflächen zu gewährleisten.
The automotive industry places significant importance on downsizing components to achieve greater efficiency. The goal of reducing CO2 emissions has led to the development of lightweight materials that are also able to enhance performance. In light of these aspirations, the aim of this study is to characterize two novel, high-performance steels, as well as a 'classical' gear steel for comparison with each other and currently applied materials. The gear steel underwent carburization and subsequent deep freezing treatments in an attempt to yield discrete sample groups with respect to residual austenite. The high-performance steels were heat treated as recommended by their respective manufacturers, and were not carburized. Elemental analyses were conducted by multiple methods to ensure accurate results. Residual austenite contents of the steels and the depth profiles of residual stresses were determined by X-ray diffraction (XRD). Hardness profiles were taken from the testing surfaces into the material core. The carburization of 20MnCr5 led to higher hardness and the greater concentration of carbon in the carburization zone more representative of a hardened SAE E52100, or 100Cr6/102Cr6, than of a non-carburized 20MnCr5. Residual austenite contents ranging from approximately 6–14 vol% were generated, though effectively providing only two, rather than the desired four discrete sample groups. Residual stresses from machining and carburization were measured directly at the sample surface, and from carburization alone below the surface. The high-performance steels fulfilled manufacturer expectations in terms of elemental content, hardness between 50 and 55 HRC and strongly martensitic microstructure character. Finally, slip-rolling endurance testing (T=+120 °C, 10,000,000 cycles, approximately 19 days in a factory fill engine oil) was carried out on all materials, whereby coefficient of friction distributions during testing and wear coefficients after testing were calculated. Testing was performed up to and including P0Mean=1.94 GPa (P0Max=2.91 GPa, FN=2000 N). Ultimately, the non-carburized high-performance steels showed competitive wear performance and better friction behaviour than the carburized 20MnCr5, which has been attributed to their work hardening capability.
This study aims at improving the detection of near-surface defects in magnetizable and conductive specimens by combining the measurements of eddy current, magnetic flux leakage and thermography testing. Different signal processing methods for data normalization are proposed to enable data fusion at the pixel level. These methods are applied to a test specimen which contains 10 variably-sized defects. We quantitatively evaluate the performances of a total of 29 detection methods with respect to false alarm reduction at a fixed level of true positive rate. We report that false positive rate could be reduced from 1.65% down to 0.28% by the best multi-sensor method compared to the best single-sensor performance on the smallest defect, when 50% found flaw pixels are required for successful detection.
In the last years, new approaches for the evaluation of the corrosion resistance of martensitic stainless steels were developed, which allow nearly non-destructive as well as short-term corrosion testing. This work analyzes the sensitive influence of microstructure and surface treatment on the corrosion resistance. The effect of alloy composition and microstructure, which is always present in addition to the influence of various surface treatments will be evaluated and discussed. The corrosion behavior was investigated with conventional evaluation of the pitting potential, electrochemical potentiodynamic reactivation (EPR), electrochemical noise (EN), and the 'KorroPad' (KP) technique. EPR provided information about the passivation ability and the extent of chromium content reduction due to chromium carbide precipitation in the microstructure. The use of EN and KP aims to detect the influence of different surface treatment parameters on the corrosion resistance in a nearly non-destructive way. Furthermore the results shall demonstrate the functionality and convenience of the short-term corrosion test methods EN and KP in order to gain more acceptance within the scientific community. The results will allow the extraction of surface treatment effects on the corrosion behavior of the martensitic stainless steels 1.4116, 1.4034, and 1.4021.
ln den letzten Jahren hat sich gezeigt, dass die Ermittlung des Schwellenwertes DeltaKth nach den bestehenden Standardvorschriften für verschiedene Materialien zu nichtkonservativen Werten führt. Das ergibt sich im Vergleich mit Schwellenwerten, die man mit Anrissen erhält, die hinsichtlich der Ober- und der Unterlast komplett im Druckbereich erzeugt wurden. Dort, wo die Diskrepanz auftritt, verstärkt sie sich mit abnehmendem Spannungsverhältnis. ln der vorliegenden Studie wurden an einem mittel- und einem hochfesten Stahl bei unterschiedlichen Spannungsverhältnissen Schwellenwerte bestimmt. Anwendung fanden die konventionelle Lastabsenkungsmethode nach ASTM-Standard und ein Verfahren, bei dem der Langrissscbwellenwert als Endpunkt der sogenannten Zyklischen R-Kurve erhalten wird. Dieses folgt im Wesentlichen der von Pippan et al. entwickelten Methode, ergänzt diese jedoch durch eine eigene Verfahrensvariante.
In Deutschland fallen aktuell über 5 Mio. Tonnen Hausmüllverbrennungsaschen (HMVA) pro Jahr an. Aus diesen werden nur ca. 8 % Metalle (davon ca. 1 % NE-Metalle) zurückgewonnen. Zur Beurteilung des Wertstoffpotentials werden die HMVA nach standardisierten Vorschriften beprobt, für die Analytik vorbehandelt/vorbereitet/aufgearbeitet und auf ihre Inhaltsstoffe analysiert. Im nachfolgenden Beitrag wird der Schwerpunkt auf die Probenvorbehandlung und -vorbereitung gelegt, wobei der Merkmalstransfer von der Ausgangs-(Feld-)Probe über die Laborprobe und die Prüfprobe bis zur Mess-(Analysen-) Probe am Beispiel von NE-Metallen einer nassaufbereiteten HMVA untersucht wurde. Die Ergebnisse wurden mit Hilfe statistischer Methoden bewertet. Die Ergebnisse zeigen, dass die Verteilung der NE-Metalle in den einzelnen Schritten der Probenbehandlung elementspezifisch ist. Bei Blei ist ein Erhalt der Merkmalsverteilung über alle Behandlungsschritte erkennbar. Bei Kupfer nehmen die Konzentrationen in den aufeinander folgenden Behandlungsschritten deutlich ab. Die Ursache könnte das in der Feinfraktion enthaltene metallische Kupfer mit seinen spezifischen Eigenschaften sein. -------------------------------------------------------------------------------------------------------------------------------------------
More than 5 billion tons of municipal solid waste incineration bottom ashes (MSWI BA) are generated by incineration per year in Germany. Currently only 8 % of metals (of these 1 % are non-ferrous metals) are recovered from MSWI BA. For characterization of recovery potential, MSWI BA samples have to be taken, pre-treated and analyzed according to standardized methods. This manuscript focuses on sample pre-treatment and preparation of a MSWI BA sample aiming to investigate the characteristics transfer over the process of sub-sampling from the original (field) sample to the laboratory sample, test sample until the analytical sample. All results have been evaluated with statistical methods. The results show that influence of each single pre-treatment and preparation step on metal content differs for the individual metals. For lead a conservation of characteristics distribution can be observed, while for copper a continuous decline of solid concentration is observed over all preparation steps. One possible reason may be the fact that copper is mainly contained in the fine fraction as metallic copper with specific properties.
