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Nanotechnology at BAM
(2017)
Several Additive Manufacturing (AM) processes are based on the deposition of a powder to form a powder bed layer-by-layer, which typically has a low packing density (35-50%) and consequently hinders the ability of sintering ceramic parts to full density.
The layerwise slurry deposition (LSD) is an innovative process for the deposition of layers in AM. In the LSD, a slurry with no or small organic content is repetitively spread as thin layers on each other by means of a doctor blade. During the deposition, the ceramic particles settle to form thin layers with a high packing density (55-60%). When coupled with a printing head or with a laser, the LSD enables novel AM technologies inspired to the 3D printing or selective laser sintering, but taking advantage of having a highly dense powder-bed.
The LSD combined with inkjet binder printing (LSD-print) was applied to a submicron Al2O3 powder to produce samples which had a comparable density to uniaxially pressed samples, both in the green and in the sintered state.
The layer-wise slurry deposition (LSD) is an innovative process for the deposition of powder layers with a high packing density for Additive Manufacturing (AM). A slurry with small organic content is repetitively spread as thin layers on top of each other by means of a doctor blade. During the deposition, the ceramic particles settle to form thin layers with a high packing density (55-60%). Each layer is then dried, resulting in the stacking of a dry powder bed with high powder packing. When coupled with a printing head or with a laser source, the LSD enables novel AM technologies inspired to the 3D printing or selective laser sintering, but taking advantage of having a highly dense powder bed.
The LSD -3D printing, in particular, offers the potential of producing large (> 100 mm) and high quality ceramic parts, with microstructure and properties similar to traditional processing.
This presentation will give an overview of the milestones in the development of this technology, with focus on the latest results applied both to silicate and to technical ceramics.
Im Bereich der optisch angeregten Thermografie haben sich Blitzlampen (impulsförmig-flächige Erwärmung) und Halogenlampen (moduliert-flächige Erwärmung) für die spezifischen Regime Impuls- und Lockin-Thermografie etabliert.
Mittels eines rasternden fokussierten Lasers wird die Flying-spot Laserthermografie z.B. zur Risserkennung (Dauerstrichbetrieb) und die photothermische Materialcharakterisierung (hochfrequent moduliert)implementiert. Durch die Verfügbarkeit neuer Technologien (schnelle und hochauflösende IR-Kameras, brillante innovativer Lichtquellen und performante Datenakquisitions- und Verarbeitungstechnik) wird ein Paradigmenwechsel von den getrennt voneinander stehenden photothermischen und thermografischen Techniken hin zu einer einheitlichen quantitativen Mess-und Prüftechnik ermöglicht, die schneller und präziser ist. Ähnlich wie ein LED-Array, jedoch mit einer um zwei Größenordnungen höheren Bestrahlungsstärke, steht jetzt eine neuartige brillante Laserquelle, das VCSEL-Array (vertical-cavity surface-emitting laser) zur Verfügung, welches die starke Beschränkung der zeitlichen Dynamik der etablierten Lichtquellen aufhebt und gleichzeitig spektral sauber von der Detektionswellenlänge getrennt ist. Es vereint somit das schnelle zeitliche Verhalten eines Diodenlasers mit der hohen optischen Bestrahlungsstärke und dem großen Beleuchtungsbereich von Blitzlampen. Darüber hinaus kann die Erwärmung auch strukturiert vorgenommen werden, da einzelne Bereiche des VCSEL-Arrays unabhängig voneinander angesteuert werden können. Dieser neue Freiheitsgrad ermöglicht die Entwicklung ganz neuer thermografischer ZfP-Verfahren.
In der Vergangenheit wurde immer wieder diskutiert, ob die Porenhalsverteilung poröser silikatischer Medien maßgeblich die Relaxationszeit in Messergebnissen der Spektralen Induzierten Polarisation (SIP) bestimmt und dementsprechend auch neuere Ansätze, Porenweitenverteilungen aus diesen Daten abzuleiten, zuverlässig sein können. Systematische Studien an Gesteinen mit sehr unterschiedlichen Porenverteilungen zeigten, dass in Materialien mit engen Porenhälsen (z.B. < 5 μm) vor allem oder zusätzlich zum vermuteten Porenhalspeak niederfrequente Relaxationen zu beobachten sind, deren Ursache noch unklar ist.
Unter Einbeziehung der Methoden Röntgen-Computertomografie (μ-CT), Quecksilberporosimetrie (MIP), Stickstoffabsortion, Nukleare Magnetische Resonanz, SIP und Auflichtmikroskopie untersuchen wir den Porenraum hinsichtlich der Parameter Porosität, Permeabilität und innere Oberfläche und bestimmen die geometrischen Eigenschaften wie Porenweitenverteilungen oder fraktale Dimension durch verschiedene Algorithmen. Dabei ist zu berücksichtigen, dass sich die Methoden hinsichtlich der Grenzen ihres Auflösungsvermögens unterscheiden. Mit einer Zusammenführung der Ergebnisse aller Methoden kann eine mehrere Längenskalen überdeckende Charakterisierung der Porenraumgeometrie erfolgen.
Die Anwendung und Auswertung der verschiedenen Methoden werden am Beispiel von Baumberger Kalksandstein und Bentheimer Sandstein verglichen und diskutiert.
If fracture mechanics shall be applied to the total lifetime respectively the fatigue limit of components (within the meaning of the S-N curve approach) it has to address four challenges:
(a) It has to adequately describe so-called short crack propagation, which cannot be based on the common long crack concepts for principle reasons. Since the crack size is in the order of the plastic zone size, the modelling of short crack propagation cannot be based on the common linear elastic Delta K concept. Instead, an elastic-plastic parameter such as the cyclic J integral has to be applied. A second point is that the crack closure concept has to be modified in that the crack opening stress is not a constant, crack size- independent parameter but shows a transient behaviour with increasing short crack size.
(b) It has to provide a meaningful definition of the initial crack dimensions as the starting point for an S-N curve relevant (residual) lifetime analysis. This can be based either on the (statistical) size of material defects which can be treated as cracks or by the size of the crack which would arrest subsequent to early crack propagation, whatever is larger.
(c) It has to cope with the problem of multiple cracks for load levels higher than the fatigue limit such as it occurs in many applications in the absence of very large initial defects.
(d) This requires consequent statistical treatment taking into account variations in the local geometry of the area where crack initiation has to be expected as well as the scatter in the initial crack size and in the material data used for the analyses.
Damage development and damage tolerance of structures manufactured by selective laser melting
(2017)
The additive manufacturing technology of Selective Laser Melting (SLM) experiences a rapid development within an increasing marked of quite different application fields. The properties of SLM materials and structures are influenced by a number of tech-nological parameters such as the metal powder (particle size, homogeneity, cleanliness), the laser tool (power, beam diameter, pulse lengths), the scanning operation (speed, sequence and orientation of melting paths), parameters of the over-all equipment (design and preheating of the base plate, currents and turbulence in the protective gas atmosphere) and, last not least, the hatching strategy including the build-up direction of the structure with respect to the loading direction of the component.
