Ingenieurwissenschaften und zugeordnete Tätigkeiten
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Eingeladener Vortrag
- nein (411)
Anoxische Objektbehandlungen gegen Schädlingsbefall stellen eine besonders materialverträgliche und umweltschonende Alternative zu chemischen Bekämpfungsverfahren dar. Die Wirksamkeit hängt jedoch von der Dauer, dem Restsauerstoffgehalt sowie der Temperatur und Feuchtigkeit ab. Unterschiedliche Arten von Schadinsekten sind verschieden tolerant gegenüber sauerstoffarmen Bedingungen. Insbesondere bei Behandlungsbedingungen von unter 24° C und mehr als 0,5 % Restsauerstoffgehalt stößt das Verfahren an die Grenze der Zuverlässigkeit. In Versuchsreihen unter standardisierten Bedingungen erwiesen sich insgesamt 12 von 34 im Projekt untersuchte Insektenarten hierbei als widerstandsfähig. Davon als besonders tolerante Arten sind Hylotrupes bajulus, Lasioderma serricorne, Trogoderma parabile und Mezium affine zu nennen.
Mit dem entwickelten UWB-Sensoriksystem können durch elektromagnetische Wellen Bewegungen von Schädlingen innerhalb geschlossener Holzobjekte berührungslos erfasst werden. Voraussetzung für die eindeutige Detektion der Schädlingsaktivität ist neben der digitalen Signalverarbeitung zur Filterung und Extraktion des Nutzsignals, die genügend hohe Eindringtiefe, die ausreichend ist, wenn Schädlingsvorkommen häufig dicht unter der Holzoberfläche gelegen sind. Die Versuchsergebnisse haben gezeigt, dass bereits eine einzelne Trockenholztermite der Art Incisitermes marginipennis hinter einer 5 cm dicken Holzplatte aufgespürt werden kann. Somit erscheint das Messsystem potentiell für die Erfolgskontrolle einer Anoxia-Behandlung an Museumsgütern geeignet.
Our research focused on Inconel 625 weld overlays on 16Mo3 steel boiler pipes. The Investigation focused on the characterization of changes in the microstructure and chemical composition after annealing. The annealing was performed for ten hours at temperatures from 600 to 1000°C. Changes in the microstructure were observed with a scanning and transmission electron microscope (SEM and TEM). The investigation was supplemented by hardness measurements.
This work presents the non-destructive spectroscopic characterisation of original Dead Sea Scrolls (DSS)parchment fragments from Ronald Reed collection. The fragments are of paramount importance becausethey have never been subjected to any treatment of preservation and restoration, this allows to investi-gate the manufacturing method of real original Jewish parchments. The manufacture of “sacred” Jewishparchments, in fact, is traditionally supposed to use a superficial tannin treatment. To study the DSS frag-ments, it was necessary both to analyse mock-up samples, especially manufactured in order to reproduceancient Oriental Jewish ritual parchments, and to compare the results with those obtained in the analysisof modern and ancient Western Jewish ritual parchments, in order to test the effectiveness of the selectedspectroscopic techniques. Traditionally, the main difference between Oriental and Western traditionalparchment preparation consisted in the dehairing method: enzymatic for Oriental and lime-based forWestern. Moreover, a finishing treatment with tannin was supposed to be applied on ritual Jewish parch-ments. The need of reference samples derives from the knowledge that each parchment preparation,treatment and degradation can induce structural modifications that affect the spectral features. FourierTransform Infrared Spectroscopy by Attenuated Total Reflection (ATR-FTIR), FT-Raman and m-Ramanwere used in this study. The experimental results allowed us to recognise, with different sensitivity, thepresence of tannin by using m-Raman and IR spectroscopies and to prove that not all the archaeologicalsamples were manufactured in the same way with vegetal extracts. Many salts (tschermigite, dolomite,calcite, gypsum and iron carbonate) were found on the surface of DSS fragments. They can derive fromthe degradation processes and storage environment before the discovery or from the manufacture. More-over, the different sensitivities and instrumental characteristics of the used techniques permitted us toestablish an analytical protocol, useful for further studies of similar materials.
Der Vortrag gibt den aktuellen Stand der Normung im Bereich der Oberflächen-technik insbesondere der Oberflächenanalytik und der Oberflächenmess- und -prüftechnik wider. Vorgestellt wird der Status technischer Berichte, Normenentwürfe und Normen u.a. zur Charakterisierung von funktionellen Glasoberflächen für bioanalytische Anwendungen, zur Messung der Schichtdicke von Nanomaterialien mittels Ellipsometrie, zur Kalibrierung von Interferometern und Interferenzmikroskopen für die Formmessung, zur Rockwelleindringprüfung zur Bewertung der Schicht-haftung, zu den Grundlagen der Ellipsometrie, zur Messung der Schichtdicke mittels Wirbelstromverfahren, zur Schichtpotentialmessung von Mehrfach-Nickelschichten, zu Filtern und Augenschutzgeräten gegen Laserstrahlung sowie zur Bestimmung der Schichthaftung mittels Zugversuch.
Foreword
(2018)
The subject of this Special Issue is the fracture mechanics-based determination of the fatigue strength of weldments. Except for one, all papers were written in closer or wider relation to a methodology developed within the framework of the German Project cluster IBESS. Some of them provide background or supplementary information needed in that context but which is also relevant in a wider frame of research activities. The acronym IBESS stands for the topic of this Special Issue (in German: „Integrale Methode zu Bruchmechanischen Ermittlung der Schwingfestigkeit von Schweißverbindungen). Eight partners were involved. The cluster was cooperatively founded by the German Research Foundation (Deutsche Forschungsgemeinschaft) and by the German AiF Network (Arbeitsgemeinschaft industrieller Forschungsvereinigungen) for industrial research.
Fiber-reinforced-polymers (FRPs) are in current research focus in the lightweight construction industry, because of their extraordinary characteristics (stiffness and strength-to-density relation). The structure of polymer matrix and the interaction with reinforcement are crucial for optimization of the mechanical and thermal properties of FRPs. Due to the macromolecular chain structure, the mechanical properties of a polymer strongly vary with temperature: Below the glass transition, the chain segments of a polymer are “frozen”. Regarding fracture, the total changed energy during fracture if only dissipates for the generation of the new surfaces. However, in the region of the glass transition, the polymer chain segments start to get “unfrozen”, and the energy is not only required for generating new surfaces, but also for irreversibly deformation. This irreversible deformation is affected by the global temperature and the local temperature near the crack tip, which is affected by the local strain rate and crack propagation velocity.
Hence, in this research project, the irreversible deformation of neat and reinforced polymers will be controlled by changing the global temperature as well as the local temperature. With using different fracture experiments, the amount of energy required for creating new surfaces and for the irreversible deformation will be separated. The fracture tests include the conventional tensile test, the macroscopic peel test and the single fiber peel – off test.
The performance of functional coatings and adhesively joined hybrid components relies strongly on the stability of the polymer-metal interface. With the increasing utilization of multi-material structures in the automotive and aerospace industry, it is of great scientific and technical interest to understand the processes leading to interface degradation and to develop novel strategies to increase corrosion and delamination resistance.
The aim of this project is to develop thin epoxy-based films on aluminium alloy AA2024-T3 as a model system and to investigate their interfacial stability under corrosive and coupled corrosive-mechanical load. Electrochemical and spectroscopic methods were used for the characterisation of the film properties and in situ corrosion experiments were performed by means of AFM. The deformation properties of the aluminium alloy and the model coatings were investigated by means of scanning Kelvin probe force microscopy (SKPFM) utilizing the integrated tensile stage.
The presentation will give a brief overview of the capabilities of the new AFM setup to foster future collaborations and summarize our work on the interface stability of model coatings.
The paper deals with the integration of a light emitting diode (LED) into an additive manufactured metal component. Selective laser melting (SLM) and laser metal deposition (LMD) are used. The material used is the chrome-nickel steel 316L. The basic component is manufactured by means of SLM and consists of a solid body and an area with grid structure. The solid body includes a duct in the shape of a groove with a recess for the positioning of the power cable. The LED is embedded in the grid structure via an inlet from the solid body. In further processing, the groove is filled with LMD. Two strategies with different parameter combinations were investigated. It shows that a high energy input near the power cable leads to its destruction. By using multiple parameter combinations during the manufacturing process, this destruction can be prevented. There was a comparison of both strategies with regard to the necessary number of tracks and duration of welding time.
The paper deals with the integration of a light emitting diode (LED) into an additive manufactured metal component. Selective laser melting (SLM) and laser metal deposition (LMD) are used. The material used is the chrome-nickel steel 316L. The basic component is manufactured by means of SLM and consists of a solid body and an area with grid structure. The solid body includes a duct in the shape of a groove with a recess for the positioning of the power cable. The LED is embedded in the grid structure via an inlet from the solid body. In further processing, the groove is filled with LMD. Two strategies with different parameter combinations were investigated. It shows that a high energy input near the power cable leads to its destruction. By using multiple parameter combinations during the manufacturing process, this destruction can be prevented. There was a comparison of both strategies with regard to the necessary number of tracks and duration of welding time.
Geosynthetics are widely used in hydraulic engineering and within coastal protection constructions at the Baltic Sea shore, such as walls, promenades, and gabions walls. Storms influence leads to deformation of some of the protection structures and cause the release of geotextiles onto the beach. Fragments of geotextile migrate along the shore, experiencing additional degradation and destruction down to macro-, meso-, and micro-particles. During October 2017 - March 2018, the Baltic Sea shore along the Sambia Peninsula (Kaliningrad Oblast of the Russian Federation) was monitored to establish the contamination of sandy beaches by geotextiles that had degraded. Several local sources of pollution of beaches by geosynthetic materials were established.
Beanspruchungsgerechtes ultraschallunterstütztes Fräsen Generativ gefertigter Turbinenbauteile
(2018)
Die Beschaffung und Verarbeitung von Werkstoffen für hochbelastete Komponenten sind meist kostenintensiv. Bestrebungen zur Kosten- und Ressourceneffizienz führen zu komplexeren Strukturen bzw. Konturen, sodass generative Fertigungsschritte zur Bauteilreparatur und -fertigung deutliche ökonomische Vorteile bieten. Hierfür sind generative und abtragende Fertigungsschritte komplementär und gezielt aufeinander abzustimmen, um beanspruchungsgerechte Funktionsflächen herzustellen.