We report on the formation of polymer-stabilized superparamagnetic single-core and multi-core maghemite nanoparticles. The particle formation was carried out by coprecipitation of Fe(II) and Fe(III) sulfate in a continuous aqueous process using a micromixer system. Aggregates containing 50 primary particles with sizes of 2 nm were formed at a reaction temperature of 30 °C. These particles aggregated further with time and were not stable. In contrast, stable single-core particles with a diameter of 7 nm were formed at 80 °C as revealed by small-angle X-ray scattering (SAXS) coupled in-line with the micromixer for particle characterization. X-ray diffraction and TEM confirmed the SAXS results. X-ray absorption near-edge structure spectroscopy (XANES) identified the iron oxide phase as maghemite.
Particle size modality in bi-modal iron oxide suspensions was resolved by exploiting complex ac-susceptibility (ACS), small angle X-ray scattering (SAXS) and photon cross-correlation spectroscopy. To explain dynamic magnetic response of bi-modal suspensions, the Debye model was expanded to a linear superposition form allowing for the contribution of both particle fractions. This modified and adopted model is able to resolve the bi-modal particle size distributions. The SAXS curves of mono- and bi-modal suspensions were fitted well using a Monte Carlo simulation scheme, allowing the detection of bi-modal particle size distributions with high precision.
Resovist® originally developed as a clinical liver contrast agent for Magnetic Resonance Imaging exhibits also an outstanding performance as a tracer in Magnetic Particle Imaging (MPI). In order to study the physical mechanism of the high MPI performance of Resovist®, we applied asymmetric flow fieldflow fractionation (A4F) and static magnetic fractionation (SMF) to separate Resovist® into a set of fractions with defined size classes. As A4F based on an elution method separates MNP according to their hydrodynamic size, SMF fractionates a particle distribution by its magnetic moment. The obtained fractions of both separation techniques were then magnetically characterized by magnetorelaxometry measurements to extract the corresponding effective magnetic anisotropy and hydrodynamic size distribution parameters. Additionally, the MPI performance of each fraction was assessed using magnetic particle spectroscopy. With both separation techniques fractions (normalized to their iron amount) an MPI signal gain of a factor of two could be obtained, even though the distribution of effective anisotropy and hydrodynamic size were significantly different. Relating these findings to the results from magnetic characterization allows for a better understanding of the underlying mechanisms of MPI performance of Resovist®. This knowledge may help to improve the design of novel MPI tracers and development of separation methods.
Shedding light onto the spectra of lime: Raman and luminescence bands of CaO, Ca(OH)2 and CaCO3
(2015)
In microscopy studies of 19th-century cement stone, we found free lime in the form of darkened spherical structures, as they were described in the literature already. When trying to determine their phase composition by Raman spectroscopy, we encountered contradictive assignments in literature spectra of the lime phases CaO, Ca(OH)2 and CaCO3 and observed strong spectral features that have been ignored or erroneously assigned so far. In this study we present Raman spectra of pure lime phases and of a naturally grown calcite crystal, burnt limestone (quick lime, mainly CaO), aged slaked lime putty (mainly Ca(OH)2), and carbonated lime putty (mainly CaCO3). Based on the results, we shed light mainly onto these two questions: (1) Does CaO have a Raman spectrum? (2) Which features in the spectra are luminescence bands that could be (and already have been) misinterpreted as Raman bands? We proof our assignment of luminescence bands in lime phases by using three different laser wavelengths for excitation, and give hypotheses on the origin of the luminescence as well as practical advices on how to identify these misleading features in Raman spectra. This article is mainly addressed to users of Raman spectroscopy in different fields of material analysis who might not be aware of the presence of interfering bands in their spectra.
Thermal ionisation, also known as surface ionisation, was one of the first ionisation techniques developed for mass spectrometry, having been invented as early as 1918. The ionization process, described by the empirically derived “fractionation laws”, is widely understood. Isotope ratio measurements can be achieved with high precision and accuracy. Due to this, thermal ionisation has paved the way for great scientific achievements including: the discovery of new isotopes, the determination of radioactive half-lives and atomic weights of the elements, the accurate determination of the age of the earth and investigations on human society in the past such as mobility and trade. TIMS is still regarded as ‘golden standard’ in isotope ratio measurements. Thus the method is a reference technique that remains at the forefront of isotopic analysis particularly in the fields of metrology. A concise overview is given here of the technical background of thermal ionisation as well as the numerous applications of this technique in earth sciences, industry, metrology, and nuclear forensics.
Measurement strategies
(2015)
Designing an appropriate measurement strategy for a particular analytical question is not always obvious, since a number of factors have to be considered, whereby some of them might be difficult to define. A set of key questions generally precede the experimental design in analytical measurements and help to choose the measurement strategy, which is fit for the intended use – in the particular case of the content of this book – either for quantification, elemental ratio or isotope ratio analyses, accordingly.
Maintenance, Repair and Overhaul (MRO) is acquiring increasing commercial and socio-economic significance. For products and goods with high investment costs and a long lifespan, especially in the sectors of energy and transportation, a considerable portion of commercial profits are generated by after-sales services. In the field of research and development, not enough attention has been paid so far to tasks and approaches involving MRO. The field thus has a limited scientific background, despite a high potential in the business sector for technological and scientific optimization. The challenges and chances of MRO for sustainable enterprises will be explained with reference to the Fraunhofer Innovation Cluster Maintenance, Repair and Overhaul in Energy and Transport. The developments and project results of the four fields of innovation »Cleaning«, »Repair and Overhaul«, »Condition Monitoring and Diagnosis«, as well as »MRO Planning and Digital Assistance« will be explained.
The application of high-strength fine-grained structural steels with yield strengths greater than or equal to 690 MPa expands because of present light weight design trends. The requirements regarding the welded components safety increased due to high loading capacity. This determines a sustainable and economic application as well. However, high welding residual stresses could diminish the components safety, especially due to high restraint conditions in component or repair welds. Therefore, this work is concerned with global and local welding stresses, especially crack-critical welding stresses in the HAZ and while root welding due to the restraint conditions. Restraint intensities of real components were analysed and realised with two different weld tests, alongside two different plate dimensions and steel grades. A comparison of the test results showed several significant effects for heat control and restraint intensity regarding restraint forces and local welding stresses. Among these effects, substantial influences were found for the filler metal selection with partially altered results for root and filler beads. Local stresses of weld seam and HAZ were affected differently.
For the description of (single) crystal orientations, e.g. as measured by electron backscatter diffraction (EBSD) & X-ray diffraction (XRD), Euler angles are still generally used to import and export data. However, because of the lack of standard definitions for the unit cell reference settings and specimen axes, several transformation descriptions exist which produce different sets of Euler angles for the same orientation. There is also no recommended region within the minimal Euler orientation space into which orientations should be placed. This is the reason why different sets of Euler angles for the same orientation are generated by the available software packages for indexing EBSD patterns. These issues are reviewed and addressed.