For the perspective use of SLM structures as load carrying, safety-relevant components the knowledge of their mechanical properties is necessary. It is essential to understand these in the context of the manufacturing-related features and at the back-ground of the basic characteristics of metallic materials: crystal lattice, microstructure and material defects. The paper provides an overview on factors which affect the mechanical parameters stiffness, strength, ductility, toughness, fatigue crack propagation and fatigue strength in the context of selective laser melting.
The paper provides an overview on the results of a German cluster project on the use of fracture mechanics to the determination of the fatigue strength of weldments with fatigue cracks originating at the weld toes. The approach includes (a) a concept for short crack propagation for which the common K concept is not applicable and the crack closure effects are still being gradually build-up, (b) a method for determining fatigue life relevant initial crack sizes as they are needed in any fracture mechanics analysis and (c) multiple cracking and crack coalescence at load levels higher than the endurance limit. The analyses are stochastically performed. Both, the endurance limit as defined for 107 loading cycles and the finite life branch of the S-N curve are determined.
Besides a brief introduction into the approach, a wide range of validation examples is presented. These comprise different weldment types (butt welds, cross joints and longitudinal stiffened plates), two steels of quite different strengths, different weld geometries due to different welding techniques (TIG, MAG), as-welded and stress relieved welds and different stress ratios varying from R = -1 to R = 0.5.
Um bruchmechanisch Schwingfestigkeiten ermitteln zu können, sind einige Voraussetzungen erforderlich:
(a) Das Wachstum sowohl langer als auch mechanisch und physikalisch kurzer Risse muss adäquat beschrieben werden. Das erfordert die Anwendung elastisch plastischer Konzepte zur Beschreibung der zyklischen Rissspitzenbeanspruchung sowie die Modellierung des graduellen Aufbaus der Rissschließeffekte im Kurzrissbereich.
(b) Es müssen physikalisch sinnvolle Ausgangsrissgrößen für die bruchmechanische Analyse bestimmt werden.
(c) Bei Spannungen oberhalb der Dauerfestigkeit respektive der Versagensspannung bei 107 Lastwechseln muss gegebenenfalls Mehrfachrisswachstum berücksichtigt werden. Der Vortrag diskutiert diese Punkte und zeigt Lösungswege auf.
The presentation provides a brief overview on results obtained in the context of fracture mechanics based flaw assessment particularly in the context of short crack propagation. Background is the planned updating of international fitness-for-service procedures such as BS 7910. Specific topics addressed are the determination of the cyclic elastic-plastic crack driving force, the description of the gradual build-up of the crack closure phenomenon at the short crack stage, cyclic R curve analysis and residual stresses.
Der Vortrag bietet eine Übersicht über die im Rahmen des IBESS-Projektes entwickelte Methodik zur bruchmechanischen Ermittlung der Schwingfestigkeit von Schweißverbindungen. Schwerpunkte sind die Beschreibung des Wachstums kurzer Risse, die mit den klassischen linear-elastischen Bruchmechanik-Konzepten nicht möglich ist, die Ermittlung einer physikalisch sinnvollen Ausgangsrissgröße für das Bruchmechanik-Modell, die Ermittlung der Bauteildauerfestigkeit und des Zeitfestigkeitsastes diverser Schweißnahtgeometrien und eine Diskussion der Eigenspannungsproblematik. Die Ergebnisse werden mittels Validierungsbespielen illustriert.
Polymeric membranes represent a cost- and energy efficient solution for gas separation. Recently superglassy polymers with high free volume outperform many conventional dense polymers in terms of gas permeability and selectivity. However, such materials with a high fractional free volume (FFV) are prone to pronounced physical aging. The initial microporous structures approach a denser state via local chain rearrangements which results in a dramatic reduction in the gas permeability. For the first time, dielectric spectroscopy with state-of-the-art high-resolution analyzers was employed to investigate the molecular mobility and physical aging of two representative groups of superglassy polymers: PIMs (PIM-1 & PIM-EA-TB) and Si-containing polynobornenes (PTCNSi1 & PTCNSi2). The dielectric behavior of the solution-cast polymeric films was measured by isothermal frequency scans during the different heating cycles in a broad temperature range. Structural relaxation of the films was observed during the measurements. Multiple dielectric processes following Arrhenius behavior were observed for all the investigated polymers. Moreover, they all showed conductivity in the glassy state. The significant increase in the conductivity with increasing temperature especially for PIMs is explained in terms of the formation of local intermolecular agglomerated structures due to interaction of π-electrons in aromatic moieties of the polymer backbone.
Thermal and dynamic glass transition of ultrathin films of homopolymers and a miscible polymer blend
(2017)
Despite the decade long controversial discussion on the effect of nanometer confinement on the glass transition temperature (Tg) of ultrathin polymer films, there is still no consistent picture. Here, the dynamic calorimetric glass transition of ultrathin films of a blend, which is miscible in the bulk, is directly investigated by specific heat spectroscopy. By a self-assembling process, a nanometer thick surface layer with a higher molecular mobility is formed at the polymer/air interface. By measuring the dynamic calorimetric Tg in dependence on the film thickness, it was shown that the Tg of the whole film was strongly influenced by that nanometer thick surface layer, with a lower Tg. Since the observed thickness dependence of the dynamic Tg is similar to the thickness dependence of the Tg for thin films of homopolymers, it is concluded that also for homopolymer a highly mobile surface layer is relevant for the widely observed Tg depression.
Super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP) or polymers with intrinsic microporosity (PIMs) play an important role in the current development of membrane materials for gas separation because of their high permeability and selectivity. Unfortunately, such materials which have a high fractional free volume (FFV) are prone to pronounced physical aging. The initial microporous structures approach a more dense state via local chain rearrangements which results in a dramatic reduction in the gas permeability. For the first time, broadband dielectric spectroscopy was employed to investigate the molecular dynamics of two representative groups of super glassy polymers: PIMs (PIM-1 & PIM-EA-TB) and Si-containing polynobornenes (PTCNSi1 & PTCNSi2). The dielectric behavior of the solution-cast polymeric films was measured by isothermal frequency scans during the different heating cycles in a broad temperature range. Structural relaxation of the films was observed during the measurements. Molecular relaxation processes following Arrhenius behavior with unusually high activation energies were observed for all the investigated polymers. The PIMs showed furthermore a significant conductivity in the glassy state which is explained with the formation of local intermolecular agglomerated structures due to interaction of π-electrons in aromatic moieties of the polymer backbone.