Hochfeste und -warmfeste Legierungen nehmen in vielen Bereichen des Maschinen- und Anlagenbaus eine immer größere Rolle ein, deren Wirtschaftlichkeit und Effizienz durch eine kostensparende und präzise fügetechnische und abtragende Fertigung bestimmt wird. Komponenten aus modernen hochfesten Werkstoffen erfordern aufgrund ihres spezifischen Legierungskonzeptes und Gefüges und der oft hohen thermo-mechanischen Belastungen speziell adaptierte Fertigungsabläufe. Der Beitrag stellt einige Themenschwerpunkte vor, bei denen fertigungsbedingte Beanspruchungen und Eigenschaftsdegradationen an hochinnovativen Werkstoffen optimiert und wirtschaftliche Fertigungsbedingungen untersucht werden.
Die Beschaffung und Verarbeitung von Werkstoffen für hochbelastete Komponenten sind meist kostenintensiv. Bestrebungen zur Kosten- und Ressourceneffizienz führen zu komplexeren Strukturen bzw. Konturen, sodass generative Fertigungsschritte zur Bauteilreparatur und -fertigung deutliche ökonomische Vorteile bieten. Hierfür sind generative und abtragende Fertigungsschritte komplementär und gezielt aufeinander abzustimmen, um beanspruchungsgerechte Funktionsflächen herzustellen. Hinsichtlich Inhomogenität und Anisotropie der Gefüge und Eigenschaften sowie fertigungsbedingter Beanspruchungen sind für den wirtschaftlichen Einsatz bei KMU, gerade für drahtbasierte Fertigungsverfahren und Wechselwirkungen nachfolgender Zerspanung dieser schwer spanbaren Werkstoffe noch viele Kenntnisse notwendig. Deshalb sind Untersuchungen zu diesen Einflüssen und Wechselwirkungen unter Nutzung innovativer Ansätze geplant. Mit typischen kostenintensiven Ni- und Co-Cr-Legierungen werden generativ Bauteile, Auftrag- und Reparaturschweißungen hergestellt und Schweißzusätze für das PTA-Verfahren modifiziert, um die Erstarrungsmorphologie und das Eigenschaftsprofil zu optimieren. Die Übertragung auf MSG-Verfahren sichert einen breiten industriellen Einsatz für hohe Auftragraten ab. Die wirtschaftliche spanende Bearbeitbarkeit wird mit Zerspanbarkeitsanalysen für Schlichtfräsen und vergleichend für ultraschallunterstütze Fräsprozesse sichergestellt. Instrumentierte Experimente und Werkstoffanalytik hinsichtlich der Einflüsse auf Schmelzbad, Gefüge und Ausscheidungen sowie auf Randzoneneigenschaften und Eigenspannungen ermöglichen umfassende Erkenntnisse zur kombinierten generativen und abtragenden Fertigung. Durch Bauteilversuche und -prüfungen, Übertragbarkeitsstudien weiterer innovativer Werkstoffe verbunden mit Handlungsempfehlungen und der Zusammenarbeit mit den jeweiligen Normungsgremien profitieren KMU von einer hochwirtschaftlichen Herstellung und Reparatur kostenintensiver Komponenten.
While today, engineers can choose from a wide range of rheology modifying admixtures, in some parts of the world, these are difficult to access, due to their complex processing. However, alternatives can be bio‐based polymers such as polysaccharides from various sources. These are easily accessible all over the world, do not demand for complicated processing, and typically they are more sustainable than many established materials, which are crude oil‐based.
The paper presents the effects of acacia gum, cassava starch and the gum of triumfetta pendrata A. Rich on the rheological performance of cementitious systems. It is shown that acacia gum can be as efficient as polycarboxylate based superplasticisers, cassava starch can reduce the yield stress slightly with little effect on the plastic viscosity, and the gum of triumfet ta pendrata A. Rich increases the thixotropy of cement pastes with plasticizing polymers significantly.
Structural design and application have always been linked to the compressive strength of concrete as the main relevant criterion. This was justifiable in the past, where concrete consisted of water, ordinary Portland cement and aggregates, but this concept is no longer relevant for modern and more sustainable cement and concrete.
Despite these new developments, existing standards, guidelines and academic curricula have not been much updated and are still used worldwide. There is a need to change this situation by proper education of the users.
This overview describes the challenges that arise at a user Level from the higher complexity of modern concrete, and defines needs and requirements for enhanced applicability of sustainable concrete concepts.
Furthermore, recommendations are given on how better concrete practice can be communicated to all the involved parties, from civil and design engineers to constructors and site-appliers on the construction site.
UV-curing coatings are nowadays widely used due to their unique advantages. High-quality coatings can be obtained at short curing times and low temperatures so that thermal stress to the substrate is minimised. Photocured Cycloaliphatic-Epoxy Oligosiloxane (CEO) resin was reported to be used as encapsulation material for organic electronics. However, further reinforcement of CEO film properties is desired to achieve requested device lifetime.
In this work we introduced Boehmite nanoparticles (BA) into CEO matrix in order to modify the film properties and study the main changes of the material behaviour with regard to its photocuring kinetics, thermal stability and glass transition. Particular interest was focused on the role of particle surface in nanocomposite properties. Hence, BA particles without (HP14) and with organic surface modifier (OS1) at different loadings (up to 10 wt%) were applied in this study. Morphology investigation with SEM operated in transmission mode showed good BA dispersion forming network-like structure. At the same time, distribution of particles differed for HP14 and OS1 as a result of different interaction in CEO-solvent-particles system. CEO structure obtained via non-hydrolytic sol-gel reaction was verified by 13C and 29Si NMR. In situ monitoring of film curing was performed using RT-IR spectroscopy. No significant modification of final convention degree with particle incorporation was observed in contrast to considerable decrease of curing efficiency reported previously for similar system by Esposito et al.,2008. Further, cured hybrid nanocomposite films were analysed by TGA and DSC, which revealed impact of surface modifier on film thermal properties.
Organic-inorganic nanostructured materials have drawn much attention over the past decade, particularly due to their versatile and outstanding properties. Possessing the properties between those of polymers and those of glasses, siloxane-based resins are non-toxic, easy to synthesize and process hybrid materials, that hold a promising potential in the field of advanced coatings.
Photocurable resins are nowadays widely used as coatings due to their unique advantages. In particular, cationic ring-opening curing is not inhibited by oxygen, leads to low degree of shrinkage and superior adhesion. The most important, it enables production of high-quality coatings within short exposure times without applying temperature, thus, minimizing the presence of the thermal stress in the substrate. Photocured Cycloaliphatic-Epoxy Oligosiloxane (CEO) resin was reported to be used as encapsulation material for organic electronics. However, further reinforcement of CEO properties is desired to achieve requested device lifetime. One of the common approaches to improve material characteristics is by embedding inorganic nanoparticles into polymer matrix. It has been shown that the resulted nanocomposites exhibit enhanced functional properties included but not limited by optical, mechanical, thermal and barrier ones.
In this work we focused on the incorporation of Boehmite nanoparticles (BA) into CEO matrix as a tool to strengthen the film properties and to study the main changes occurred in the material behavior with regard to its photocuring kinetics, thermal stability and glass transition. Particular interest was focused on the role of particle surface in nanocomposite properties. Hence, BA particles without (HP14) and with organic surface modifier (OS1) at different loadings
(up to 10 wt%) were applied in this study. Morphology investigation with SEM operated in transmission mode showed good BA dispersion forming
network-like structure. At the same time, distribution of particles differed for HP14 and OS1 as a result of different interaction in CEO-solvent-particles system. CEO structure obtained via non-hydrolytic sol-gel reaction was verified by 13C and 29Si NMR. In situ monitoring of film curing was performed using
RT-IR spectroscopy. A slight increase of final convention degree with particle incorporation was observed in contrast to the considerable decrease of curing efficiency reported previously for similar system. Further, the cured hybrid nanocomposite films were analyzed by TGA and DSC, which revealed impact of surface modifier on thermal stability and glass transition temperature.
Optical spectroscopy – Techniques, instrumentation, and typical molecular and nanoscale reporters
(2018)
Different types of optical spectroscopies are introduced with special emphasis on method-inherent limitations and reliable instrument calibration and performance validation. In addition, different classes of molecular and nanocrystalline emitters are presented and the underlying photophysical processes are briefly described.
In einer Vielzahl technischer Anwendungen spielt die Aufrechterhaltung eines definierten Reibungs- und Verschleißverhaltens zwischen bewegten Oberflächen für die Sicherheit und Funktionalität eine entscheidende Rolle. Die Oberflächentechnik versucht durch geeignete Verfahren die Randschichten zu ertüchtigen, um Reibung und Verschleiß zu kontrollieren. Eine Verbesserung der Materialeigenschaften kann durch flächige Beschichtungen erreicht werden. Zusätzlich ermöglichen Oberflächenstrukturierungen breite Möglichkeiten zur Beeinflussung des Schmierungszustandes bzw. der Kontaktbedingungen. Neben Negativstrukturen bieten ebenfalls erhabene Mikrostrukturen großes Potenzial zur Beeinflussung des tribologischen Verhaltens. Ihr Einsatz ist aber aufgrund der besonderen Verschleißproblematik erhabener Strukturen momentan limitiert, so dass in der Regel zusätzliche verschleißreduzierende Beschichtungen notwendig werden.
In diesem Beitrag wurde das Verfahren der Laserimplantation angewandt, mit dem erhabene und separierte Oberflächenstrukturen hoher Verschleißfestigkeit in einem Fertigungsschritt erzeugbar sind. Das Verfahren basiert auf einem lokalisierten Dispergieren von Hartstoffpartikeln. Hierfür wurde erstmalig ein gepulster Faserlaser mit hoher Strahlqualität zur Erzeugung punkt- und linienförmiger Mikrostrukturen angewandt. Versuche wurden auf dem Kaltarbeitsstahl X153CrMoV12 unter Anwendung von Titandiborid als Hartstoff durchgeführt. Anhand von Härtemessungen konnte gezeigt werden, dass sowohl punkt- als auch linienförmige Strukturen mit Härten über 1000 HV1 und einer feinkörnigen Mikrostruktur mit feinverteilten Hartstoffpartikeln herstellbar sind. Des Weiteren war es möglich, die Implantgeometrien, welche an Querschliffen und durch Weißlichtinterferometeraufnahmen erfasst wurden, durch die Pulsleistung und Pulsdauer zu steuern.