The influence of crystal symmetry in form of chiral (enantiomorphic) groups is discussed, as well as how multiple, but symmetry-equivalent sets of Euler angles can be reduced in order to deliver a unique orientation description. The Euler coloring algorithms applied to EBSD map data is critically discussed. The specific case of cubic symmetry, especially the effect of the three-fold rotation on the Euler space is investigated in more detail for the highest-symmetric chiral group 432. Recommendations for standard settings of the unit cell to orthogonal coordinate system transformation are given which exploit inherent symmetry.
The formation of laser-induced periodic surface structures (LIPSS) on different materials (silicon, fused silica, quartz) with linearly polarized fs-laser irradiation is studied experimentally. In dielectrics, the importance of transient excitation stages in the LIPSS formation is demonstrated by using (multiple) cross-polarized double-fs-laser-pulse irradiation sequences. A characteristic decrease of the spatial LIPSS periods is observed for double-pulse delays of less than 2 ps along with a characteristic 90°-rotation of the LIPSS orientation.
A two-step separation procedure for the quantification of Pd and Pt in automotive exhaust emissions using isotope dilution mass spectrometry was established using a combination of cation and anion exchange chemistry. AG 50W-X12 was used as cation exchange resin and DGA as weakly basic anion exchange resin. This procedure enabled the effective separation of Pd and Pt from the matrix and from interfering elements. Additionally Pd and Pt were collected in separate chromatographic fractions, which increased the precision of the isotope ratio determination by separate measurements using single collector sector field ICPMS. The analytical procedure was validated by analysing the synthetically prepared samples and the certified reference materials BCR-723 (road dust) and IAEA-450 (algae). For the SI-traceable results complete uncertainty budgets were calculated yielding relatively expanded uncertainties (k = 2) of ≈1% for analyte masses in the ng range. Procedure blanks of 55 pg Pd and 3 pg Pt were obtained. The detection limits were calculated as 12 pg for Pd and 7 pg for Pt. Additionally, Pd and Pt blank levels of different filter materials are presented as well as the first results for automotive exhaust particles collected on cellulose filters.
Beim Abreißen von Flaschenventilen an Atemluftflaschen wird schlagartig sehr viel Energie frei. Im Beitrag wird auf Unfälle im Zusammenhang mit Atemschutzgeräten, welche gerade nicht im Einsatz verwendet werden, eingegangen. Es wird beschrieben, welche die häufigsten Fehler bei der Handhabung solcher Geräte sind, was im schlimmsten Fall passieren kann und an welchen Stellen welche Maßnahmen ergriffen werden sollten, um die Unfallfolgen zu begrenzen bzw. den Unfall zu vermeiden.
Effective cleanup of groundwater contaminated with radionuclides using permeable reactive barriers
(2015)
The mining of natural resources always causes environmental impacts such as land use, large quantities of waste, destruction of habitat, impairment of groundwater regime, and quite possibly contamination of soil, water, or air (Dudka and Adriano 1997). The environmental impact of mining cannot be estimated easily. The concept of total material requirement (TMR) is an attempt to quantify the environmental impact of materials. TMR is the sum of domestic and imported primary natural resources and their hidden flows (Adriaanse et al. 1997). Hidden flows are often not considered in environmental analyses because they are attributed with no cost. However, overburden from mining, earth moving for construction, and soil erosion are major sources of ecological damage. From the mining of minerals to the final products, a number of process steps take place (exploration, mine site development, extraction, milling, washing, concentration, smelting, refining, fabrication), each step being connected to other input flows such as energy or other resources. The hidden flows for metals related to metal ore mining have been investigated by Halada et al. (2001). Table 9.1 lists the data for some metals, together with the data for some other minerals and fuels. The TMR in the United States in the 1990s was between 80 and 100 tonnes per capita; in the European Union (EU-15) approximately 50 tonnes per capita (Bringezu 2002).
Mit einer neuartigen analytischen Zentrifuge können Klebverbindungen, Beschichtungen und Kompositwerkstoffe untersucht werden. Die Idee der Wissenschaftler an der BAM Bundesanstalt für Materialforschung und -prüfung: Die Proben müssen nicht mehr eingespannt, sondern nur noch eingesteckt werden. Durch das einfache Einstecken der Prüfkörper ist eine sehr schnelle Beladung möglich. Zudem können bis zu acht Proben gleichzeitig unter identischen Bedingungen geprüft werden. Konventionelle Zugprüfmaschinen waren und sind nur in der Lage, einen (eingespannten) Probekörper zu testen. Das von BAM-Forschern bereits 2004 zum Patent angemeldete Funktionsprinzip wurde seitdem von der Berliner LUM GmbH als Lizenznehmer zum marktreifen Produkt weiterentwickelt.
Radiologic evaluation techniques are nondestructive testing (NDT) used to detect the bulk of explosives and contraband materials in large objects. As compared to conventional low-energy (<450 key) X-ray imaging, high-energy (>1 MeV) digital X-ray radiography is required for the NOT of large containers because of the need for high penetration through thick materials, sensitivity, and the ability to distinguish between low-and high-Z materials. Mobile, high-energy, and high-resolution radiologic techniques are useful to detect contraband and threat materials in digital radiographic images of containers with complex packing. This paper presents a mobile, high-energy X-ray radiographic technique for the in-field nondestructive inspection of cargo containers. The developed experimental technique consisted of a betatron as a high-energy (7.5 MeV) X-ray source and a high-resolution (400 mu m) matrix detector for the digital X-ray imaging. In order to evaluate the detection efficiency and image quality of the measurement technique, a test specimen was proposed that was made of a 3 mm thick steel container with an inner dimension of 60 x 30 x 40 cm(3) comprising different low-and high-Z materials. Image quality indicators were used to assess the essential image quality parameters such as image basic spatial resolution, effective attenuation coefficient, and signal-to-noise ratio (SNR). Experimental investigations were performed on a 6.1 m sea freight container with mockup dangerous materials in complex packing. Preliminary experimental results showed that the proposed technique was able to distinguish between liquids and solids, as well as detect contraband materials. Furthermore, a remarkable SNR of 400 was achieved in the measured digital X-ray images. The influence of temperature on X-ray radiation dose rate at different X-ray energies was also investigated. Finally, important applications of the proposed technique in the context of maritime security are discussed.
In den Untersuchungen zum Zündvermögen von Filmeffektzündern wurde nachgewiesen, dass diese einen Plastiksprengstoff auf Basis von PETN nicht zu einer detonativen Umsetzung anregen können. Die Erfüllung der grundlegenden Sicherheitsanforderung (ESR) des Anhanges 1 der Richtlinie 2013/29/EG und die Kategorisierung als pyrotechnischer Gegenstand für Theater (T2) kann somit als gegeben angesehen werden, da der verwendete Explosivstoff zur Gruppe der sensibelsten Sprengstoffe (Initiierung mit geringen Zündenergien) gehört. Es wurde weiterhin nachgewiesen, dass der Untemassertest nach DIN EN 13763 Teil 15 aussagekräftige Ergebnisse liefert, welche die Fähigkeit von Filmeffektzündern und vergleichbaren pyrotechnischen Gegenständen bestätigen respektive widerlegen, einen Sekundärsprengstoff zu zünden (eine Detonation zu initiieren).