Discotic liquid crystals (DLCs) are a promising class of soft matter for electronic applications. This is due to their ability to organize and stack themselves into columns in a hexagonal columnar mesophase, driven by the overlapping of the π orbitals of their aromatic core. This leads to a high charge-carrier mobility along the column axis. Previous studies on DLCs showed that their properties, such as phase transition temperatures and enthalpies, are susceptible to nanoconfinement. In this study, 2,3,6,7,10,11 hexakis[hexyloxy] triphenylene (HAT6), a triphenylene based DLC, was confined into parallel aligned cylindrical nanopores of anodic aluminum oxide (AAO) membranes by melt infiltration in the isotropic phase under an argon atmosphere. Furthermore, the pore surfaces of a series of membranes were chemically modified, resulting in a more hydrophobic pore surface than the unmodified ones. The structure, dynamics, and the phase behavior of HAT6 confined into modified and unmodfied nanopores of AAO were investigated by broadband dielectric spectroscopy and differential scanning calorimetry. Results will be discussed in detail.
Discotic liquid crystals (DLCs) are a promising class of soft matter for electronic applications. This is due to their ability to organize and stack themselves into columns in a hexagonal columnar mesophase, a mesophase in between the plastic crystalline and isotropic phase, driven by the overlap of the π orbitals of their aromatic core. This leads to a high charge-carrier mobility along the column axis. Further, these columns could then be considered as “molecular nanowires”.
Spatial confinement of soft matter in nanoporous media influences its structure, thermodynamic properties, and mobility. Embedding liquid crystals and polymers into nanopores of anodic aluminum oxide (AAO) results in a 2D nanoconfinement of these materials. This confinement affects their properties, compared to the bulk, such as phase transition temperatures and enthalpies, molecular mobility, and architecture of the crystallization.
In this study, 2,3,6,7,10,11 hexakis[hexyloxy] triphenylene (HAT6), a triphenylene-based DLC, was confined into nanoporous AAO membranes. The structure, dynamics and the phase behavior of the confined HAT6 were investigated by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). HAT6 was embedded into nanoporous AAO membranes by melt infiltration in the isotropic phase under argon atmosphere. The membranes have parallel aligned cylindrical nanopores, with different pore diameters in the range of 10-180 nm. Bulk HAT6 forms a hexagonal columnar phase; in between the isotropic phase above 371 K and the plastic crystalline phase below 340 K. Unlike the bulk, the confined HAT6 split the phase transitions in two or more, which might be interpret as different phase structures; close to the wall and at the pore center. Moreover, the phase transitions of the confined HAT6 shifted, with decreasing pore diameter, to lower temperatures. The dependencies of the phase transition temperatures on the pore size was well-described by the Landau-de Gennes model. Furthermore, pore surfaces of a series of membranes were chemically modified, resulting in a more hydrophobic pore surface than the unmodified ones. HAT6 was embedded into the modified membranes by the same aforementioned preparation. The influence of the changed host-guest-interaction, on the structure, dynamics, and the phase behavior of HAT6 confined in the modified membranes, was also investigated by BDS and DSC.
In this study, the molecular dynamics of two linear-shaped tetramethylated guanidinium triflates ionic liquid crystals were investigated by a combination of Broadband Dielectric Spectroscopy (BDS) and Specific Heat Spectroscopy (SHS). Three processes were detected by BDS; at low temperature γ-process, at higher temperatures α-process and at even higher temperatures conductivity. The γ-process indicates localized fluctuations, and the α-process designates cooperative fluctuations. Slightly different restrictions were found for conductivity processes of LC536 and LC537 due to the slightly different lengths of alky chains. Furthermore, the cooperative dynamics were also probed by SHS. The cooperative dynamics probed by the different techniques (BDS and SHS) compared, and assigned to the different restrictions on the cooperativity due to the difference in the sensitivity of the techniques.
Trends in fluorometry and fluorescence imaging are increasing applications of molecular and nanoscale reporters with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, bioimaging, and safety barcodes. Mandatory for the comparison of different emitter classes and the rational design of the next generation of reporters for the short wavelength infrared (SWIR) region are reliable and quantitative photoluminescence measurements in this challenging wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as lanthanide-based upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable photoluminescence quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Such measurements are currently hampered by the lack of suitable methods and standards for instrument calibration and validation and quantum yield standards with emission > 800 nm and especially > 1000 nm.
In this respect, we present the design of integrating sphere setups for absolute and excitation power density-dependent measurements of emission spectra and photoluminescence quantum yields in the wavelength region of 650 to 1650 nm including calibration strategies and first candidates for potential fluorescence standards. Subsequently, selected examples for spectroscopic studies of different types of nanocrystals are presented including the upconversion and downconversion emission of differently sized and surface functionalized lanthanide-doped nanoparticles
Niobium-titanium carbide cermets with nickel binder have been prepared by colloidal processing in water without a milling step by using Poly-diallyl-dimethyl-ammonium chloride (Poly-DADMAC) as a dispersant. Homogeneous microstructures with relative densities larger than 99% of the theoretical density have been achieved by gas pressure sintering in argon atmosphere. However, mechanical properties like hardness and strength were slightly decreased due to precipitation of free carbon.
Microbiologically influenced corrosion (MIC) on steel occurs where the presence and activity of microbes change the localized conditions on the surface of a metal substrate. For instance, metal reducing bacteria (MRB) are capable of utilizing metal compounds in the passive layer on stainless steel as electron acceptors during their metabolism. This weakening of the passive film not only leads to an acceleration of the general corrosion processes, but also increases the susceptibility of stainless steels to pitting corrosion. Even though the electron transfer mechanisms are not yet fully understood, recent research shows that the secretion of electron shuttles like flavins contribute significantly to the extracellular electron transfer (EET). Electron shuttle molecules like riboflavin (RB) or flavin mononucleotide (FMN) are secreted by MRB after the transition from planktonic to sessile mode and exist in the biofilm at low concentrations. Therefore, they are precise early phase indicators of bacterial settlement.
This project aims at clarifying the electrochemical interaction mechanisms of MRB with stainless steel surfaces, with a special focus on the role of the extracellular redox molecules. The analysis of corrosion processes as a function of chloride and flavin concentration have been performed by means of electrochemical methods. Due to the differences in their chemical structure, FMN and RB have shown significant differences in terms of their adsorption behavior and the stability of the formed films, which directly influences the electron transfer processes. Therefore, Electrochemical Quartz Crystal Microbalance (eQCM) studies have been performed on sputtered FeCr electrodes to investigate the adsorption/desorption kinetics of flavins.
The results of electrochemical studies are complemented by the analysis of the changes in the passive film chemistry and the chemical composition of the adsorbed films by means of Fourier Transform Infrared Reflection Absorption Spectroscopy (FT-IRRAS) and X-ray photoelectron spectroscopy (XPS). Changes in surface morphology have been investigated by means of Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM).The presentation will summarize our results on the degradation mechanisms of passive films on stainless steel surfaces in the presence of flavins and provide useful insights from a fundamental aspect for the understanding of the initial stages of microbiologically influenced corrosion.