The aim of this study was to develop a lightweight composite facade element for new buildings and for the refurbishment of existing facades. These composite elements have been developed combining an insulation layer of autoclaved aerated concrete (AAC) with an external ultrahighperformance concrete (UHPC) supporting layer. This solution allows avoiding the use of connectors and facilitates the production procedure. The structural behavior of the facade elements is mainly influenced by the presence of the upturning edges that are able to increase the stiffness of the element and reduce the thickness of the external layer. The insulation material has no influence on the structural behavior of the UHPC boxes. Flexural tests were carried out to investigate a potential detachment of the external layer from the upturning edge. The photogrammetric Analysis used during the flexural tests essentially confirmed that the bond between the two UHPC layers cast in two steps is reliable. The quality of the bond between the external layer and the upturning edge is a key parameter to define the bearing capacity of the element.
The mayor part of the Berlin collection `Manuscripta Americana´ consists of documents compiled by Alexander von Humboldt. The diversity of the written fragments and their shape presume few accordance concerning purpose, place or time of production. Even before the papers came to Berlin, manuscripts were copied, divided and collected by famous scholars also in Mexico. Back in Europe, Humboldt visited further collections and published the detected hieroglyphic writings altogether with cultural objects and landscapes in the book `Vues des Cordillères et Monuments des Peuples Indigènes de l`Amerique, voyage de Humboldt et Bonpland´, labelled corresponding to the cultural background.
By scientific and culture historical analyses, the Humboldt codices are revised and related to each other and others. In especial, the compilation of fragments shown on plate 36 in the book is looked at more closely. Whereas most of the plates represent only one sheet of painted amate paper, here segments with details of seven fragments are put together. It is tried to comprehend why these pieces are on one plate.
To find out a common feature of the documents, their content and represented form are compared. A correlation between some pieces is obvious and thus is also expected in the manufacture of the codices, in the kind of material used. For this the inks and colors are determined by scientific analysis including XRF-, Raman-, FTIR- and VIS- spectroscopy. Special material is detected and related to results of former analysis of codices written during the colonial period of America. Herewith a clear cultural assignment of the manuscripts is performed.
A relation of the fragments represented on plate 36 among each other and to other codices of the collection Manuscripta Americana in Berlin is discussed. Also, if the manuscripts are unique `originals´ or represent fragments of documents, whose corresponding pieces maybe found- in the best case- incorporated in other collections. We detected, that at least two of them can be put into relation to similar manuscripts deposited in Mexico. Further material analysis should clarify, if the corresponding pieces are identical- from one document, or if one of them is a copy. Herewith an approximation to authenticity features and history is issued.
Mandatory for the comparison of different emitter classes and the rational design of the next generation of molecular and nanoscale reporters are reliable and quantitative photoluminescence measurements. This is of special relevance for all fluorescence applications in the life and material sciences. In the following, procedures for the determination of this spectroscopic key parameter are presented including pitfalls and achievable uncertainties and material-specific effects related to certain emitter classes are addressed.
Optical spectroscopic studies of the influence of size, particle architecture, and surface chemistry of different types of photoluminescent nanocrystals with emission in the vis/NIR will be presented including semiconductor quantum dots and lanthanide-based upconversion nanoparticles. This will include the photophysics of these materials assessed with steady state and time-resolved fluorometry on the ensemble and single particle level and concepts for the quantification of surface groups at nanomaterials with optical methods using cleavable probes and catch-and-release assays.
Nanomaterials are used in many different applications in the material and life sciences. Examples are optical reporters, barcodes, and nanosensors, magnetic and optical contrast agents, and catalysts. Due to their small size and large surface area, there are also concerns about their interaction with and uptake by biological systems. This has initiated an ever increasing number of cyctoxicity studies of nanomaterials of different chemical composition and surface chemistry, but until now, the toxicological results presented by different research groups often do not address or differ regarding a potential genotoxicity of these nanomaterials. This underlines the need for a standardized test procedure to detect genotoxicity.1,2
Aiming at the development of fast, easy to use, and automatable microscopic methods for the determination of the genotoxicity of different types of nanoparticles, we assess the potential of the fluorometric γH2AX assay for this purpose. This assay, which can be run on an automated microscopic detection system, relies on the determination of DNA double strand breaks as a sign for genotoxicity.3 Here, we present first results obtained with broadly used nanomaterials like CdSe/CdS and InP/ZnS quantum dots as well as iron oxide, gold, and polymer particles of different surface chemistry with previously tested colloidal stability. These studies will be also used to establish nanomaterials as positive and negative genotoxicity controls or standards for assay performance validation for users of this fluorometric genotoxicity assay. In the future, after proper validation, this microscopic platform technology will be expanded to other typical toxicity assays.
References. (1) Landsiedel, R.; Kapp, M. D.; Schulz, M.; Wiench, K.; Oesch, F., Reviews in Mutation Research 2009, 681, 241-258. (2) Henriksen-Lacey, M.; Carregal-Romero, S.; Liz-Marzán, L. M., Bioconjugate Chem. 2016, 28, 212-221. (3) Willitzki, A.; Lorenz, S.; Hiemann, R.; Guttek, K.; Goihl, A.; Hartig, R.; Conrad, K.; Feist, E.; Sack, U.; Schierack, P., Cytometry Part A 2013, 83, 1017-1026.
Up to now, the mechanisms of surface nucleation and surface-induced texture formation are far from being understood. Very few observations of crystal orientation were focused on separately growing surface crystals. In conclusion, no systematic studies on initially oriented crystal growth or nucleation from defined active surface nucleation sites exists. Therefore, the main objective of this just is to advance the basic understanding of the mechanisms of surface-induced microstructure formation in glass ceramics. As a first attempt, we focus on reorientation of separately growing surface crystals during their early growth.
Uptake and molecular impact of aluminum-containing nanomaterials on human intestinal caco-2 cells
(2018)
Aluminum (Al) is one of the most common elements in the earth crust and increasingly used in food, consumer products and packaging. Its hazard potential for humans is still not completely understood. Besides the metallic form, Al also exists as mineral, including the insoluble oxide, and in soluble ionic forms. Representatives of these three species, namely a metallic and an oxidic species of Al-containing nanoparticles and soluble aluminum chloride, were applied to human intestinal cell lines as models for the intestinal barrier. We characterized physicochemical particle parameters, protein corona composition, ion release and cellular uptake. Different in vitro assays were performed to determine potential effects and molecular modes of Action related to the individual chemical species. For a deeper insight into signaling processes, microarray transcriptome analyses followed by bioinformatic data analysis were employed. The particulate Al species showed different solubility in biological media. Metallic Al nanoparticles released more ions than Al2O3 nanoparticles, while AlCl3 showed a mixture of dissolved and agglomerated particulate entities in biological media. The protein corona composition differed between both nanoparticle species. Cellular uptake, investigated in transwell experiments, occurred predominantly in particulate form, whereas ionic Al was not taken up by intestinal cell lines. Transcellular transport was not observed. None of the Al species showed cytotoxic effects up to 200 mg Al/mL. The transcriptome analysis indicated mainly effects on oxidative stress pathways, xenobiotic metabolism and metal homeostasis. We have shown for the first time that intestinal cellular uptake of Al occurs preferably in the particle form, while toxicological effects appear to be ion-related.
The Ni-Cr-Mo-W alloy is characterized by the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. To protect the surface of the substrate 13CrMo4-5 steel against aggressive environments the Inconel 686 as clad layer was used. The corrosion process was performed in oxidizing mixture of gases like O2, COx, SOx. The second part of corrosion Experiment concerned the corrosion test of the coating in reducing atmosphere of the specified gases with ashes, which contained e.g. Na, Cl, Ca, Si, C, Fe, Al.
Im Rahmen der Erstellung einer fraktographischen online-Datenbank an der BAM wurden systematisch Schwingversuche an einem Sinterstahl vorgenommen, dessen Sinterdichte variiert wurde. Die erzeugten Bruchflächen wurden analysiert, mit der Literatur verglichen und Datensätze in die Datenbank eingefügt.
Im Rahmen der DGM/DVM AG Fraktographie wird an der BAM eine fraktographische online-Datenbank aufgebaut. Während von metallischen Werkstoffen viele Beispiele vorliegen, die auch gut verstanden sind, sind die Brüche von Kunststoffen bislang weniger prominent vertreten. Eine teils ungeklärte Frage ist, in welcher Form sich an Kunststoffen klassische Schwingbrüche nachweisen lassen, wie sie von metallischen Werkstoffen bekannt sind. Der Vortrag zeigt einige Beispiele im Detail und stellt diese zur Diskussion.
Strong coupling effects in magnetocaloric materials are the key factor to achieve a large magnetic entropy change. Combining insights from experiments and ab initio calculations, we review relevant coupling phenomena, including atomic coupling, stress coupling, and magnetostatic coupling. For the investigations on atomic coupling, we have used Heusler compounds as a flexible model system. Stress coupling occurs in first‐order magnetocaloric materials, which exhibit a structural transformation or volume change together with the magnetic transition. Magnetostatic coupling has been experimentally demonstrated in magnetocaloric particles and fragment ensembles. Based on the achieved insights, we have demonstrated that the materials properties can be tailored to achieve optimized magnetocaloric performance for cooling applications.
Ferritic-martensitic Fe-Cr alloys are widely utilised as materials for high temperature applications such as super heater tubes in coal, biomass or co-fired power plants. Various corrosive gases are produced in combustion processes, but especially SO2 is known to cause catastrophic application failure. In order to understand the effect of orientation and grain size of the alloy on the initial corrosion processes we analysed metal coupons of Fe-Cr- alloys (2-13 wt. % Cr) by electron backscattered diffraction (EBSD) before and after exposure to SO2 containing atmospheres in 650°C for short time spans (2 min – 12 h). An infra red heated furnace with integrated water-cooling was used for the ageing procedures to conduct short time experiments and to keep the reaction products in a ‘frozen’ state.
EBSD characterization of oxides formed on the surface of the alloys showed a topotactic relationship between grain orientation of the alloys and the oxides. With increasing scale thickness this relation diminishes possibly due to lattice strain. There appears to be no correlation between oxide growth and absolute, initial orientation, grain size, or the quality of polishing. An initially topotactic relationship between scale and steel had been already described for the formation of magnetite in hot steam environments, indicating that the initial corrosion mechanisms are mainly depending on the presence of Oxygen, and not changed by the presence of Sulphur. However, Sulphur is incorporated into the oxide scale in the low Cr alloy, and mainly observable in the inner corrosion zone for the higher alloyed material. Furthermore, oxides formed directly on grain boundaries in higher Cr alloyed materials are enriched in Cr compared to oxides on grain faces.