Für eine allgemeine Einschätzung des Zündvermögens von Filmeffektzündern und vergleichbaren pyrotechnischen Gegenständen ist ein Grenzbereich für ein äquivalentes Zündvermögen in g PETN auf Basis der Experimente mit dem o. g. Unterwassertest bestimmt worden. Filmeffektzünder und vergleichbare pyrotechnische Gegenstände sind nicht in der Lage, einen Sekundärsprengstoff zur Detonation anzuregen, wenn das aus dem Unterwassertest ermittelte äquivalente Zündvermögen unter 0,25 g PETN liegt.
Auswirkungen von Ermüdungsbeanspruchungen auf Struktur und Eigenschaften von Fahrbahndeckenbeton
(2015)
Ausgehend von der Zielsetzung der DFG-Forschergruppe 1498, die Einflüsse auf den AKR-Schädigungsprozess in Fahrbahndecken aus Beton grundlegend zu klären, sind zwei aufeinander aufbauende Untersuchungsschwerpunkte Gegenstand dieses Beitrags. Im ersten Schwerpunkt wurden die prüftechnischen Voraussetzungen für die Charakterisierung der Degradation und damit der Rissbildung im Fahrbahndeckenbeton durch die Vorschädigung infolge von Ermüdungsbeanspruchungen geschaffen. Realisiert wurde dies durch die Implementierung und Optimierung eines Monitoringsystems im zyklischen 4-Punkt-Biegeversuch zur simultanen Erfassung der Rissbildung im großformatigen Schwingbalken. Zusätzlich wurde die Röntgen-3D-Computertomografie für die hochauflösende räumliche quantitative Rissanalyse in den Bohrkernen aus den Schwingbalken ohne und mit Vorschädigung weiterentwickelt. Im zweiten Untersuchungsschwerpunkt wurde mittels vielfältiger Experimente an kleinformatigen Probekörpern aus dem Schwingbalken gezeigt, dass durch die Ermüdungsbeanspruchung die bruchmechanischen Materialkennwerte des Betons zum Teil eine signifikante Veränderung erfahren. Based on the objective of the DFG (German research foundation) funded research group 1498 to clarify the influences on the ASR damage process, this paper deals with two focuses of investigation. In the first focus the technical requirements for the characterisation concerning the degradation and the formation of cracks in concrete pavements by the pre-damage as a result of fatigue loading were created. This was realized by the implementation and the optimisation of a monitoring system in the cyclic four point bending test to capture simultaneously the formation of cracks in the beam under sinusoidal bending load. In addition, the X-ray 3D-computed tomography was enhanced for the high-resolution quantitative spatial crack analysis in the drilling cores extracted of the beam under sinusoidal bending load without and with a pre-damage. Building on the first focus, in the second focus of investigation a significant change of the fracture-mechanical properties of the concrete as a result of fatigue loading has been demonstrated in numerous experiments using small specimens extracted from the beam under sinusoidal bending load.
This paper presents a new X-ray backscatter technique (XBT) for non-destructive imaging of aerospace materials with only a single-sided access. It uses a special twisted slit collimator to inspect the whole object by changing the viewing direction of the X-ray backscatter camera. For the first time, the X-ray backscatter measurements were conducted using high-energy (>500 keV) X-ray sources. Experiments were performed on thick complex structured aluminium components, stringers and honeycomb structures to validate the applicability of the present technique to image small changes in the material properties and also to detect low-density material inclusions. In order to reduce the inspection time from hours to several seconds and to improve the image quality of the X-ray backscatter image, the backscattered signals were measured using a digital detector array with high spatial resolution (200 µm). The influence of the energy of the X-ray source and the slit width of the camera on the X-ray backscatter image were also investigated. In the proposed technique, the whole object is irradiated by an un-collimated X-ray beam resulting in a low image acquisition time of 3 min that facilitates the use of XBT for the real time NDT&E of aerospace materials.
The ground vibrations, which are generated by trains on different tracks, have been calculated by finite-element boundary-element models. The ballasted track is modelled in detail by the finite element method. The infinite soil is modelled by the boundary element method as a homogeneous or layered half-space. The track-soil system is coupled to a simple rigid mass model of the vehicle so that the vehicle-track interaction is completely included. Transfer functions are calculated in frequency domain without and with vehicle-track interaction, the compliance of the track and the mobilities of the soil at different distances from the track. Finally, the ratios between the ground vibration amplitudes with and without mitigation measures are calculated to quantify the effectiveness of the mitigation measures.
Tracks with under-sleeper pads have been investigated in a wide parameter study for the RIVAS project. The main parameters that influence the reduction of ground vibration are the stiffness of the under-sleeper pad, the mass and the width of the sleeper. The softest sleeper pad yields the best reduction of the ground vibration. The influence of the sleeper mass is not so strong, as the characteristic frequency is ruled by the mass of the sleeper and the mass of the wheelset as well.
Behavior of dust/air mixtures is very complex and difficult to predict since it depends on material properties as well as boundary conditions. Without other influences airborne particles deposit due to gravity but the time it takes for total deposition as well as easiness of resurrection depends very much on the specific dust sample and the boundary conditions. It still lacks a complete understanding of all interacting reasons and one approach is using experimentally determined characteristics, one is named dustiness.
Dustiness is the tendency of dust to form clouds and to stay airborne. Dustiness is determined with two basic principles, which are light attenuation and ratio of filled-in and measured mass. Assessment of dustiness of industrial powders has been done for a long time regarding work place safety. Dustiness is used there to determine inhalable fraction and to evaluate health risks. Lately it became interesting in dust explosion protection as well. Dustiness could be used to optimize determination of zones, adaption of venting area and/or for positioning of suppression systems.
Dustiness can be useful in many ways but is not a physical property of dusts, therefore it depends on material properties such as density, particle size distribution, shape and water content as well as boundary conditions or determination method. This makes it very difficult to compare dustiness for different techniques and apparatuses and determination method as well as results should be considered carefully. This work gives an overview of existing standards, recent research and suggests improvements to the new dustiness as proposed for dust explosion protection.
Pd/TiO2 coatings with template-controlled mesopore structure as highly active hydrogenation catalyst
(2015)
Micro-structured reactors offer excellent mass and heat transport capabilities and can therefore sustain very high reaction rates and space–time-yields also for highly exothermic catalytic reactions. However, such high rates cannot be reached when the reactors are coated or filled with conventional catalysts powders. We present a strategy for the direct synthesis of highly active wall-coated supported catalysts via co-deposition of a pore template (here micelles formed from PEO-b-PPO-b-PEO) and a precursors for the metal oxide (TiCl4) along with a compatible precursor for the active metal (PdCl2). The obtained catalytic coatings possess a template-controlled open pore structure and excellent mechanical stability. Moreover, the active metal is highly dispersed and well-distributed across the coating also at high Pd loadings. The corresponding high activity along with rapid mass transfer enabled by the open pore system results in the best space–time-yields in the gas-phase hydrogenation of butadiene reported so far in literature for a supported catalyst.