Metal reducing bacteria (MRB) are capable of utilizing different metals, such as iron, chromium, manganese or uranium as well as many organic compounds, as electron acceptors for their metabolism. Via direct and indirect electron transfer processes MRB are able to convert insoluble passive film species like Fe(III)-oxides to soluble Fe(II)-oxides and hydroxides. This weakening of the passive film not only leads to an acceleration of the general corrosion processes, but also increases the susceptibility of stainless steels to pitting corrosion. Electron transfer mechanisms are not yet fully understood and the role of bacteria in corrosion processes is controversially discussed in the literature. Moreover, recent research indicates that the secretion of electron shuttles like riboflavins by MRB also contributes to the extracellular electron transfer.
This project aims at clarifying the chemical and electrochemical interaction mechanisms of MRB with stainless steel surfaces. To investigate the changes in the oxide chemistry on the stainless steel surface in the presence of biomolecules and MRB a new flow cell has been designed and constructed which enables the collection of XANES (X-ray Absorption Near Edge Structure) spectra in fluorescence mode at the Fe K-edge and electrochemical analysis. Availability of oxygen and the pre-exposure of the MRB to Fe(III) during cultivation have been investigated as parameters with significant effect on the corrosion rates. XANES analysis is supplemented by ex-situ X-Ray Photoelectron Spectroscopy (XPS) and Fourier Transform Infrared Reflection Absorption Spectroscopy (FT-IRRAS) to complete the surface characterisation in terms of the oxide chemistry and the composition of organic residues. Complementary electrochemical quartz crystal microbalance (e-QCM) measurements have been performed to quantify the kinetics of bacterial attachment and biofilm formation. Together with the frequency shift, the evolution of the dissipation signal has been analyzed to investigate the changes in viscosity and structure of the biofilm from initial stages up to maturation. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) has been used to study the structure and viscoelastic properties of the biofilms after e-QCM experiments.
The presentation will summarize our results on the effects of individual surface and environment related parameters on the chemical/electrochemical interaction mechanisms of MRB leading to passive film degradation on stainless steel surfaces and provide useful insights from a fundamental aspect for the development of novel mitigation strategies for microbiologically influenced corrosion.
The interface of a metal substrate and a biofilm can differ significantly from the surrounding environment. Metal reducing bacteria (MRB), for instance, are capable of utilizing various metallic compounds as electron acceptors. Besides chromium, uranium and manganese as well as many organic compounds, Fe(III) is converted to the soluble form Fe(II) during the bacterial metabolism. This could lead to a weakening of the protective passivation layer on stainless steel and thereby facilitate microbiologically influenced corrosion (MIC). Even tough the processes of electron transfer are not yet entirely explained, the contribution of flavins and other humic substances as electron shuttles is widely discussed in the literature. Moreover, the adsorption of organic thin films on steel surfaces can lead to surface preconditioning and thus to changes in adhesion behavior of bacteria.
The aim of this work is to understand the chemical and electrochemical interaction mechanisms of MRB with steel surfaces by combining electrochemistry and surface-analytical techniques. The investigations primarily focus on the effect of pre-adsorbed thin organic films and self-assembled monolayers (SAMs) on the electron transfer processes between bacteria and steel surfaces. Electrochemical Quartz Crystal Microbalance (eQCM) studies have been performed to investigate the adsorption/desorption kinetics of organic films as well as the formation of biofilms on FeCr electrodes. Furthermore, the evolution of the biofilms on steel surfaces has been analyzed by means of electrochemical impedance spectroscopy (EIS) to support the QCM studies with information on structural changes during different stages of biofilm growth. Electron transfer and corrosion processes have been analyzed by means of square wave voltammetry (SWV) and linear sweep voltammetry (LSV), respectively. The results of electrochemical studies are complemented with microscopic and spectroscopic characterisation of organic adsorbates and analysis of changes in the passive film chemistry and surface morphology.
This presentation will summarize our results on the chemical and electrochemical interaction mechanisms of MRB on steel surfaces leading to passive film degradation. The role of flavins in accelerating corrosion processes will be elucidated in detail to provide useful insights from a fundamental aspect for the understanding of the initial stages of microbiologically influenced corrosion in the presence of MRB.
The differences between the binary phase diagrams W-C and Nb-C illuminate several parameters for tailoring the properties of NbC. In the region of homogeneity of NbCx, with Nb4C3 and Nb6C5 other Niobium carbide phases occur. Properties, like micro-hardness, hot hardness, sliding wear, elastic modules and toughness can be tailored by the C/Nb Ratio, secondary carbides and the type of binder. Supporting results from different grades with varying C/Nb ratio or binder types will be illuminated. Thus, the NbC system offers to producers a wider parameter window, than WC.
The wear rates of self-mated alumina couples show that friction as well as wear is largely determined by the above mentioned hydro-thermal conditions. The presence of water and its amount available in the surrounding system either in liquid or in gaseous form plays a key role for friction and wear behavior and can be beneficial for the tribological profile of steam degradation resistant materials. Hot steam enhances the tribo-chemical formations of oxides and hydroxides on MgO-ZrO2, alumina and antimony impregnated carbon.
Niobium is today largely available. The initial NbC grade was substoichiometric, SPS sintered and cobalt bonded. The NiMo-bonded stoichiometric NbC1.0 grades enable the substitution of cobalt by nickel, SPS by conventional sintering and NbC0.88 by NbC1.0 in view of functional properties. Nickel bonded NbC grades have improved toughnesses versus cobalt NbC grades, but lose hardness. NiMo and NiMo2C bonded NbC1.0 grades compensated the loss in hardness while keeping the toughness.
The frictional response of molybdenum bis(C11-14 branched and linear alkyl) carbamodithioate oxo thioxo complex (Mo-dttc) versus bismuth dimethyldithiocarbamate (Bi-dtc) and bismuth dodecylbenzene Sulfonate (Bi-ddbsa) slip-rolling under mixed/boundary lubrication (T=120°C, n=10 millions of cycles, P0max=2.25 GPa) in PAO-based formulation against three different steel alloys were compared.
The tribotesting categories have different scopes with associated "pros" and "cons" and results obtained in one category cannot be simply transferred to another. The impact of design overrules in general the influence of the metallurgy or materials choice. The "cheap" test methods aim pre-screening and assessment of basic properties as well as use mainly for the test specimens SAE E52100 (100Cr6, SUJ2) ball bearing steel and carbon steels. The main test geometries are ball-on-flat/(disk) or block-on-ring apart 4-ball geometry. The tribological test conditions. This enabled "dynamic" testing, where during a test the "critical" solicitations were repeatedly and freely passed.
The slip-rolling 2Disk tribometer from Optimol Instruments represented the technological evolution in tribotesting of the well-known AMSLER-type tribometer marketed in 1922. Both use two discs with the same outer diameter rolling against each other on their circumference. In the AMSLER, the lower disc dips into an oil reservoir, whereas in the 2Disk the oil is injected into the contact. The oil supply of the 2Disk is controlled by pump and temperature by a heat exchanger.