Ferritic high temperature alloys are widely used as boiler tube and heat exchanger materials in coal, biomass and co-fired power plants. All technologies have in common that the applied materials are exposed to different temperatures, process pressures and reactive atmospheres that lead to a change of the material properties and a further degradation of the material. Material changes caused by aging in highly corrosive and toxic gases such as SO2 are mainly studied ex situ after the reaction is finished. The solid material is deposited in the atmosphere for a certain period of time, and material changes are then examined by various microscopic techniques such as optical microscopy (OM), electron microprobe analysis (EMPA), scanning electron microscopy (SEM and TEM) and X-ray diffraction (XRD). Nevertheless, extensive efforts were made to study material changes of high temperature alloys under oxidizing and reducing atmospheres by environmental scanning electron microscopy or in situ TEM techniques However, the possibilities of microscopic in situ techniques are very limited for the use of highly corrosive and toxic gases such as SO2. Since Sulfur induced corrosion at temperatures relevant for coal and biomass fired power plants, which is causing breakaway oxidation and sulfide precipitation at grain boundaries, is still of scientific interest, the current work focuses on the effect of SO2 in an initial stage of corrosion of ferritic alloys. For the analysis of early stages of combined oxidation and sulphidation processes of Fe-Cr model alloys the usage of a light furnace to conduct a rapid reactive annealing experiment is feasible. Previous studies presented distinct results of the influence of chromium on early high temperature corrosion by SO2 by this technique and subsequent classical metallographic analyses. However, it is still not possible to trace the corrosion mechanism in real time by conducting single aging experiments. The current work introduces two different approaches to study the initial stages of high temperature oxidation processes by applying above state of the art X-ray diffraction and spectroscopy methods. One part focuses on the real time observation of the formation of corrosion products such as oxides and sulfides by energy dispersive X-ray diffraction (EDXRD). The potential of this technique to study crystallization and growth processes of thin films in a reactive environment in real time was previously shown for different compound semiconductors. This approach was now applied to follow oxidation and sulphidation processes of ferritic model alloys in SO2 and SO2/H2O environments. The diffraction signals of the X-rays were detected during the corrosion process and the peak area and positions were analyzed as a function of time. This procedure enables monitoring external oxide growth and material loss in real time in an early stage of corrosion.
The other part of the current work presents the possibilities of X-ray absorption near edge structure spectroscopy (XANES) to characterize oxide scales and their growth mechanisms. Precise phase identification and quantification of corrosion products in a multi-phase oxide/sulfide scale is a pre-requisite to understand diffusion paths of metal ions and gas components. It is a challenging task to distinguish structurally similar reaction products such as Fe3O4 and FeCr2O4 especially in thin films with texture effects by diffraction. To illustrate for example Cr-out diffusion of an alloy throughout an inner and external oxide scale the differentiation of Fe3O4 and FeCr2O4 is indispensable. XANES uses the photoionization effect at the metal absorption edge in an aging product and accesses by this structural and chemical information. The current work uses XANES at the Fe-K and Cr-K absorption edge to identify various aging products grown as thin layers on alloys after short time aging experiments. A reaction chamber for combining high temperature oxidation experiments with surface sensitive X-ray absorption near edge structure spectroscopy will be introduced and first results of XANES on scales at high temperatures will be presented.
Ferritic-martensitic alloys with 12-16 % Cr in weight are subject to devices for various energy systems, such as coal power plants and waste incineration plants. These materials are exposed to a highly corrosive environment which lead to a degradation of the material. Especially the simultaneous oxidation and sulfidation is thereby of special interest. Proper spatially resolved measurements that determine not only chemical compositions but phases are rare. However, precise phase identification and quantification of corrosion products within the multi-phase corrosion scales is a key aspect to understand diffusion paths of metal ions and gas ions/molecules. This study investigated Fe-Cr model alloys with Cr contents from 0 to 13 % in weight in 0.5 % SO2 and 99.5 % Ar atmosphere to aim in a fundamental and systematic analysis. Samples were aged at 650 °C for time scales from 12 h to 250 h. The results presented here correspond to depth dependent phase identification of oxide and sulphide phases in the corrosion scales by using X-ray absorption near edge spectroscopy (XANES). Per sample a series of ca. 20 spots (1-5 µm spot size) from scale-gas to scale-metal interface were measured. XANES spectroscopy was performed at the Fe-K edge (7.11 keV) on polished cross sections. The collected spectra were fitted to a combination of reference materials to quantify the present phases at different positions within the scale.The phase distribution differs with Cr content and the Cr diffusion through pure Fe-oxide and mixed Fe-Cr-oxide phases is discussed.
An increase in the thermal diffusivity of Fe2TiO5 is observed after only three cycles of measurement. X-ray refraction shows an increase in the mean specific surface. A segregation of Ca- and F-rich nanocrystals at grain boundaries is also observed by SEM and STEM-EDX. This emphasizes the importance of precursor purity and the influence of redistribution of impurities on thermoelectric properties.
Up to now THz-TDS-systems aren’t considered to be nondestructive testing facilities for large scale industrial applications, despite it was proven that they provide a comprehensive set of quality parameters. A practical approach to bring THz-TDS in addition to already existing testing systems into the industrial mainstream is systematic development of future test procedures and test facilities for dielectrics. For this purpose polyeth-ylene test specimen with introduced artefacts were designed, to evaluate the detection sensitivity of Time of Flight measurements based on dielectrics. SAFT reconstructed tomograms are presented which visualize the sizes and location of artificially introduced flaws.
Additive Manufacturing (AM) offers the opportunity to produce easier geometrically complex parts compared to traditional production technologies. An important AM technology for metals is selective laser melting (SLM) where a part is produced by melting and solidifying powder in layers. This technique is known to cause a pronounced texture in the produced AM products due to the specific heat flow and the associated solidification of the material during SLM deposition. In order to evaluate the influence of the deposition hatch length during SLM of nickel based superalloy Inconel 718 samples on the texture and in order to identify any preferred crystallographic direction, we performed monochromatic neutron radiography scans (using wavelength from 1.6 Å to 4.4 Å, step size 0.05 Å) to image the samples while rotating it through 90°. Samples produced with short hatch length showed fine textured columnar grains oriented along the sample building direction in high-resolution radiographs. Whereas processing the sample using a ten-fold longer hatch length reduced the texture. The neutron radiographic experiments were accompanied by scanning electron microscopy including electron back-scattered diffraction to visualize and verify the microstructure and texture.
Dissimilar metal weld overlays of nickel-base alloys on low-alloy steel components are commonly used in the oil and gas, petrochemical, and power generation industries to provide corrosion and oxidation resistance in a wide range of service Environments and temperatures. Traditionally, dissimilar weld overlays are produced using cold or hot wire gas tungsten arc welding.
This study aims to identify and evaluate potential advantages of low heat input gas metal arc welding processes over the conventional gas tungsten arc welding in the production of such overlays. Parts I and II of this publication series described characteristics of the heat-affected zone and the transition zone region of alloy 625 on grade 22 steel overlays. These results indicate a good resistance against hydrogen-assisted cracking, which is being verified within this third part of the publication series. To determine the hydrogen-assisted cracking susceptibility, welded samples are tested using the delayed hydrogen-assisted cracking test. Fractography is performed using scanning electron microscopy along with energy dispersive spectroscopy. The results confirm the suitability and efficiency of low heat input gas metal arc welding for dissimilar weld overlays. Variation of the postweld heat treatment procedure bears potential for improvement in this respect.
With the recent rise in the demand for additive manufacturing (AM), the need for reliable simulation tools to support experimental efforts grows steadily. Computational welding mechanics approaches can simulate the AM processes but are generally not validated for AM-specific effects originating from multiple heating and cooling cycles. To increase confidence in the outcomes and to use numerical simulation reliably, the result quality Needs to be validated against experiments for in-situ and post-process cases. In this article, a validation is demonstrated
for a structural thermomechanical simulation model on an arbitrarily curved Directed Energy Deposition (DED)part: at first, the validity of the heat input is ensured and subsequently, the model’s predictive quality for in-situ
deformation and the bulging behaviour is investigated. For the in-situ deformations, 3D-Digital Image Correlation measurements are conducted that quantify periodic expansion and shrinkage as they occur. The results show a strong dependency of the local stiffness of the surrounding geometry. The numerical Simulation model is set up in accordance with the experiment and can reproduce the measured 3-dimensional in-situ displacements. Furthermore, the deformations due to removal from the substrate are quantified via 3D-scanning, exhibiting considerable distortions due to stress relaxation. Finally, the prediction of the deformed shape is discussed in regards to bulging simulation: to improve the accuracy of the calculated final shape, a novel Extension of the model relying on the modified stiffness of inactive upper layers is proposed and the experimentally observed bulging could be reproduced in the finite element model.
The presence of polycarboxylate ether (PCE) based superplasticizers (SPs) has an enormous influence on the early hydration of cement. The hydration is retarded and the timing of formation and the morphology of hydrates is affected. This short paper presents experimental results about the influence of delayed addition time of PCE SPs on hydration of cement and alite pastes, investigated by isothermal heat flow calorimetry. For cement as well as for alite pastes the hydration is retarded with SP, whereby the high charge PCE has a stronger retarding effect than the low charge PCE. The retardation caused by PCE is much more pronounced for alite than for cement mixes. If PCE is added later to the mix, the induction period is shortened and the hydration is accelerated compared to simultaneous addition. This applies for cement and alite pastes. With delayed PCE addition the alite shows a clearly less retarded setting and main hydration than after simultaneous addition. It is obvious that for alite pastes there is less retardation the later the addition of SP.
Clustering of magnetic nanoparticles can drastically change their collective magnetic properties, which in turn may influence their performance in technological or biomedical applications. Here, we investigate a commercial colloidal dispersion (FeraSpinTMR), which contains dense clusters of iron oxide cores (mean size around 9 nm according to neutron diffraction) with varying cluster size (about 18–56 nm according to small angle x-ray diffraction), and its individual size fractions (FeraSpinTMXS, S, M, L, XL, XXL). The magnetic properties of the colloids were characterized by isothermal magnetization, as well as frequency-dependent optomagnetic and AC susceptibility measurements. From these measurements we derive the underlying moment and Relaxation frequency distributions, respectively. Analysis of the distributions shows that the clustering of the initially superparamagnetic cores leads to remanent magnetic moments within the large clusters. At frequencies below 105 rad s−1, the relaxation of the clusters is dominated by Brownian (rotation) relaxation. At higher frequencies, where Brownian relaxation is inhibited due to viscous friction, the clusters still show an appreciable magnetic relaxation due to internal moment relaxation within the clusters. As a result of the internal moment relaxation, the colloids with the large clusters (FSL, XL, XXL) excel in magnetic hyperthermia experiments.