The hepatotoxin phomopsin A (PHO-A), a secondary metabolite mainly produced by the fungus Diaporthe toxica, occurs predominantly on sweet lupins. Along with the growing interest in sweet lupins for food and feed commodities, concerns have been raised about fungal infestations, and consequently, about the determination of PHO-A.
High performance liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) represents the most suitable analytical technique for sensitive and selective detection of mycotoxins including PHO-A. However, isotopic labeled substances are needed as internal standards for a reliable and convenient quantification.
As no isotope standard for PHO-A is currently available, a biosynthesis of fully 15N6-labeled PHO-A was established by cultivation of D. toxica on defined media containing Na15NO3 and 15N-labeled yeast extract as the only nitrogen sources. The identity of 15N6-PHO-A was confirmed by high resolution mass spectrometry.
The new 15N6-labeled standard will facilitate the method development for PHO-A including a more accurate quantification by LC-MS/MS.
Austenitic stainless steels provide a beneficial combination of chemical and mechanical properties and have been used in a wide field of applications for over 100 years. Further improvement of the chemical and mechanical properties was achieved by alloying nitrogen. But the solubility of N within the melt is limited and can be increased in substituting Ni by Mn and melting under increased pressure. In order to avoid melting under pressure and decrease production costs, a part of N can also be substituted by C. This leads to austenitic high interstitial steels (AHIS). Within the solution annealed state strength and ductility of AHIS is comparable or even higher of those of AHNS and can be further improved by cold working. Unfortunately the endurance limit does not follow this trend as it is known from cold-worked austenitic CrNi steels. This is due to the differences of the slip behavior which is governed by the stacking fault energy as well as other near field effects. Construction components operating under cyclic loads over long periods of time cannot be considered being free of voids or even cracks. Thus the crack propagation behavior is of strong interest as well. This contribution presents the tensile, fatigue, crack propagation and fracture toughness properties of AHNS and AHIS in comparison to those of CrNi-steels. The differences are discussed in relation to microstructural characteristic as well as their alterations under cyclic loading.
In Betonbauteilen unter gleichzeitiger zyklischer Beanspruchung und externer Alkalizufuhr ist die Gefahr von Schäden infolge oder unter Mitwirkung einer Alkali-Kieselsäure-Reaktion (AKR) besonders hoch. Dies betrifft insbesondere Fahrbahndecken, bedingt durch den zunehmenden Schwerlastverkehr und den winterlichen Auftrag des Enteisungsmittels NaCl. Speziell die Rolle einer mechanischen Vorschädigung des Betons infolge der Verkehrsbeanspruchungen auf den Ablauf einer AKR ist dabei aber noch nicht in ausreichendem Umfang geklärt. Ein Teil der dazu seit 2012 durchgeführten Untersuchungen im Rahmen der DFG-Forschergruppe 1498 soll im Folgenden vorgestellt werden. Es zeigte sich, dass eine AKR in definiert mechanisch vorgeschädigten Betonprobekörpern mit alkalireaktiven Gesteinskörnungen und unter äußerer Alkalizufuhr vor allem früher beginnt als in äquivalenten Probekörpern ohne Vorschädigung. Grund dafür ist das schnellere und tiefere Eindringen von Wasser und insbesondere gelöstem NaCl in den Beton, wodurch Na-Ionen als Reaktionspartner für eine AKR früher und langfristig auch in größerer Menge verfügbar sind.------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
In concrete elements, simultaneously subjected to cyclic loadings and external alkalis, the risk for damages caused by or under participation of an alkali-silica reaction (ASR) is particularly high. This concerns especially concrete pavements due to the increasing heavy load traffic and the wintry application of NaCl deicer. Notably the role of a mechanical pre-damage of concrete caused by traffic loadings on the course of the ASR is largely unclear. A part of the investigations that has been conducted since 2012 into this issue within the scope of the DFG (German research foundation) funded research group 1498 shall be introduced in the following. It was evident that an ASR in defined mechanically pre-damaged concrete prisms with alkali-reactive aggregates and under an external supply of alkalis started earlier than in equal prisms without a pre-damage. The reason for this is the faster and deeper ingress of water and particularly of dissolved NaCl into the concrete, by what Na ions as reaction partner for an ASR are available earlier and, in the long-term, in greater amounts too.
Die "Empfehlungen für die Beförderung gefährlicher Güter, Handbuch über Prüfungen und Kriterien" ergänzen die "Empfehlungen für die Beförderung gefährlicher Güter, Modellvorschriften" und das "Global harmonisierte System zur Einstufung und Kennzeichnung von Chemikalien (GHS)". Sie enthalten Kriterien, Prüfmethoden und –verfahren, die angewendet werden sowohl für die Einstufung gefährlicher Güter nach den Vorschriften der Teile 2 und 3 der Modellvorschriften als auch für Chemikalien, von denen nach dem GHS physikalische Gefahren ausgehen.
Bright emitters with photoluminescence in the spectral region of 800–1600 nm are increasingly important as optical reporters for molecular imaging, sensing, and telecommunication and as active components in electrooptical and photovoltaic devices. Their rational design is directly linked to suitable methods for the characterization of their signal-relevant properties, especially their photoluminescence quantum yield (Φf). Aiming at the development of bright semiconductor nanocrystals with emission >1000 nm, we designed a new NIR/IR integrating sphere setup for the wavelength region of 600–1600 nm. We assessed the performance of this setup by acquiring the corrected emission spectra and Φf of the organic dyes Itrybe, IR140, and IR26 and several infrared (IR)-emissive Cd1-xHgxTe and PbS semiconductor nanocrystals and comparing them to data obtained with two independently calibrated fluorescence instruments absolutely or relative to previously evaluated reference dyes. Our results highlight special challenges of photoluminescence studies in the IR ranging from solvent absorption to the lack of spectral and intensity standards together with quantum dot-specific challenges like photobrightening and photodarkening and the size-dependent air stability and photostability of differently sized oleate-capped PbS colloids. These effects can be representative of lead chalcogenides. Moreover, we redetermined the Φf of IR26, the most frequently used IR reference dye, to 1.1 × 10-3 in 1,2-dichloroethane DCE with a thorough sample reabsorption and solvent absorption correction. Our results indicate the need for a critical reevaluation of Φf values of IR-emissive nanomaterials and offer guidelines for improved Φf measurements.
Critical review of the determination of photoluminescence quantum yields of luminescent reporters
(2015)
A crucial variable for methodical performance evaluation and comparison of luminescent reporters is the photoluminescence quantum yield (Φ pl). This quantity, defined as the number of emitted photons per number of absorbed photons, is the direct measure of the efficiency of the conversion of absorbed photons into emitted light for small organic dyes, fluorescent proteins, metal–ligand complexes, metal clusters, polymeric nanoparticles, and semiconductor and up-conversion nanocrystals. Φ pl determines the sensitivity for the detection of a specific analyte from the chromophore perspective, together with its molar-absorption coefficient at the excitation wavelength. In this review we discuss different optical and photothermal methods for measuring Φ pl of transparent and scattering systems for the most common classes of luminescent reporters, and critically evaluate their potential and limitations. In addition, reporter-specific effects and sources of uncertainty are addressed. The ultimate objective is to provide users of fluorescence techniques with validated tools for the determination of Φ pl, including a series of Φ pl standards for the ultraviolet, visible, and near-infrared regions, and to enable better judgment of the reliability of literature data.