A study on metal sulphides in tribofilms of modelled brake wear debris under variable humidity
(2017)
Metal sulphides are needed in brake pad formulations in addition to graphite to compensate the influence of different environments. The sensitivity to humidity differs a lot for each single constituent. Only one component is not sufficient for stabilising the COF and it is also necessary to add more components than only one metal sulphide to graphite. Furthermore, a good mixing process inside the third body during braking is necessary to prevent formation of solid lubricant films which are detrimental for braking. Nevertheless, not every metal sulphide acts as a solid lubricant but most of them have the ability for stabilizing the friction coefficient.
A bottom-up approach to study metal sulphides in brake friction materials at higher temperatures
(2017)
The impact of metal sulphides in brake friction materials on the friction behaviour of disc brakes was studied at two different temperatures and in two different atmospheres using a pin-on-disc device with powder supply. Powder mixtures were prepared by using a bottom-up approach, where magnetite is the main component, in which different metal sulphides are mixed in. At 400 °C, the resulting coefficients of friction are higher in air than in nitrogen atmosphere, which can be attributed to the generation of metal oxides and were confirmed by doing thermal analysis.
Im Chemikalienrecht ergeben sich laufend Änderungen durch die regelmäßige Überarbeitung des UN-GHS. Konsequenzen hat dies auch für andere Vorschriften, die auf Einstufungen von gefährlichen Stoffen Bezug nehmen. In diesem Beitrag werden für die chemische Sicherheitstechnik wichtige aktuelle Änderungen im Chemikalienrecht und nationalen Arbeitsschutzvorschriften vorgestellt.
Wood-based materials are well-known sources for formaldehyde emission in the indoor environment. Different testing standards lead to different emission values for the materials. Such standards are compared in this study. Besides scenarios with varying loading factors, air exchange rates and climatic conditions were investigated to evaluate the formaldehyde emission potential of different building products.
Under realistic indoor conditions used for the emission chamber tests, exceeding of formaldehyde indoor guide values were obtained. Results showed the need for improvement of wood-based materials with lower formaldehyde emissions and the adaption of testing parameters closer to realistic conditions.
Fiber-reinforced-materials become increasingly being used, also in the range of safety-relevant components.(tail unit A380, pressure receptacles)
Failure criteria is widely unknown,when available it results from empirical data.
Every fiber-reinforced construction shows different properties according to its specific values.
This is due to the fact that the real material is produced whilst the process of construction –in difference to e.g. metals.
Die BAM-Liste - Anforderungen an Tanks für die Beförderung gefährlicher Güter – mit den Beständigkeitsbewertungen metallischer und polymerer Werkstoffe ist Grundlage für die stoffbezogenen Baumusterzulassungen für Tankcontainer und ortsbewegliche Tanks zur Beförderung gefährlicher Güter durch die BAM seit der Herausgabe der 1. Auflage 1989. Diese Beständigkeitsbewertungen werden nicht nur bundesweit, sondern weltweit als Erkenntnisquelle genutzt. Für die Zulassung von Kesselwagen und Tankfahrzeugen werden diese Daten auch herangezogen. Die Werkstoffbeständigkeitsdaten und der damit verbundene Informationsservice der BAM haben mit Sicherheit dazu beigetragen, Leckagen von Tanks aufgrund des Einsatzes von Tanks/Kesselwagen aus einem gegenüber dem Füllgut unbeständigem Tankwerkstoff oder Dichtungswerkstoff zu vermeiden.
The objective of this research was to determine the resistance of frequently used sealing materials such as EPDM, FKM, FVMQ, CR, CSM, IIR, NBR, PA, PUR and VMQ in aged biodiesel and heating oil B10 with 10 % biodiesel.
The mass, tensile strength, breaking elongation and Shore hardnesses of the test specimens were determined before and after exposure in non-aged, one-year, two-year, three-year and four-year aged biodiesel and B10 at 20 °C, 40 °C and 70 °C.
A threshold for the reduction in tensile properties and Shore hardness is not set in the international standards. Therefore, a threshold of 15 % was set for the evaluation of the compatibility. The decrease in tensile properties and Shore hardness increased with the age and the temperature of the biodiesel and the heating oil.
The age of the biodiesel was not relevant for the sealing materials CR, CSM, EPDM, IIR and NBR, which were generally not resistant to biodiesel and B10. FKM and PA showed high compatibility in non-aged and aged biodiesel. FVMQ and PA could be evaluated as resistant in non-aged and aged B10 at 20°C and 40°C, whereas FKM was resistant up to 70°C despite of the age of B10.
Changes in fuel composition and the introduction of alternative fuels often create problems of corrosion and degradation in materials. The objective of this research was to determine the corrosion behaviour of commercial metallic tank materials (unalloyed steels, austenitic CrNi- and CrNiMo-steels, aluminium and its alloys) in fuels and heating oil with admixtures of biogenic sources, such as gasoline with addition of ethanol (E10, E85), pure biodiesel and heating oil with 10 % biodiesel (B10).
Metallic tank materials were evaluated as resistant in a liquid if the annual corrosion rate due to uniform corrosion did not exceed 0.1 mm/year, and localized corrosion effects in the form of pitting corrosion, stress corrosion cracking and crevice corrosion did not occur.
The corrosion rates of the tank materials after exposure to E10, E85, non-aged and two-year aged pure biodiesel, and non-aged and one-year aged heating oil B10 for four weeks at 50 °C, according to DIN 50905/4, were well below the limit of 0.1 mm/year. For the unalloyed steels, the formation of rust was observed independently of the biofuels amount of ageing. U-bend specimens made of unalloyed steel were not damaged in form of stress corrosion cracking in all test fuels at this test temperature.
Ziel dieser Untersuchungen war die Bewertung der Beständigkeit häufig eingesetzter Dichtungswerkstoffe, wie Fluorkautschuk (FKM), Fluorsiliconkautschuk (FVMQ), Siliconkautschuk (VMQ), Ethylen-Propylen-Dien-Kautschuk (EPDM), Chloroprenkautschuk (CR), chlorsulfoniertes Polyethylen (CR), Butylkautschuk (IIR), Acrylnitril-Butadien-Kautschuk (NBR), Polyes-terurethankautschuk (PUR) und Polyamid (PA) in Kraftstoffen und Heizöl mit und ohne bioge-ne Zusätze bei 20 °C, 40 °C und 70 °C. E10 (Kraftstoff mit max. 10 % Ethanol), E85 (Kraftstoff mit 85 % Ethanol), Dieselkraftstoff mit max. 5 % Biodiesel, Super mit max. 5 % Ethanol, un-gealtertes und gealtertes B10 (Heizöl mit 10 % Biodiesel) sowie zum Vergleich reiner Dieselkraftstoff, Heizöl und Kraftstoff Super plus zählten zu den Testsubstanzen.