We investigated the growth of β-phase NaYF4:Yb3+,Er3+ upconversion nanoparticles synthesized by the thermal decomposition method using a combination of in situ and offline analytical methods for determining the application-relevant optical properties, size, crystal phase, and chemical composition. This included in situ steady state luminescence in combination with offline time-resolved luminescence spectroscopy as well as small-angle X-ray scattering (SAXS) transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), and inductively coupled Plasma optical emission spectrometry (ICP-OES). For assessing the suitability of our optical monitoring approach, the in situ-collected spectroscopic data, which reveal the luminescence evolution during nanocrystal synthesis, were compared to measurements done after cooling of the reaction mixture of the as-synthesized particles. The excellent correlation of the in situ and time-resolved upconversion luminescence with the nanoparticle sizes determined during the course of the reaction provides important insights into the various stages of nanoparticle growth. This study highlights the capability of in situ luminescence monitoring to control the efficiency of UCNP synthesis, particularly the reaction times at elevated temperatures and the particle quality in terms of size, shape, and crystal structure, as well as luminescence lifetime and upconversion quantum yield.
Additive Manufacturing by Selective Laser Melting (SLM) offers an ample scope for producing geometrically complex parts as compared to the traditional subtractive manufacturing strategies. However, the residual stresses (RS) developed during the processing can reduce the load bearing capacity as well as induce unwanted distortion, limiting the life time and the application of SLM parts.
The fluorescence lifetime is a key property of fluorophores that can be utilized for microenvironment probing, analyte sensing, and multiplexing as well as barcoding applications. For the rational design of lifetime probes and barcodes, theoretical methods have been developed to enable the ab initio prediction of this parameter, which depends strongly on interactions with solvent molecules and other chemical species in the emitters' immediate environment. In this work, we investigate how a conductor-like screening model (COSMO) can account for variations in fluorescence lifetimes that are caused by such fluorophore−solvent interactions. Therefore, we calculate vibrationally broadened fluorescence spectra using the nuclear ensemble method to obtain distorted molecular geometries to sample the electronic transitions with time-dependent density functional theory (TDDFT). The influence of the solvent on fluorescence lifetimes is accounted for with COSMO. For example, for 4-hydroxythiazole fluorophore containing different heteroatoms and acidic and basic moieties in aprotic and protic solvents of varying polarity, this approach was compared to experimentally determined lifetimes in the same solvents. Our results demonstrate a good correlation between theoretically predicted and experimentally measured fluorescence lifetimes except for the polar solvents Ethanol and acetonitrile that can specifically interact with the heteroatoms and the carboxylic acid of the thiazole derivative.
Due to the advantages of additive manufacturing (AM), it has been increasingly integrated into many industrial sectors.
The application of AM materials for safety-critical parts requires the detailed knowledge about their microstructure stability under thermo-mechanical or mechanical load and knowledge on ageing process mechanisms. Ageing processes are characterized by change of the material microstructure that is to be initially investigated. This work deals with the Investigation of 316L stainless steel manufactured by selective laser melting (SLM). Describing Parameters must be defined and applied on the microstructure of these materials in their initial state and after loads were applied. The findings of this work form the basis for the investigation of AM material ageing.
Die Untersuchung stellt eine Technologie einer Hochtemperatur-Ultraschallankopplung zwischen einem Lithiumniobat-Piezokristall und einer Elektrode aus rostfreiem Stahl dar. Die Ultraschallankopplung erfolgt durch das Diffusionslotprozess mit einem Aktivlot auf Silber-Kupfer-Basis.
Die beschriebene Technologie ermöglicht die Herstellung eines hochtemperaturbeständigen Ultraschallprüfkopf zum Dauereinsatz bis 600 °C.
A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12–43 nm is presented utilizing steady-state and time-resolved fluorometry.
Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by highenergy O–H and C–H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated Population pathways of the 4F9/2 energy level of Er3+ were examined. Our results Highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under “strongly quenched” conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the 4F9/2 energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels.
Producing active polymer optical fibers (POFs) is a key step towards new applications such as fluorescent fiber solar concentrators (FFSCs), sensors, contactless coupling devices, or fiber integrated light sources and lasers. Therefore, integration of fluorescent nanoparticles into the polymer matrix is necessary and becomes accessible via in situ polymerization. For optical applications, the polymer has to fulfill various requirements such as chemical and physical stability, optical transparency in the application-relevant spectral region as well as a good synthetic accessibility. A common material for these is poly(methyl methacrylate) (PMMA). The beta-phase NaYF4 : Yb3+, Er3+ upconversion nanoparticles (UCNP) were synthesized from the rare earth salts via thermal decomposition method in high-boiling point solvent 1-octadecene and capping agent oleic acid. Current results show hazy samples of the polymer with integrated nanoparticles made from monomer solution of methyl methacrylate. However, further optical tuning such as increasing the transparency of the bulk samples by changing the monomer solution to non-polar n-butyl methacrylate (nButMA) or cyclohexyl methacrylate (CHMA) or further optimization of the UCNP shell could lead to more suitable polymer bulk samples.
Environmental conditions are known to influence sub-critical crack growth (SCCG) that are released from microscopic flaws at the glass surface, leading to stress corrosion phenomena at the crack tip. The processes at the crack-tip are complex and water has been identified as a key component governing SCCG at low crack velocities (region I). In particular, the influence of humidity accelerating crack propagation is well studied for industrial soda-lime silicate glasses, which are practically free (< 1000 ppm) of dissolved water. To shed light on the corrosion process, the situation at the crack-tip is reversed in the present study as dissolved water in larger fractions is present in the glass and crack propagation is triggered in dry environment. For this purpose, water-bearing silicate glasses of up to 8 wt% total water were synthesized in an internally heated pressure vessel at 0.5 GPa and compared to dry glasses of standard glass manufacturing. SCCG was measured using the double cantilever beam technique and by Vickers indentation. For dry glasses, three trends in the crack growth velocity versus stress intensity curve were found. The slope in region I limited by environmental corrosion increases in the order sodium aluminosilicate < sodium borosilicate ≲ sodium lead silicate. The velocity range of region II reflecting the transition between corrosion affected and inert crack growth (region III), varies within one order of magnitude among the glasses. The KI region of inert crack growth strongly scatters between 0.4 and 0.9 MPam1/2. For hydrous glasses, it is found that those of low Tg are more prone to SCCG. As water strongly decreases Tg, it promotes SCCG. First results indicate that molecular water has a dominating influence on SCCG.
Microstructure characterisation of advanced materials via 2D and 3D X-ray refraction techniques
(2018)
3D imaging techniques have an enormous potential to understand the microstructure, its evolution, and its link to mechanical, thermal, and transport properties. In this conference paper we report the use of a powerful, yet not so wide-spread, set of X-ray techniques based on refraction effects. X-ray refraction allows determining internal specific surface (surface per unit volume) in a non-destructive fashion, position and orientation sensitive, and with a nanometric detectability. We demonstrate showcases of ceramics and composite materials, where microstructural parameters could be achieved in a way unrivalled even by high-resolution techniques such as electron microscopy or computed tomography. We present in situ analysis of the damage evolution in an Al/Al2O3 metal matrix composite during tensile load and the identification of void formation (different kinds of defects, particularly unsintered powder hidden in pores, and small inhomogeneity’s like cracks) in Ti64 parts produced by selective laser melting using synchrotron X-ray refraction radiography and tomography.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons in electrical contact with the metal. Methanogenic archaea can also cause MIC by directly withdrawing electrons from the iron surface for methanogenesis. However, the mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite, a by-product of methanogenesis, (4Fe + 5HCO3 + 5H+ 4FeCO3 + CH4 + 3H2O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO3 precipitation may be significantly influenced by environmental conditions such as pH and advective processes.
The age hardening response of a high-purity Al–4Cu–1Li–0.25Mn alloy (wt. %) during isothermal aging without and with an applied external load was investigated. Plate shaped nanometer size T1 (Al2CuLi) and θ′ (Al2Cu) hardening phases were formed. The precipitates were analyzed with respect to the development of their structure, size, number density, volume fraction and associated transformation strains by conducting transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) studies in combination with geometrical Phase analysis (GPA). Special attention was paid to the thickening of T1 phase. Two elementary types of single-layer T1 precipitate, one with a Li-rich (Type 1) and another with an Al-rich (Defect Type 1) central layer, were identified. The results show that the Defect Type 1 structure can act as a precursor for the Type 1 structure. The thickening of T1 precipitates occurs by alternative stacking of These two elementary structures. The thickening mechanism was analyzed based on the magnitude of strain associated with the precipitation transformation normal to its habit plane. Long-term aging and aging under load resulted in thicker and structurally defected T1 precipitates. Several types of defected precipitates were characterized and discussed. For θ′ precipitates, a ledge mechanism of
thickening was observed. Compared to the normal aging, an external load applied to the peak aged state leads to small variations in the average sizes and volume fractions of the precipitates.
The current competitive situation on electricity markets forces power plants into cyclic operation regimes with frequent load shifts and starts/shutdowns. In the present work, the cyclic mechanical behavior of ferritic-martensitic 9-12 % Cr steels under isothermal and thermomechanical loading was investigated for the example of grade P92 material. A continuous softening was observed under all loading conditions. The introduction of hold periods to the applied cycles reduced material lifetime, with most prominent effects at technologically relevant small strain levels. The microstructural characterization reveals a coarsening of the original “martensitic” lath-type microstructure to a structure with polygonal subgrains and reduced dislocation density. The microstructural data forms the input for a physically-based modelling approach.
9-12% Cr ferritic-martensitic stainless steels are widely used as high temperature construction materials in power plants due to their excellent creep and oxidation resistance. The growing share of renewable energy sources in power generation forces many of these plants into more flexible operation with frequent load shifts or shutdowns. These cyclic operation profiles constitute a major lifetime issue.
The present contribution reports on current findings obtained in a multidisciplinary project which combines cyclic mechanical and cyclic oxidation testing with detailed microstructural analyses. Mechanical analyses are carried out on P92 and P91 steel grades to give an overview of softening phenomena and lifetimes obtained in isothermal cyclic loading (low cycle fatigue, LCF), non-isothermal cyclic loading (thermo-mechanical fatigue, TMF), and service-like combinations of creep and fatigue periods (creep-fatigue interaction).