Two-color double-fs-pulse experiments were performed on silicon wafers to study the temporally distributed energy deposition in the formation of laser-induced periodic surface structures (LIPSS). A Mach-Zehnder interferometer generated parallel or cross-polarized double-pulse sequences at 400 and 800 nm wavelength, with inter-pulse delays up to a few picoseconds between the sub-ablation 50-fs-pulses. Multiple two-color double-pulse sequences were collinearly focused by a spherical mirror to the sample. The resulting LIPSS characteristics (periods, areas) were analyzed by scanning electron microscopy. A wavelength-dependent plasmonic mechanism is proposed to explain the delay-dependence of the LIPSS. These two-color experiments extend previous single-color studies and prove the importance of the ultrafast energy deposition for LIPSS formation.
Development of a multi-VOC reference material for quality assurance in materials emission testing
(2015)
Emission test chamber measurement is necessary to proof building materials as sources of volatile organic compounds (VOCs). The results of such measurements are used to evaluate materials and label them according to their potential to emit harmful substances, polluting indoor air. If only labelled materials were installed indoors, this would improve indoor air quality and prevent negative impacts on human health. Because of the complex testing procedure, reference materials for the quality assurance are mandatory. Currently, there is a lack of such materials because most building products show a broad variation of emissions even within one batch. A previous study indicates lacquers, mixed with volatile organic pollutants, as reproducible emission source for a wide range of substances. In the present study, the curing of the lacquer-VOC mixture inside micro-chambers was optimised. Therefore, the humidity and the chamber flow were varied. Typical indoor air pollutants with a wide range of volatilities, for example, styrene, n-hexadecane, dimethyl and dibutyl phthalate were selected. It turned out that, under optimised curing parameters inside the micro-chamber, their emission can be reproduced with variations of less than 10 %. With this, a next important step towards a reference material for emission testing was achieved.
Fukuda et al. published a paper (Scripta Mater. 68 (2013) 984–987) in which they claimed to be able to determine the isothermal nature of the martensitic transformation in a Ti–Ni alloy. They analyzed the evolution of electrical resistance during isothermal holding stages and concluded that the variations were a consequence of the isothermal transition between austenite and martensite. In the following we will demonstrate that the discussed data do not allow the interpretation presented and that the isothermal nature is not proved.
Sulphurous additives for polystyrene: Influencing decomposition behavior in the condensed phase
(2015)
The thermal decomposition behaviour of polystyrene (PS) containing sulphur and phosphorus additives was investigated, using thermogravimetry coupled with Fourier transform infrared spectroscopy (TGA-FTIR). It was found that the additives influence the decomposition process of the polymer in the condensed phase, resulting in a decrease in styrene monomer formation and an increase in styrene oligmer derivatives. Via reference measurements with binary mixtures it was found that the presence of sulphur additives influences the radicalic decomposition process of PS. In combination with quantum chemical calculations it was concluded that this is due to the formation of radicals that abstract hydrogen from the polymer matrix at lower temperatures, disfavouring the radicalic decomposition pathway leading to styrene.
The effect of structural constriction on molecular mobility is investigated by broadband dielectric spectroscopy (BDS) within three types of molecular arrangements: monomers, oligomers and self-assembled monolayers (SAMs). While disordered monomers exhibit a variety of cooperative and local relaxation processes, the constrained nanodomains of oligomers and highly ordered structure of monolayers exhibit much hindered local molecular fluctuations. Particularly, in SAMs, motions of the silane headgroups are totally prevented whereas the polar endgroups forming the monolayer canopy show only one cooperative relaxation process. This latter molecular fluctuation is, for the first time, observed independently from other overlapping dielectric signals. Numerous electrostatic interactions among those dipolar endgroups are responsible for the strong cooperativity and heterogeneity of the canopy relaxation process. Our data analyses also revealed that the bulkiness of dipolar endgroups can disrupt the organization of the monolayer canopy thus increasing their ability to fluctuate as temperature is increased.
An approach is presented to model elastic waveguides of arbitrary cross-section coupled to infinite solid media. The formulation is based on the scaled boundary-finite element method. The surrounding medium is approximately accounted for by a dashpot boundary condition derived from the acoustic impedances of the infinite medium. It is discussed under which circumstances this approximation leads to sufficiently accurate results. Computational costs are very low, since the surrounding medium does not require discretization and the number of degrees of freedom on the cross-section is significantly reduced by utilizing higher-order spectral elements.
Epoxy carbon-fibre prepreg, Hexcel Type 6376 HTS, was investigated using Dynamic Mechanical Analysis (DMA). The DMA characteristic parameters are storage modulus E', loss modulus E' and loss factor tanδ. These parameters are ideally suited to observe the vitrification, referred to as glass transition, resulting from the cross-linking reaction. Detection of the cure state may also be achieved by determining the momentary glass transition temperature of partially cured samples. The consequent use of a multi-frequency measuring regime was used to derive the apparent activation energy for the glass transition process. Different temperature programs were also applied to monitor the curing process directly, as well as to investigate the different states of incomplete cure reached in preceding curing steps. The intention was to provide better understanding of the consequences of an interrupted autoclave curing process and to use DMA to detect the cure state achieved. With DMA, the continuation of an incomplete curing process also can be monitored. DMA measurements up to 300 °C showed, furthermore, that the final glass transition temperature was reduced by thermal degradation at high temperatures.
ISO standards for gas cylinders made from aluminum alloys generally require heat treatment after the forming process. Such heat treatment is a costly part of the manufacturing process. Particularly due to increasing international trade, market-surveillance authorities need simple and reliable methods to field-test cylinders for proper heat treating. By the present contribution the difference in strength of heat-treated and non-heat-treated gas cylinders is exemplarily shown and several material analysis methods are investigated for their suitability as field tests.
This article presents an analytical approach for simulation of ultrasonic diffracted wave signals from cracks in two-dimensional geometries based on a novel Huygens–Fresnel Diffraction Model (HFDM). The model employs the frequency domain far-field displacement expressions derived by Miller and Pursey in 2D for a line source located on the free surface boundary of a semi-infinite elastic medium. At each frequency in the bandwidth of a pulsed excitation, the complex diffracted field is obtained by summation of displacements due to the unblocked virtual sources located in the section containing a vertical crack. The time-domain diffracted wave signal amplitudes in a general isotropic solid are obtained by standard Fast Fourier Transform (FFT) procedures. The wedge based finite aperture transducer refracted beam profiles were modelled by treating the finite dimension transducer as an array of line sources. The proposed model is able to evaluate back-wall signal amplitude and lateral wave signal amplitude, quantitatively. The model predicted range-dependent diffracted amplitudes from the edge of a bottom surface-breaking crack in the isotropic steel specimen were compared with Geometrical Theory of Diffraction (GTD) results. The good agreement confirms the validity of the HFDM method. The simulated ultrasonic time-of-flight diffraction (TOFD) A-scan signals for surface-breaking crack lengths 2 mm and 4 mm in a 10 mm thick aluminium specimen were compared quantitatively with the experimental results. Finally, important applications of HFDM method to the ultrasonic quantitative non-destructive evaluation are discussed.