Masse, Zugfestigkeit und Bruchdehnung wurden von den Prüfkörpern vor und nach der 84-tägigen Auslagerung in den Kraftstoffen und Heizöl bestimmt. Die visuelle Begutachtung einiger Elastomerprüfkörper zeigte eindeutig die hohe Quellung bis zur partiellen Auflösung.
Die Shore-Härte A und D (für PA) der Prüfkörper wurden vor und nach der 42-tägigen Auslagerung in den Kraftstoffen bestimmt.
In den internationalen Normen wird zur Bewertung der Beständigkeit von Elastomeren kein Grenzwert der Reduzierung der Zugeigenschaften und der Shore-Härte definiert. Deshalb wurde für die Beständigkeitsbewertung ein Grenzwert von 15 % festgelegt. Zusammenfassend kann die Aussage getroffen werden, dass die Beständigkeit der Fluorpolymere FKM und FVMQ in den Kraftstoffen und Heizöl mit und ohne biogene Zusätze die beste ist.
Die BAM-Liste - Anforderungen an Tanks für die Beförderung gefährlicher Güter – mit den Beständigkeitsbewertungen metallischer und polymerer Werkstoffe ist Grundlage für die stoffbezogenen Baumusterzulassungen für Tankcontainer und ortsbewegliche Tanks zur Beförderung gefährlicher Güter durch die BAM seit der Herausgabe der 1. Auflage 1989. Diese Beständigkeitsbewertungen werden nicht nur bundesweit, sondern weltweit als Erkenntnisquelle genutzt. Für die Zulassung von Kesselwagen und Tankfahrzeugen werden diese Daten auch herangezogen. Die Werkstoffbeständigkeitsdaten und der damit verbundene Informationsservice der BAM haben mit Sicherheit dazu beigetragen, Leckagen von Tanks aufgrund des Einsatzes von Tanks/Kesselwagen aus einem gegenüber dem Füllgut unbeständigem Tankwerkstoff oder Dichtungswerkstoff zu vermeiden.
Seitens der Industrie besteht großes Interesse, Polyethylenterephthalat (PET) als Werkstoff für Verpackungen zum Transport von Gefahrgütern einzusetzen, da aufgrund der hohen Festigkeit und Steifigkeit von PET die Wanddicken und somit die Kosten der Verpackungen reduziert werden können. Die Prüfung der Spannungsrissbeständigkeit von Polyethylenformstoffen als Werkstoffe von Verpackungen erfolgt mit Labormethoden unter Verwendung einer Standardflüssigkeit als Prüfmedium für die Spannungsrisse auslösende Wirkung auf Polyethylen (PE), wodurch Zeit und Kosten der Prüfungen reduziert werden.
Ziel dieser Arbeit war es, eine Laborprüfmethode zum Vergleich der Spannungsrissbeständigkeit von PE und PET auf ihre Anwendbarkeit zu prüfen, wie z.B. den Full Notch Creep Test (FNCT). Es wurde untersucht, ob die Prüfkörper aus PE und PET mit umlaufender Kerbe in dieser durch die chemische Industrie entwickelten und von der BAM konzipierten Apparatur auf der Basis des FNCT zu messbaren Ergebnissen unter Einfluss eines Ölsäureamidethoxylates als Netzmittel bei 50 °C führen.
Die Testergebnisse bestätigten die Eignung des Prüfverfahrens für die acht eingesetzten Formstoffe aus PE. Dieses Prüfverfahren konnte nicht für PET angewandt werden, da die Prüfkörper aufgrund der hohen Festigkeit und Steifigkeit des PET beim Kerbvorgang zerbrachen. Die gleiche Aussage konnte für den Nachweis der der Spannungsrissbeständigkeit von Verpackungen, der in der BAM Gefahrgutregel BAM-GGR 015 beschrieben wird, getroffen werden. Die einzige Möglichkeit zum Nachweis der Spannungsrissbeständigkeit von PET besteht in der Durchführung von Stapeldruckprüfungen.
Plastic storage tanks for heating oil have been on the market since the early 1970s in Germany, mainly made from polyethylene grades. Tank manufacturers and experts examining the tanks recommend the replacement of the tanks to ensure the safety after a period of 30 years. The tank manufacturer is legally obliged to specify the service life of the tanks.
Polyethylene is subject to ageing by alteration of the properties during its life cycle. A distinction is made between internal and external ageing processes. The internal ageing, such as the breakdown of internal stresses, post-crystallization, phase sepa-ration of multicomponent systems and plasticizer migration is attributed to thermodynamically instable conditions of the plastic material. The external ageing in form of stress cracking, fatigue cracking, thermooxidative degradation or swelling is based on physical or chemical effects of the environment of the polyethylene grade. The degree of ageing and the nature of the degradation process mainly depend on the chemical degradation of the polyethylene, the wall thickness of the tank and the environmental conditions. There are no results available on the long-term behaviour of the polyethylene grades used as materials for heating oil storage tanks, especially after a service life of more than 25 years.
The aim of this investigation was the determination of the factual degree of damage in comparison to the uncontaminated polyethylene grades. Data on the melt flow rate (MFR) and density of the used polyethylene grades are available because the BAM was the competent authority for the approval of the plastic heating oil storage tanks until the end of the 1980s.
The technical service of specialist companies for fuel tank disposal supplied tank sections from the bottom, the shell and the roof of 8 segregated heating oil storage tanks. Some of the tanks had been in service for more than 30 years. Two polyethylene grades mainly were used as materials for these tanks over this time. The determination of the MFR according to EN ISO 1133 and the FTIR spectroscopy followed standard test methods.
The highest average percentage increase in the MFR was determined as 31- 43 % for the bottom section of the tanks, for both the inner shell and the outer shell. The lowest increase in MFR was measured for the top of the tank, with 6 - 12 % for the inner shell and 0 - 8 % for the outer shell. The tank shell sections had an average percentage increase in MFR of 10 - 33 % for the inner shell and of 14 - 40 % for the outer shell.
The oxidative damage of the polyethylene grades was highest in the bottom area due to the permanent contact with the heating oil and degradation products.
The microtome cuttings were analyzed with image-guided infrared microscopy in the transmission mode and confirmed the results obtained with the MFR measurements.
In summary it can be concluded that the oxidative damage of the polyethylene grades after long-term contact with heating oil is relative low.
Surface water-induced broadening of crack initiation probability of zinc aluminosilicate glasses
(2017)
The crack generation probability by Vickers indentation of glass surfaces is known to be influenced by the atmospheric conditions under which the Vickers experiment is performed [1]. However, the effect of surface water due to preparation and storage of the glass surfaces prior to the indentation is less understood. Therefore, zinc aluminosilicate glasses of perzinc, peraluminous as well as nominally NBO-free meta-aluminous composition were prepared by melt quenching. Surfaces of cut and polished specimens of these glasses were either stored for seven days under constant atmosphere (50 °C; 55% RH) or etched (HF: 20vol%; 20 min) shortly before indentation. The obtained results show a strong variation of crack initiation behavior depending on chemical composition of the glasses as well as sample preparation. All experiments were performed in dry nitrogen gas to minimize the influence of atmospheric humidity during indentation. While the regular glass surfaces exposed to humid air prior to Vickers indentation show a broad distribution of crack initiation probability, this distribution narrows down if etched glass surfaces are tested. SNMS depth profiling shows a water enriched layer at the surface (150 μm) for the non-etched and stored specimens leading to the conclusion that surface water causes broadening of the crack initiation probability of glass surfaces.