Oxidation testing focuses on the grades P92 and VM12 with the intention of clarifying the impact of frequent passes through intermediate temperature levels on the kinetics of steam-side oxidation and the characteristics of the evolving oxide scales. An attempt is made to evaluate their composition, strength, integrity and adhesion after up to 250 temperature cycles. Flat coupons as well as curved tube sections are tested to assess the mutual influence of geometry on oxide scale integrity.
Complementary microstructural investigations by scanning and transmission electron microscopy plus EBSD are used for phase identification and substrate/oxide interface characterisation. The evolutions of grain size and dislocation density under different test conditions are quantified.
9-12% Cr ferritic-martensitic stainless steels are widely used as high temperature construction materials in power plants due to their excellent creep and oxidation resistance. The growing share of renewable energy sources in power generation forces many of these plants into more flexible operation with frequent load shifts or shutdowns. These cyclic operation profiles constitute a major lifetime issue. The present contribution reports on current findings obtained in a multidisciplinary project which combines cyclic mechanical and cyclic oxidation testing of different 9-12% Cr grades with detailed microstructural analyses.
Mechanical analyses are carried out on P92 and P91 steel grades to give an overview of softening phenomena and lifetimes obtained in isothermal cyclic loading (low cycle fatigue, LCF), non-isothermal cyclic loading (thermo-mechanical fatigue, TMF), and service-like combinations of creep and fatigue periods.
Complementary microstructural investigations by scanning and transmission electron microscopy plus EBSD are used for phase identification, substrate/oxide interface characterization and quantification of the microstructure evolution under cyclic conditions.
Laser-Metal-Deposition (LMD) and Plasma-Transferred-Arc (PTA) are well known Technologies which can be used for cladding purposes. The prime objective in combining LMD and PTA as a Hybrid Metal Deposition-Technology (HMD) is to achieve high Deposition rates at low thermal Impact. Possible applications are coatings for wear protection or repair welding for components made of steel. The two energy sources (laser and Plasma arc) build a Joint process Zone and are configurated to constitute a stable process at laser powers between 0.4-1 kW (defocused) and Plasma currents between 75-200 A. Stainless steel 316L serves as filler material. For this HMD process, a Plasma Cu-nozzle is designed and produced by powder bed based Selective Laser Melting. The potential of the HMD Technology is investigated and discussed considering existing process. This paper demonstrates how the interaction of the two energy sources effects the following application-relevant properties: Deposition rate, powder Efficiency and energy Input.
Pores in additive manufactured metal parts occur due to different reasons and affect the part Quality negatively. Few investigations on the origins of porosity are available, especially for Ni-based super alloys. This paper presents a new study to examine the influence of common processing Parameters on the Formation of pores in parts built by laser metal Deposition using Inconel 718 powder. Further, a comparison between the computed tomography (CT) and the Archimedes method was made. The Investigation Shows that CT is able to identify different kinds of pores and to give further Information about their distribution. The identification of some pores as well as their shape can be dependent on the Parameter Setting of the Analysis tool. Due to limited measurement Resolution, CT is not able to identify correctly pores with Diameters smaller than 0.1 mm, which leads to a false decrease on Overall porosity. The applied Archimedes method is unable to differentiate between gas porosity and other Kinds of holes like internal cracks or lack of Fusion, but it delivered a proper value for Overall porosity. The method was able to provide suitable data for the statistical Evaluation with design of Experiments, which revealed significant Parameters ont he Formation of pores in LMD.
In den letzten Jahren hat vor allem die Nachfrage nach additiven Fertigungstechnologien und Reparaturverfahren für Hochfeste Werkstoffe einen starken Aufschwung erlebt. Ein Verfahren, welches sich neben der Herstellung von Beschichtungen besonders für diese Anwendungen eignet, ist das Laser-Pulver-Auftragschweißen. Es wird besonders für Reparaturen bzw. zur Herstellung von teuren Bauteilen, wie Werkzeuge oder Turbinenteilen, eingesetzt. Da diese Teile oft großen mechanischen sowie thermischen Belastungen ausgesetzt sind, ist es besonders wichtig, dass die erzeugte Struktur eine hohe Qualität aufweist. In dieser Arbeit wird die statistische Versuchsplanung genutzt, um Modelle für die Oberflächenbeschaffenheiten von Inconel 718 zu generieren. Als Grundlage dient hierbei ein zentral zusammengesetzter Versuchsplan mit großem Parameterfenster. So wird die Leistung zwischen 550 Watt und 1950 Watt, der Vorschub von 530 mm/min bis 920 mm/min, der Pulvermassenstrom von 3 g/min bis 12 g/min sowie der Spotdurchmesser von 1 mm bis 2 mm variiert. Auf diese Weise wird die Spurgeometrie beeinflusst. Darüber hinaus wird das Überlappungsverhältnis zwischen 20% bis 50% verändert. Die Auswertung der Oberflächenbeschaffenheit erfolgt mit dem auf der Fokusvariation basierendem Oberflächenmessgerät Alicona Infinite-Focus. Dieses Verfahren der 3D Mikrokoordinatenmesstechnik gewährleistet eine zuverlässige Auswertung der Spurgeometrie, der Welligkeit sowie die Messung der mittleren arithmetischen Höhe Sa zur Bestimmung der Oberflächenrauheit. Anschließend werden die generierten Modelle verifiziert. Ziel dabei ist, kostenintensive Vorversuche in Zukunft einzusparen. Darüber hinaus wird das Prozessverständnis erweitert und signifikante Einflussfaktoren identifiziert.
Die Ausführung von Abdichtungssystemen insbesondere an Ingenieurbauwerken der Verkehrsinfrastruktur greift in die unmittelbare Verfügbarkeit/Nutzbarkeit des Bauwerks ein und erfolgt deshalb i.a.R. unter höchstem Zeitdruck. Neuere materialtechnische Entwicklungen im Bereich der Flüssigkunststoff-Systeme erlauben kürzere Ausführungszeiten in einem erweiterten Einsatzspektrum. Zur Sicherstellung anforderungsgerechter Gebrauchseigenschaften des gesamten Brückenabdichtungssystems gibt die vorliegende Veröffentlichung Hinweise für die einzuhaltenden Baugrundsätze, bautechnologische Besonderheiten und Erfordernisse im Umgang mit Polymethylmethacrylat (PMMA) sowie qualitätssichernde Maßnahmen.
To investigate early stage corrosion processes of stainless steel 1.4301 taking place during the biofilm formation of the organism Shewanella putrefaciens electrochemical impedance spectroscopy (EIS) in a multielectrode approach has been used. The multielectrode array consisted of up to 25 electrically isolated electrodes made of stainless steel wires of diameters ranging from 100 µm to 500 µm. They were connected to a multichannel microelectrode analyzer (MMA) electrically coupled through zero resistance ammeters. Current flow between electrodes in the array as well as changes in impedance of individual electrodes over time were recorded and analyzed with respect to the onset of localized corrosion and biofilm formation. The results were complemented by optical microscopy, SEM and AFM images which were taken immediately after the respective experiment. To verify that the multielectrode arrays correctly indicated the initial stages of the corrosion process and of biofilm formation they were introduced in a flow cell reaction vessel containing test specimens made from stainless steel 1.4301, which were checked regularly for signs of localized corrosion and biofilms. Preceding results with the multielectrode array in solutions containing high amounts of chloride ions and hydrogen peroxide at low pH also showed that it is possible with the MMA to monitor individual electrodes becoming local anodes as local corrosion set in, while the remaining electrodes predominantly acted as cathodes.
The governing load bearing mechanism of multi-pile foundations is often the shaft friction. Under cyclic loading the soil particles next to the foundation rearrange and tend to compact leading to a decrease of the surrounding normal stress. The reduction of the normal stress leads to a lower threshold for shear stress (friction fatigue), which results in a degraded shaft bearing capacity. The common interface models used for numerical simulations (e.g. Mohr-Coulomb) are not able to capture such behavior. This work aims to develop an interface material model that incorporates such features of the contact behavior at the soil-structure interface.
Fugenfüllsysteme für Fahrbahnbeläge unter höchsten Beanspruchungen bestimmen in zunehmenden Maße die sichere Verfügbarkeit des Autobahnnetzes. Die aktuellen europäischen technischen Regelungen zu deren Verwendbarkeit folgen noch einem spezifikatorischen Ansatz auf empirischen Grundlagen. Es hat sich gezeigt, dass ein solcher Ansatz den Dauerhaftigkeits- und Nutzungsanforderungen nicht mehr entsprechen kann. Der Autor plädiert in seinem Vortrag für einen Paradigmenwechsel hin zu einem funktionsanalytischen Bewertungsansatz. Es werden Vorschläge für eine versuchstechnische Lösung des Problems und die damit verbundenen Chancen für Optimierung und Innovation aufgezeigt.
Einfluss der Schweißnaht-Nachbehandlung auf die Korrosionsbeständigkeit des Duplex-Stahls 1.4062
(2018)
Die Korrosionsbeständigkeit von Schweißverbindungen aus dem Duplex-Stahl 1.4062 wird, neben dem Grundwerkstoff, dem Schweißzusatzwerkstoff und dem Schweißverfahren, auch sehr stark von der Oberflächennachbehandlung der Schweißnaht beeinflusst. Je nach zukünftigem Anwendungsbereich und geforderter Korrosionsbeständigkeit wird die Schweißnaht geschliffen, gebeizt, elektropoliert oder gestrahlt, um die beim Schweißen entstandenen Anlauffarben zu entfernen. Gestrahlte Oberfläche sind in der industriellen Praxis häufig anzutreffen, da sie deutlich einfacher und kostengünstiger herzustellen sind als gebeizte oder elektropolierte Oberflächen. Die Auswahl des Strahlmittels bestimmt auch die Prozesskosten, wobei das Strahlen mit Korund effektiver als das Strahlen mit Glasperlen ist. Ziel der Untersuchungen war es festzustellen, ob das Strahlen aus Sicht der Korrosionsbeständigkeit äquivalent zu anderen Nachbehandlungsverfahren ist. Diese Fragestellung wird im Vortrag beantwortet indem geschliffene, gebeizte, mit Korund gestrahlte und mit Glasperlen gestrahlte Schweißverbindungen vergleichend untersucht werden. Die Ergebnisse der Untersuchungen von den Strahlmitteln und den gestrahlten Oberflächen werden mit den Ergebnissen der Salzsprühnebelprüfung, den kritischen Lochkorrosionspotentialen und der KorroPad-Prüfung korreliert.