A software prototype is developed for assessing and updating the reliability of single-cell prestressed concrete box girders subjected to chloride-induced reinforcement corrosion. The underlying system model consists of two integrated sub-models: a condition model for predicting the deterioration state of the box girder and a structural model for evaluating the overall system reliability. The condition model is based on a dynamic Bayesian network (DBN) model which considers the spatial variation of the corrosion process. Inspection data are included in the calculation of the system reliability through Bayesian updating on the basis of the DBN model. To demonstrate the effect of partial inspections, the software prototype is applied to a case study of a typical highway bridge with six spans. The case study illustrates that it is possible to infer the condition of uninspected parts of the structure due to the spatial correlation of the corrosion process.
First developments of a new test to evaluate the fire behavior of photovoltaic modules on roofs
(2015)
A new test for photovoltaic (PV) modules exposed to an external fire source on roofs is proposed, and first results are presented. This is a simplification of the standards commonly in use for testing PV modules as roofing parts, roofing components or building components. Most of the tests required different fire scenarios and the use of burning brands such as wood cribs. In our study we proposed replacing wooden burning brands with a propane burner, the output of which is close to the one that can be observed in the burning of wooden cribs 500 g and 2 kg in size. The fire behavior was assessed by measuring smoke evolution, burning drips, flaming debris, and the time to burn-through of monocrystalline, polycrystalline and amorphous silicon panels. Two different configurations of the burner were tested, with the fire source on the top of the module or under the tilted module, respectively. The fire behavior of the modules was dependent on the burner output (16 to 46 kW), but also on the construction type of the panel (glass/glass or glass/plastic sheet) and on the position of the fire source (top or bottom). These preliminary tests for further development of the procedure yielded encouraging results for the evaluation of PV panels on roofs.
The aim of this study was the development of a low volume air sampling strategy for biocides and polychlorinated biphenyls (PCB) at low air change rates in modern, air-tight showcases as they are present in museums. Lindane, pentachlorophenol, dichlofluanid, tolyfluanid, isodrin, p,p-dichlorodiphenyl trichloroethane and permethrin were the biocides and PCB 28 and PCB 153 were the PCBs studied, all of which are semi volatile organic compounds (SVOC). Their occurrences in the museum environment originate from various sources e.g. preventive treatment of organic exhibits or organic building materials. Exhibits are long-term exposed to these pollutants due to storing in showcases or other storage equipment at low air change rates. To achieve air sampling under the aforementioned conditions the influences of temperature, air circulation, air change rate and relative humidity on the emission behavior of the selected biocides and PCBs had to be determined. This was carried out with pre-soaked wood samples in low volume air sampling experiments using 27 L test showcases and 23 L and 24 L emission test chambers and also diffusive sampling with glass as the sampling material.
The pore structure of lightweight granules made from masonry rubble was studied in order to better understand their engineering properties. Thermally and hydrothermally hardened granules were tested. Analysis by ESEM, mercury porosimetry and sorption methods yield important insight into their microstructure. The thermal granules are characterised by partly melted vitreous areas and large internal macropores that are connected via narrow throats. They show a marginal specific surface area along with a hydrophobic behaviour. In contrast, the hydrothermal granules have an accessible mesoporous system containing plate-like and ink-bottle pores. The shape of their water isotherms depending on the granules CaO content is sensitive to the morphology of calcium silicate hydrate phases (CSH). The hysteresis changes from a narrow loop that closes at low pressures, which can be attributed to coarser more crystalline CSH, to a large triangular-shaped loop along with a low pressure hysteresis, which is characteristic for fine fibre-like CSH with ink-bottle and plate-like pore morphologies. Granules with fibre-like CSH have the higher specific surfaces areas but those with more crystalline CSH show stronger physisorption of water molecules.
The aim of the joint project ViPQuali (Virtual Product Qualification) was to describe a components ageing behaviour in a given environment, by numerical simulation.
Having chosen polypropylene (PP) as the material, which does not show sensitivity to moisture, the relevant weathering parameters of the doseresponse functions could be limited to spectral irradiance and temperature.
In artificial irradiation tests, for PP plates of varied stabiliser content, spectral sensitivity as well as temperature dependence of irradiation-caused crack formation was quantified. For that purpose, samples were exposed both to artificial weathering tests at various constant temperatures and to spectrally resolved irradiation. The temperature dependence could be modelled by an Arrhenius fit. For fitting the spectral sensitivity, a plateau function was chosen. Subsequently, the stabiliser content was parameterised and extrapolated.
The formed dose–response functions were incorporated into a Computational Fluid Dynamics (CFD) software program, simulating the environment of a sample within a Phoenix-exposed IP/DP (Instrument Panel/Door Panel box) box, based on sun position and weather conditions, including radiation interactions. Observed local effects as well as the general ageing advance of PP hats are compared with respect to simulation and experiment.
Resulting from this project, for this most simple example of PP of varied stabiliser content, the time to failure can be estimated for each weathering exposure environment with known time-resolved irradiance and temperature conditions.
NbC has a relatively high hardness (19.6 GPa) and melting temperature (3600 °C) and is usually applied as a grain growth inhibitor in WC–Co hardmetals. The current study reports on the influence of the sintering technology and overall chemical composition on the microstructure and mechanical properties of NbC-based hardmetals, using Co as a binder. The partial replacement of NbC by 5 wt.% WC, Mo2C, VC or TiC allows one to significantly improve the hardness and toughness of the NbC–Co materials. The influence of different binders, i.e., Co, 316L stainless steel and Fe3Al on the microstructure and mechanical properties of NbC-based hardmetals was also investigated. The powder mixtures were sintered in the solid state by PECS and liquid state by conventional vacuum sintering. Detailed microstructural analysis was conducted by EPMA elemental mapping and WDS point analysis. Mechanical properties, including Vickers hardness and indentation toughness were assessed.
In this paper, a method to determine the complex dispersion relations of axially symmetric guided waves in cylindrical structures is presented as an alternative to the currently established numerical procedures. The method is based on a spectral decomposition into eigenfunctions of the Laplace operator on the cross-section of the waveguide. This translates the calculation of real or complex wave numbers at a given frequency into solving an eigenvalue problem. Cylindrical rods and plates are treated as the asymptotic cases of cylindrical structures and used to generalize the method to the case of hollow cylinders. The presented method is superior to direct root-finding algorithms in the sense that no initial guess values are needed to determine the complex wave numbers and that neither starting at low frequencies nor subsequent mode tracking is required. The results obtained with this method are shown to be reasonably close to those calculated by other means and an estimate for the achievable accuracy is given.