Im deutschen Bundesautobahnnetz treten vor allem an den vor 2005 errichteten Betonfahrbahndecken vermehrt Schäden auf, die mit einer AKR in Verbindung gebracht werden. Sie äußern sich zunächst in einer Dunkelfärbung in den Fugenbereichen der Betonfahrbahndecke. Oft wird diese Erscheinung von einer von der Fuge ausgehenden horizontalen Rissbildung parallel zur Fahrbahnoberfläche begleitet. Durch den Einsatz der NMR-Technik konnte erstmals zerstörungsfrei der erhöhte Feuchtegehalt in der Betonrandzone als Ursache für diese Erscheinung nachgewiesen werden. Zusätzlich durchgeführte Radaruntersuchungen und Darr-Wäge-Versuche zeigten, dass die erhöhte Durchfeuchtung in der Betonrandzone in der Regel den gesamten Fahrbahnquerschnitt erfasst. Weiterhin wurde aufgezeigt, dass vor allem die akustischen Verfahren eine zerstörungsfreie Detektion der von der Fuge ausgehenden lateralen Ausdehnung der oberen Rissebene in die Fahrbahnplatte ermöglichen. Im Gegensatz zum Impakt-Echo-Verfahren erlaubt das Ultraschall-Echo-Verfahren zusätzlich die Ermittlung der Tiefenlage der oberen Rissebene. Es wird eine weitere Ertüchtigung der akustischen Verfahren für die Strukturaufklärung in Betonfahrbahndecken angeregt.
It is known that the spalling risk of dense, high-strength concretes (HSC) can be reduced by the addition of polypropylene (PP) fibres and, in particular, PP-fibres that have been pre-treated using electron irradiation. It is presumed that the enhanced reduction in spalling resulting from electron irradiation pre-treatment of the fibres can be attributed to enhanced penetration of the molten fibre material into the micro-cracks around the fibres, due to their significantly decreased viscosity. So far there has been no experimental evidence for this. Against this background, this paper gives a com-parative analysis of the mode of action of PP-fibres with and without pre-treatment using multi-scale test methodology.
Initially, fire tests on small-scale building components with accompanying damage monitoring veri-fied that the amount of PP-fibres can be halved by using pre-treated PP-fibres without reducing the fire performance of HSC. Detailed investigations of PP-fibres carried out in a completed research project funded by DFG (the German Research Foundation) using digital scanning calorimetry and thermogravimetry measurements (DSC/TG) as well as viscometer measurements showed that the pre-treatment has no significant influence on the melting temperature of the PP-fibres. However, a drastic reduction of the melt viscosity due to the electron irradiation was detectable. Additional dila-tation tests showed that the expansion behaviour of both fibre types and their melts do not differ significantly [1]. Rather, both fibre types generate high pressures when their thermal expansion is hindered. Further detailed investigations by means of continuous heating tests with a low heating rate were carried out on separately produced concrete cylinders. These tests showed that the pre-treatment of the PP-fibres causes earlier dehydration in conjunction with stagnation of thermal expansion of the concrete cylinders (temperature reduction from 180 °C to 170 °C). This is accompanied by in-creased acoustic emission activity during the thermal expansion tests. This leads to the assumption that the pre-treatment of PP-fibres results in earlier micro-crack development. However, it was not possible to confirm this assumption by microscopic examination of drilling cores with a diameter of 30 mm exposed to defined temperatures in the range between 150°C and 300°C. Microscopic obser-vations and additional X-ray 3D computed tomography (3D-CT) scans on miniaturised drilling cores exposed to temperature cycles showed a similar networking of fibre beds by means of micro-cracks in HSC for both fibre types. However, energy dispersive X-ray spectroscopy and wavelength disper-sive X-ray spectroscopy revealed fundamental differences in the penetration capacity of the fibre melts of the two fibre types. The increased penetration of the pre-treated PP-fibre melt revealed in these tests, confirms the initial working hypothesis.
Aufbauende Untersuchungen an Laborbetonen: Parameterstudie zu ausgewählten AKR-Einflussgrößen
(2017)
Gegenstand des Vortrags ist die Vorstellung der Ergebnisse der aufbauenden Untersuchungen an Laborbetonen im Forschungsvorhaben FUTURUM. Im konkreten Fall werden die Ergebnisse der Parameterstudie zu nachstehenden ausgewählten Einflussgrößen auf die schädigende AKR präsentiert:
- zyklische Beanspruchung durch Klima und Verkehr
- Einbautemperatur und Nachbehandlung
- Art der Oberflächentextur
- ausgewählte Prüfbedingungen bei der Klimawechsellagerung (KWL)
Die Basis für diese Untersuchungen bildeten großformatige Balken sowie Platten mit behinderter Schwindverformung, die aus den im ARS 04/2013 vorgegebenen Fahrbahndeckenbetonrezepturen unter Verwendung einer alkaliempfindlichen Gesteinskörnung hergestellt wurden. Folgende Ergebnisse wurden erzielt:
- moderate Förderung schädigender AKR durch zyklische Beanspruchung aus Klima und Verkehr
- unterschiedliche Förderung des AKR-Schädigungsprozesses bei verschiedenen Fahrbahn-deckenbetonen bei Erhöhung der Einbautemperatur von 15 auf 30 °C und sonst gleichbleibender Nachbehandlung (Folie)
(Oberbeton >8 / Unterbeton: moderat, Oberbeton 0/8: stärker ausgeprägt)
- verminderte KWL-Dehnung bei AKR-provozierender Lagerung beider Betonarten bei 30 °C durch Verschlechterung der Nachbehandlung (Windkanal, 5 m/s)
- Zunahme schädigender AKR in Abhängigkeit von der Art der Oberflächentextur (Besenstrich, Grinding/Grooving, Waschbeton)
- nichtlineare Zunahme der KWL-Dehnung mit Erhöhung der NaCl-Konzentration der Prüflösung (Bestätigung der Richtigkeit gewählter normativer NaCl-Konzentration)
- Verminderung der KWL-Dehnung durch Substitution der Frost-Tauwechselphase trotz vermindertem Tausalzeintrag
Here, we report on the recent advancements in the synthesis and optical properties of novel core-shell CdSe semiconductor nanocrystals (SCNC) with either a thick monolithic shell of CdS or thin multi-shells of succeeding CdS and ZnS monolayers, characterized by steady state and time-resolved fluorescence spectroscopy at the ensemble level. SCNC samples, chosen upon the size of their photoluminescence quantum yield (PL QY), were subsequently investigated at the single particle level using a custom build confocal laser scanning microscope to obtain information on brightness, blinking behavior, and decay kinetics of single SCNCs and correlate these properties with their surface morphology. The results of this study can help to identify new synthetic routes and surface modifications to colloidally and photochemically stable SCNCs with a PL QY of close to unity.