Einfluss industrieller Korundschleifprozesse auf die Korrosionsbeständigkeit nichtrostender Stähle
(2018)
Im Vortrag werden Ergebnisse des AiF Forschungsvorhabens "Optimierung industrieller Korundschleifprozesse zur Sicherstellung der Korrosionsbeständigkeit nichtrostender Stähle" vorgestellt, die den Einfluss verschiedener Schleifmittel auf die Korrosionsbeständigkeit geschliffener Oberflächen nichtrostender Stähle belegen. Es konnte ein signifikanter Einfluss durch die Verwendung von Granulatschleifbändern nachgewiesen werden, der die Korrosionsbeständigkeit der Oberflächen reduziert. Grund sind auf der Oberfläche zurückbleibende Materialaufplattungen von Eigenmaterial aus dem Schleifprozess. Es wurden unterschiedliche Korrosionsuntersuchungen durchgeführt und durch Oberflächenanalytik im Rasterelektronenmikroskop untermauert.
Normung der KorroPad-Prüfung zum Nachweis lochkorrosionsanfälliger Oberflächen und Werkstoffzustände
(2018)
Mit der KorroPad-Prüfung kann die Lochkorrosionsbeständigkeit nichtrostender Stähle auf sehr einfache, schnelle und kostengünstige Weise eingeschätzt werden. Das KorroPad ist damit für Hersteller, Verarbeiter und Anwender nichtrostender Stähle eine interessante Alternative zu zeitintensiven Langzeitversuchen und komplexen elektrochemischen Untersuchungsmethoden. Die prinzipiellen Funktionsweise der KorroPad-Prüfung wird im Vortrag beschrieben, um anschließend verschiedene Anwendungen vorzustellen. Exemplarisch werden dazu die Bewertung von Schleif-, Strahl- und Passivierungsprozessen, die der Einfluss von Schwefel und die werkstoffbezogene Nachweisgrenze der KorroPad-Prüfung. Abschließend wird auf ein geplantes Vorhaben zur Normung der KorroPad-Prüfung eingegangen.
Different strategies for the synthesis of polylactides were presented with special focus on Ring-opening Polymerization (ROP) and simultaneous ROP and Polycondensation (ROPPOC) mechanism. The mechanism of the formation of cyclic Polyesters is discussed in detail and established theories about the formation of cycles in polycondensation reactions are critically reviewed.
In context of CLUSTER project, impacts of impurities (SO2, NO2, O2, CO, H2S, H2, N2, Ar and H2O) in CO2 streams captured from different sources in a regional cluster on transport, injection and storage were investigated. Corrosion studies of oxidizing, reductive or mixed atmospheres towards transport pipeline steel X70 were carried out applying high pressure (10 MPa) at low temperatures (278 K or 313 K).
We present the synthesis of four mesoporous templated iron oxides: Ferrihydrite, Hematite, Maghemite, Magnetite/Maghemite and the influence of water on the crystallization mechanism and the kinetics. The absence of water stabilize the ferrihydrite structure. By monitoring the dissolution in situ by using a QCMB and ex situ microscopy we got details in the dissolution mechanism of ferrihydrite.
Polynuclear aluminium species (Al13 keggin cluster) find application in different areas like water purification [1], contaminant transport [2], and as pilling clays with high specific surface areas[3], due to their strong binding ability to aggregates and high positive charge.
In the present contribution, we report on the in situ investigation of the Al13 sulfate synthesis by synchrotron wide-angle X-ray scattering (WAXS). Al13 cluster were crystallized by precipitating hydrolyzed aluminum solutions by the addition of sodium sulfate. The measurements were performed using a custom-made acoustic levitator as sample holder. The study provides information about the intermediates during the crystallization process. From the data, a mechanism was derived indicating the influence of the crystallization process.
Es konnte anhand einer numerischen Voruntersuchung gezeigt werden, dass anhand der kombinierten Auswertung der im Versuch verwendeten Sensorik eine Einteilung der unter Ermüdung in Bohrlochproben auftretenden Rissformen in verschiedene Hauptkategorien (Eckriss, Oberflächenriss, Durchgangsriss) möglich ist.
Es wird eine neu entwickelte Methode zur Thermographiebasierten Rissmessung vorgestellt. Darüber hinaus wird eine numerische Vorarbeit präsentiert, die zeigt, dass anhand der gemeisamen Auswertung der Versuchsdaten aus unterschiedlicher Sensorik die Möglichkeit besteht, die unter Ermüdungsbelastung in Bohrlochproben auftretenden Risse in Geometriekategorien zu unterteilen.
The state of fresh concrete is predominantly determined by the rheological properties of the cement paste. In order to control performance spectra and requirements of novel concretes and to better understand macroscopic phenomena, comprehensive knowledge of the material behavior of fresh cement suspensions as well as of the complex relationships of mechanisms at the nano and micro scale are necessary. This work focuses on micro and nano rheology of suspensions of cementitious model systems and the influence of polycarboxylate-based admixtures on the rheology. The phenomena are driven by multiple parameters such as adsorption and particle interactions. Hence, the first part examines the interaction between polycarboxylate ether (PCE) and synthesized clinker phases and hydration products as model systems with regard to early hydration products.
Spec2Seq
(2018)
Unter der zyklischen R-Kurve versteht man die Abhängigkeit des Schwellenwertes gegen Ermüdungsrissausbreitung von der Risstiefe im Kurzrissbereich. Bei Spannungsverhältnissen R = omin/omax < ca. 0,7 erhöht sich der Schwellenwert AKltl ausgehend von einer intrinsischen, werkstoffspezifischen Untergrenze mit zunehmender Risstiefe, bis er einen risslängenunabhängigen Wert erreicht.
Ursache ist der graduelle Aufbau unterschiedlicher Rissschließeffekte. Die besondere Bedeutung des Kurzrisswachtums allgemein und der zyklischen R-Kurve speziell besteht darin, dass sie ein physikalisches Bindeglied zwischen der konventionellen Schwingfestigkeit (Wöhlerkurve) und der Bruchmechanik repräsentieren. Der Beitrag befasst sich sowohl mit der experimentellen Ermittlung der zyklischen R-Kurve als auch mit ihrer Anwendung auf Rissarrest im Zusammenhang mit Schwingfestigkeitsbetrachtungen.
Die experimentelle Ermittlung der zyklischen R-Kurve erfordert einen experimentellen Aufwand, der deutlich über den der Langrissbruchmechanik hinausgeht. Insbesondere im Anfangsbereich ist eine sehr genaue Messung der Risstiefe erforderlich, was eine Verbesserung etwa der konventionellen Potentialmethode erforderlich macht. Von wesentlicher Bedeutung ist auch, dass der Ausgangsriss vor
Beginn des eigentlichen Versuchs keine Rissschließeffekte gesehen haben darf. Realisiert wird das durch eine vorgeschaltete Phase von sog. „Compression Pre-cracking“, d.h. durch Anschwingen komplett im Druckbereich.
Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic[1], metal-organic[2], and inorganic[3] compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms remain often unclear. In the last years, have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy.[4] Here, we present an in situ coupling of synchrotron XRD, Raman spectroscopy, and thermography allowing the observation of mechanochemical reactions in real time.[5] Information on the crystalline, molecular, and temperature state of the materials during grinding could be collected. The chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. Furthermore, the presented setup allows the detection of crystalline, amorphous, eutectic as well as liquid intermediates. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses.
The methods of computational damage mechanics are well-established for the description of degradation of materials under monotone loading. An extension to structural damage induced by cyclic loading is however significantly limited. This is due to enormous computational costs required to resolve each load cycle by conventional temporal incremental integration schemes while a typical fatigue loading history comprises between thousands and millions of cycles. Despite the permanent increase of computational resources and algorithmic performance, a successful approach is rather based on the development of novel multiscale in time integration schemes.
A Fourier transformation-based temporal integration (FTTI) is represented, which takes advantage of temporal scale separation incorporated into the cycle jump method. The response fields are approximated by a Fourier series whose coefficients undergo the evolution on a long-time scale. This is correlated with the evolution of the history variables, including damage, by means of the adaptive cycle jump method of various orders. The necessary extrapolation rates are obtained from the underlying solution of a short-time scale problem, which results from the oscillatory boundary condition and fulfills the global equilibrium of the Fourier coefficients. In this way, a remarkable speedup is achieved because the number of cycles to be fully integrated dramatically decreases.
The key idea behind the FTTI method is that the global in space equilibrium problem is linear since it is decoupled from the evolution equations. The latter are solved in the quadrature points under response fields prescribed throughout the whole load cycle. Consequently, integration of a single load cycle is much more efficient than the conventional single scale integration where the global equilibrium iteration and the local iteration of the evolution equations are coupled. This results in an additional speedup of the FTTI method.
The performance of the FTTI technique is demonstrated for two different constitutive behaviors: a viscoplastic model with a damage variable governed by the local equivalent viscoplastic strain; a quasi-brittle response where the damage variable is driven by a non-local equivalent strain. The latter is implicitly introduced as proposed by Peerlings. Both, the explicit and implicit extrapolation schemes are validated. The FTTI solutions agree very well with the reference cycle-by -cycle solutions, while significantly reducing the computational costs. The adaptive determination of the jump length can properly recognize the particular responses throughout the fatigue loading history (stationary fatigue, acceleration of fatigue damage when approaching failure) as well as stress redistribution phenomena.
Mechanochemistry is increasingly used for synthesizing various materials including metal organic compounds and cocrystals. Although this synthesis approach offers a fast and pure synthesis in high yields, there is a lack in understanding the mechanisms of milling reactions. The necessary data can only be obtained in in situ experiments, which were only recently established for milling reactions. Herein, we present a novel setup enabling a combined in situ investigation of mechanochemical reactions using synchrotron XRD and Raman spectroscopy.
Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. The exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades due to their structural diversity. We synthesized manganese phosphonates in milling reactions. The mechanochemical reactions were investigated in situ to reveal the underlying mechanisms.
Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic[1], metal-organic[2], and inorganic[3] compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms remain often unclear. In the last years, have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy.[4] Here, we present an in situ coupling of synchrotron XRD, Raman spectroscopy, and thermography allowing the observation of mechanochemical reactions in real time.[5] Information on the crystalline, molecular, and temperature state of the materials during grinding could be collected. The chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. Furthermore, the presented setup allows the detection of crystalline, amorphous, eutectic as well as liquid intermediates. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses.
The exploration of metal phosphonates chemistry has gained great interest during the last decades, because of their structural diversity. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reactions (OER).
Here, we present the in situ investigation of mechanochemical syntheses of different manganese phosphonates by synchrotron X-ray diffraction. Nitrilotri(methylenephosphonic acid) and N,N-Bis(phosphonomethyl)glycine were chosen as ligands. The liquid-assisted milling process can be divided into three steps, including an amorphous stage. One of the products has not been obtained by classical solution chemistry before.