Bile acids are relevant markers for clinical research. This study reports the production of antibodies for isolithocholic acid, the isomer of the extensively studied lithocholic acid. The IgG titer and affinity maturation were monitored during the immunizations of three mice and two rabbits. In both animal models, polyclonal antibodies with a high selectivity and affinity were produced. The development of a direct competitive ELISA with a test midpoint of 0.69 ± 0.05 µg/L and a measurement range from 0.09–15 µg/L is reported. Additionally, the crystal structure of isolithocholic acid is described for the first time.
Pectin-water interactions: comparison of different analytical methods and influence of storage
(2015)
Interactions of pectin with water are essential for nearly all pectin applications. It was assumed that these interactions strongly depend not only on chemical molecular parameters but also on physical powder material properties and that they might be affected by storage. This was examined with nine different pectin samples from three suppliers. Storage at 60 °C and 80% humidity for two weeks was used in order to simulate long term storage at moderate conditions. Material properties were tested by measuring solid density and BET surface and by mercury porosimetry and X-ray analysis. Pectin-water interactions were examined with two different methods, a modified sorption method at αw around 1.0 and the capillary sucking method (Baumann method). After storage, the BET surface of the pectin samples was reduced, solid density was altered differently and crystalline structures became amorphous. It is assumed that storage at high heat and humidity caused particle surfaces softening, swelling and partly dissolution. The particle surfaces smoothed, small inter-particle voids were reduced or sealed and particles agglomerated. These alterations caused a reduced water uptake of stored pectins. In general, the accessibility of hydrophilic groups in pectin was more important for pectin-water interactions than their number. All applied methods for testing pectin-water interactions detected special sample properties and their combination allowed an extensive evaluation of the water binding properties.
The distribution and speciation of zinc were studied in the body of female specimens of the soil-inhabiting, plant-feeding nematode, Xiphinema vuittenezi treated with nano-ZnO and its bulk counterpart. Lyophilized nematodes were studied by X-ray absorption near edge structure spectrometry (XANES) in order to characterize the zinc speciation. Furthermore, in the cross-sections prepared by focused ion beam technique, elemental maps were obtained using the electron probe microanalysis (EPMA) technique. XANES spectra were collected from three different regions (head, midbody and tail region) of nematodes in case of two different treatments (50 mg/L bulk and nano-ZnO suspension, 24 h long treatment). The sample spectra were fitted by the spectra of several reference compounds, the main components of the fitted spectra are the following in all cases: bulk/nano-ZnO; ZnHis and Zn3(PO4)2 * xH2O. Consequently, partial biotransformation takes place for both treatments, histidine- and phosphate-rich ligands play dominant role in the binding of zinc. According to the result of the EPMA analysis, it can be established that the distribution of zinc correlates with the calcium and phosphorus distribution for both treatments. Considering the results of the investigations performed by the two microanalytical techniques, it is likely that calcium phosphate granules were formed in order to bind zinc and hereby to take part in zinc detoxification. Apparent difference in the behavior of bulk and nano-sized ZnO in the body of the investigated nematodes was not found.
Carrier gas hot extraction (CGHE) technique was used for measurement of hydrogen in press-hardened (and as delivered) condition of 22MnB5 steel primarily coated with a thin layer of Al–Si. The CGHE technique was applied using different temperature programs: isothermal heating, temperature step, and linear heating in solid state. The effusing hydrogen was measured using thermal conductivity device (TCD) and high resolution mass spectroscopy (MS). Single isothermal heating at 400 and 900 °C allowed determining absolute value of effusing hydrogen. The linear heating, also known as thermal desorption analysis (TDA), revealed temperature dependent hydrogen effusion peaks. The deconvolution of the TDA spectra by peak fitting allowed the calculation of hydrogen desorption energies for each peak. The results showed good agreement between hydrogen concentrations measured with MS and TCD. In addition, the as-received ferrite-perlite microstructure showed only hydrogen effusion above 400 °C. The subsequent press hardening process leads to hydrogen uptake in the microstructure. In general, the press-hardened 22MnB5 revealed a hydrogen concentration of 0.4 to 0.5 ppm. The biggest concentration was released at isothermal holding at 400 °C indicating reversibly trapped hydrogen. TDA results with different heating rates confirmed mostly diffusible and reversible trapped hydrogen due to calculated activation energies in the range from 4 to 20 kJ mol-1; it was ascertained that nearly 90 % of the hydrogen left the specimens below 400 °C. Melt extraction (ME) was performed to measure the total hydrogen amount (including the diffusible and trapped hydrogen) and showed that above 900 °C up to 1 ppm hydrogen is trapped.
We demonstrate the determination of crystal chirality using electron backscatter diffraction (EBSD) in the scanning electron microscope. The chirality of a-quartz as a space-group-dependent property is verified via direct comparison of experimental diffraction features to simulations using the dynamical theory of electron diffraction.
The paper presents an experimental program aiming at assessing the mechanical performance of rammed earth walls, namely under compression and shear loading. Axial compression and diagonal compression tests were carried out for this purpose, which allowed determining important mechanical parameters, such as compressive strength, Young's modulus, Poisson's ratio, shear strength and shear modulus. Furthermore, it allowed assessing the level of non-linear behaviour of the respective stress–strain relationships as well as the failure modes. The experimental results were then used in the calibration of numerical models (finite element method) for simulating the non-linear behaviour of rammed earth under shear loading. Both macro- and micro modelling approaches were considered for this purpose. The total strain rotating crack model was used to simulate the behaviour of the rammed earth material, while the Mohr–Coulomb failure criterion was used to simulate the behaviour of interfaces between layers. In general, the numerical models achieved good agreement with the experimental results, but uncertainties related to the definition of the input parameters required to perform a sensitivity analysis. The compressive strength, the Poisson's ratio, the tensile strength and the tensile fracture energy revealed to be the most important parameters in the analyses.
This article describes a simple and quick in silico method for the prediction of cytochrome P450 (CYP)-mediated hydroxylation of drug-like compounds. Testosterone and progesterone, two known substrates of CYP3A4, are used to test the method. Further, we apply the procedure to predict sites of hydroxylation of isomers of the flame retardant hexabromocyclododecane by CYP3A4. Within the method, the compound is rotated in the binding pocket of the cytochrome, so that each hydrogen under consideration is placed near the active centre. Afterwards, short molecular dynamics simulations are provided for each step of the rotation. All steps of the simulation are compared concerning the distances between the hydrogens and the active centre and the corresponding energies. The computational results correlate well with experimental results.
Condensates from the gas stream in simulated CO2 transport pipelines have been identified during the experiments in the laboratory. Because of their acidic origin the corrosion resistance of pipeline steels used for CCS (carbon capture and storage) technology might be limited. Over the last years it has become clear that the amount of water and acid building constituents in the CO2 stream has to be controlled very well. In this work, condensates formed in experiments using gaseous CO2 containing high amounts of water, NO2 and SO2 were analyzed, replicated, and used for extensive electrochemical experiments. These highly acidic condensates were enriched with CO2 and then applied to characteristic steels planned to use in the CCS transport chain. Even high alloy steels are susceptible to localized corrosion under these conditions. The results implicate that condensation of aggressive acid droplets has to be avoided or the locations where condensation takes place have to be controlled extensively.