These metal phosphonates and/or their derivatives are considered to be active in electrochemical energy conversion. The verification of their applicability is one of the topics of our resent research.
Mechanochemistry is known for short reaction times, nearly quantitative conversions, and decreasing amount of solvents. Among organic syntheses, the Knoevenagel condensation is an important C-C bond forming reaction. We investigated the reaction of benzaldehyde derivates (nitro- and fluoro-derivates) with malononitrile syntheses by a combination of different in situ investigation techniques.
Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. By milling the reactants, various organic, inorganic, and metal-organic compounds can be obtained in high yields. Although mechanochemistry is widely used, the underlying mechanisms are not fully understood making mechanochemical reactions difficult to predict. Metal phosphonates are metal-organic compounds accessible by grinding. Because of their structural diversity, the exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reaction (OER). Here, we present the in situ investigation of the mechanochemical synthesis of a manganese(II)-phosphonate by synchrotron X-ray diffraction and thermography. The product has not been obtained by classical solution chemistry before and its crystal structure was determined from PXRD data. The milling process can be divided into different steps, with the product crystallization corresponding with the highest temperature rise. The activity of this metal phosphonate towards OER was measured and is presented here.
A constitutive model for the mechanical behaviour of single crystal Ni-base superalloys under high temperature conditions has been developed in the framework of a Cooretec project in cooperation with Siemens AG, MTU Aero Engines AG and University Bayreuth. In addition to the conventional material properties e.g. elastic constants, the model requires the parameters of the initial microstructure as an input. Thus, the γ’-precipitate size and the channel width of the γ-matrix were obtained from SEM micrographs. The model uses the slip system theory and describes the movement, multiplication and annihilation of dislocations in the channels. Furthermore, the cutting of precipitates is another mechanism contributing to the plastic flow. The evolution of the morphology due to rafting and its effects on the deformation have been implemented according to. The kinematic hardening is introduced as a stress tensor to realistically represent the strain hardening of arbitrary oriented single crystals.
The mechanical behaviour of single crystal specimens has been experimentally investigated in tension tests at different strain rates and in creep tests under various loads. The constitutive model has been calibrated based on the experimental data for temperatures of 950°C and 850°C and the [001] and [111] crystallographic orientations.
Finally, a micromechanical model was created to simulate the creep response of additive manufactured polycrystalline structures. An EBSD image is taken to obtain the grain geometry and their respective orientation. The grain boundaries are discretised using cohesive elements, whereas the single crystal model was applied to each grain in the representative volume. The polycrystal model is generated using Dream3D, NetGen and other software previously developed at the BAM.
In this contribution we describe an in-situ study of the crystallization of simvastatin in three solvents. The studies were carried out by solvent evaporation at the µSpot beamline using acoustically levitated solution droplets in combination with simultaneous X-ray diffraction, Raman spectroscopy, and imaging analysis.
Die Verwendung von Low Transformation Temperature (LTT) Schweißzusatzwerkstoffen ist eine innovative Möglichkeit, um beim Schweißen von hochfesten Stählen die schweißbedingten Zugeigenspannungen zu reduzieren. Durch die Zugabe von Legierungselementen, wie beispielsweise Nickel oder Mangan haben diese Werkstoffe eine, im Vergleich zu herkömm-lichen Schweißzusatzwerkstoffen deutlich herabgesetzte Martensitstarttemperatur (MS). Dadurch ist es möglich, die schweißbedingten Zugeigenspannungen mit LTT-Schweißzusatz-werkstoffen gezielt zu reduzieren oder sogar Druckeigenspannungen zu erzeugen.
Im Verlauf vorangegangener Arbeiten hat sich herausgestellt, dass einige der untersuchten LTT-Legierungen aufgrund ihres Erstarrungs- bzw. Seigerungsverhaltens eine gegenüber vielen konventionellen Schweiß-zusatzwerkstoffen erhöhte Heißrisssensibilität aufweisen.
Die aktuellen Arbeiten zielen darauf, die Heißrissneigung neuartiger LTT-Schweißzusatzwerkstoffe weiter zu ergründen.
Die chemische Zusammensetzung der Schweißnaht und WEZ haben einen wesentlichen Einfluss auf die Schweißnahtqualität. Aktuelle Prüfmethoden für Schweißnähte können post factum messen und die Schweißfehler nicht verhindern.
Das Abbrandverhalten kann über die Erstarrung wesentlichen Einfluss haben und zu Versprödung oder Rissbildung führen. Die in situ Überwachung der chemischen Zusammensetzung der Schweißnähte gewährleistet eine kontrollierte Verfestigung und Beständigkeit gegen Schweißfehler. Ein in situ Schweißnahtprüfverfahren mittels LIBS wurde entwickelt.
Long Term Temperature and Humidity Evolution Forecast in Near Field of Nuclear Waste Container
(2018)
The paper aims to simulate the corrosion environment of nuclear waste containers at different geological disposal periods to obtain temperature and humidity information at the interface between the container and the surrounding environment. The simulated data and calculation results of long term temperature evolution at the surface of nuclear waste (HLW) containers from some typical nuclear countries about the safety disposition were reviewed. Combining different burial patterns, this paper speculated the long term temperature evolution rule for China. According to the study about saturation variation of buffer/backfill material at home and abroad, the humidity evolution of bentonite at the surface of HLW containers was specu- lated. The study showed that the temperature of the container surface increased rapidly at the beginning, and gradually decreased after the climax. For safety reasons, the maximum temperature was designed below 100°C. The saturation of bentonite was af- fected by the mutual influences of the heat released by nuclear waste decay and the infiltration of groundwater. It was dominated by the released heat in the early stage, and later was influenced greatly by the infiltration of groundwater. It is generally believed that the water content at the surface of the container will increase obviously in about 3 years, and will be saturated in about 10 years. The prediction of long-term temperature and humidity evolution will lay a foundation for study of corrosion evolution of nuclear waste containers in China.
Surface environment changes of nuclear waste container, mainly including oxygen contents, buffer pore water components and pH under the conditions of “borehole” type and “In-floor” type with bentonite buffer/backfill and concrete buffer were summarized. This summarization provides a basic corrosion environment reference for the corrosion evolution re- search of high-level radioactive waste disposal repository in our country.
Elektro"älter"geräte
(2018)
Die warmfeste austenitische Gusseisenlegierung EN-GJSA-XNiSiCr35-5-2 (häufig auch als Ni-Resist D-5S bezeichnet) wurde hinsichtlich ihres mechanischen Verhaltens bei hoher Temperatur charakterisiert. Dazu wurden (isotherme) niederzyklische (LCF-) und (nicht-isotherme) thermomechanische Ermüdungsversuche (TMF) zwischen Raumtemperatur und 900 °C durchgeführt. Diese Ergebnisse dienten (zusammen mit weiteren Versuchsdaten) der Kalibrierung werkstoffmechanischer Modelle. Bei den höchsten Prüftemperaturen wurde Schädigung in Form von Kriechen beobachtet und metallographisch dokumentiert.
: Simvastatin is one of the most widely used active pharmaceutical ingredients for the treatment of hyperlipidemias. Because the compound is employed as a solid in drug formulations, particular attention should be given to the characterization of different polymorphs, their stability domains, and the nature of the phase transitions that relate them. In this work, the phase transitions delimiting the stability domains of three previously reported simvastatin forms were investigated from structural, energetics, and dynamical points of view based on single crystal X-ray diffraction (SCXRD), hot stage microscopy (HSM), and differential scanning calorimetry (DSC) experiments (conventional scans and heat capacity measurements), complemented with molecular dynamics (MD) simulations. Previous assignments of the crystal forms were confirmed by SCXRD: forms I and II were found to be orthorhombic (P212121, Z′/Z = 1/4) and form III was monoclinic (P21, Z′/Z = 2/4). The obtained results further indicated that (i) the transitions between different forms are observed at 235.9 ± 0.1 K (form III → form II) and at 275.2 ± 0.2 K (form II → form I) in DSC runs carried out at 10 K min−1 and close to these values when other types of techniques are used (e.g., HSM). (ii) They are enantiotropic (i.e., there is a transition temperature relating the two phases before fusion at which the stability order is reversed), fast, reversible, with very little hysteresis between heating and cooling modes, and occur under single crystal to single crystal conditions. (iii) A nucleation and growth mechanism seems to be followed since HSM experiments on single crystals evidenced the propagation of an interface, accompanied by a change of birefringence and crystal contraction or expansion (more subtle in the case of form III → form II), when the phase transitions are triggered. (iv) Consistent with the reversible and small hysteresis nature of the phase transitions, the SCXRD results indicated that the molecular packing is very similar in all forms and the main structural differences are associated with conformational changes of the “ester tail”. (v) The MD simulations further suggested that the tail is essentially “frozen” in two conformations below the III → II transition temperature, becomes progressively less hindered throughout the stability domain of form II, and acquires a large conformational freedom above the II → I transition. Finally, the fact that these transitions were found to be fast and reversible suggests that polymorphism is unlikely to be a problem for pharmaceutical formulations employing crystalline simvastatin because, if present, the III and II forms will readily convert to form I at ambient temperature.
Das polnische Bergbauinstitut GIG richtet alle zwei Jahre eine Fachtagung mit dem Thema „Sicherheit bei Sprengarbeiten“ im kleinen Bergstädtchen Ustroń (Polen) aus. Die Tagung hat eine internationale Ausrichtung und bietet Vorträge und Themen sowohl in englischer als auch polnischer Sprache. Es werden Ergebnisse anwendungsorientierter Forschung sowie aus der Praxis der Sprengarbeit vorgestellt. Teilnehmer und Beiträge kommen sowohl von großen Bergbaubetrieben und in Polen tätigen Herstellern als auch von Instituten und Behörden. Im Jahr 2018 war auch die BAM vertreten und der Autor möchte hiermit von den vielfältigen Themen berichten. Es gibt eine gewisse Ähnlichkeit zu der jährlich in Siegen stattfindenden „Informationstagung Sprengtechnik“ des Deutschen Sprengverbandes, wobei bisher wenig inhaltlicher Austausch stattfindet.
The basics of broadband dielectric spectroscopy were introduced in detail. The analysis of the data was discussed. As application of broadband dielectric spectroscopy the alpha-relaxation (dynamic glass transition) and the chain dynamics of polymers were ilustrated. Further the application of dielectric spectroscopy to polymerbased nanocomposites and high preformance polymers was discussed in detail.