Ausgehend von der in der TRAS 410 beschriebenen Notwendigkeit zur Veranlassung besonderer Maßnahmen beim Umgang mit deflagrations-und/oder detonationsfähigen Stoffen werden die Explosionsmechanismen für Stoffe in kondensiertem Zustand beschrieben. Reaktive organische Stoffe sind u. a. anhand ihrer Struktur insbesondere bei Vorhandensein bestimmter funktioneller Gruppen identifizierbar. Durch eine Reihe von international eingeführten Prüfmethoden lassen sich solche Stoffe z. B. hinsichtlich ihrer mehr oder weniger ausgeprägten explosiven Eigenschaften charakterisieren. Anhand konkreter Beispiele werden die Prüfergebnisse erläutert und die Stoffe aufgrund ihrer Eigenschaften klassifiziert. Maßnahmen zur Vermeidung kritischer Zustände bei der Herstellung und Lagerung sowie beim Transport gefährlicher Stoffe werden auch am Beispiel von Unfällen erläutert.
The accelerated concrete prism test (ACPT-60 °C) facilitates testing of alkali-silica reactivity of aggregates within five months. Manual measurement is usually conducted to determine expansion of test specimen every 28 days. This conventional procedure gives only limited insight to expansion behaviour of ASR-affected prisms. Due to the large time intervals, expansion exceeding the critical value of 0.3 mm/m is likely to be noticed late. Continuous recording resolves this problem and delivers beneficial information on the shape of the expansion curve.
Displacement transducers integrated into a special testing equipment developed at BAM put continuous measurement into practice. Additionally, ultrasonic velocity and acoustic emissions are measured in-situ and provide deeper insights into hydration and crack formation processes during the test.
Aiming for an automated testing method close to the German guideline, the following technical and methodical challenges arise. Changing of the vertical orientation of the prisms with every manual measurement as standardised cannot be implemented. Furthermore, preliminary results already proved true that cooling and heating cycles, as necessarily associated with each manual measurement, can evoke additional expansion. Therefore, interrupted and continuously measured expansions reveal systematic differences, indicating the necessity to adjust the threshold expansion value for automated testing.
Results presented in the paper: Different types of reactive aggregate have been tested applying continuous and manual expansion measurement to the concrete specimens. Development of continuously measured ultrasonic velocity and acoustic emissions of the aggregates tested diverge significantly while the expansion curves vary in shape and maximum strain. Prisms produced from a slowly reacting aggregate do not exhibit noticeable crack formation. It shows that comprehensive measuring helps describing and distinguishing ASR-damage mechanisms.
Models of ASR-induced expansion, available in the open literature, so far are validated with discontinuous data hardly tracing the modelled curve. Continuous measurement improves validation and further model development.
2,4-Dichlorophenoxyacetic acid (2,4-D) is an important and well-known herbicide that is widely used in agriculture because of its advantages to regulate plant growth.1 However, the use of large quantities of the treated plants as animal feed leads to residues in meat, milk and eggs. Furthermore, the herbicide can drain off and contaminate ground and drinking water. The ingestion of 2,4-D-contaminated food and water can cause damage to the inner organs of humans and animals, e.g., the kidneys and the liver.
Analytical assays based on molecularly imprinted polymers (MIPs) have emerged as a valuable tool in the field of environmental analysis due to the low production costs, high stability, format adaptability and the possibility to imprint—and thus their ability to recognize—a wide variety of target analytes. Regarding optical sensing technologies, however, MIPs have only been used in considerably few applications, especially in fluorescence sensors. This limitation is basically because the incorporation of a fluorescently responding moiety into a polymer matrix is challenging. One way to overcome this limitation is to use tailor-made fluorescent indicator monomers or cross-linkers for direct transfer of the binding event into an optical signal and to coat the MIP via reversible addition-fragmentation chain transfer (RAFT) polymerization as a thin layer onto the surface of silica nanoparticles as primary sensing element.
Here, we present the response behaviour of fluorescent MIP sensor particles in terms of sensitivity for 2,4-D detection (the so-called imprinting factor), discrimination ability against structurally similar compounds (the discrimination factor) and performance in a phase-transfer assay (PTA) on chip, i.e., the implementation of the assay into a microfluidic chip environment, offering a novel simple and rapid way for the detection of herbicides in water.
One of the most significant limitations for the quantum efficiency of group III-nitride based light emitters is the spatial electron-hole separation due to the quantum-confined Stark effect (QCSE). To overcome this problem, Hönig et al. [1] proposed a novel concept, the Internal-Field-Guarded-Active-Region Design (IFGARD), which suppresses the QCSE for wurtzite crystals in the [0001] direction. Here, we show how encapsulating the active region by additional guard layers results in a strong reduction of the built-in electric field in c-plane wurtzite nanostructures. Even more importantly, we demonstrate the first experimental evidence for the successful realization of an IFGARD structure based on GaN/AlN heterostructures embedded in GaN nanowires. By means of power-dependent and time-resolved µ-photoluminescence (µ-PL) we experimentally proof the validity of the unconventional IFGARD structure. We managed to tune the emission of 4-nm-thick GaN nano-discs up to 3.32 eV at low excitation powers, which is just 150 meV below the bulk GaN bandgap. Our results demonstrate an almost complete elimination of the QCSE in comparison to conventional structures which show approximately 1 eV red-shifted emission. The suppression of the QCSE results in a significant increase of the radiative exciton decay rates by orders of magnitude and demonstrates the potential of IFGARD structures for future light sources based on polar heterostructures.
[1] Hönig et al., Phys. Rev. Applied 7, 024004 (2017)
Einfluss von Feuchte und Nässe auf die Witterungs-induzierte Alterung am Beispiel eines Polyurethans
(2017)
Bei der Bewitterung von Polymeren kommt es auf molekularer Ebene zur Alterung, die sich in verschiedenen Eigenschaften als unterschiedlich starke Änderung äußert. Art und Geschwindigkeit dieser molekularen Alterung und die damit einhergehenden Eigenschaftsänderungen hängen dabei neben einer Reihe anderer Einflussfaktoren von der Art und Intensität der Beanspruchung ab.
In diesem Beitrag soll der relative Einfluss des Wassers als Feuchte und Nässe unter den Beanspruchungsfaktoren untersucht werden. Die Unterscheidung von Luftfeuchte und Nässe bezüglich ihrer Wirkung ist dabei notwendig, weil die stehende Nässe zusätzliche Extraktionswirkung besitzt und auch die verfügbare Sauerstoffmenge beeinflusst.
Dazu wurde ein Polymer, das im Rahmen des BAM-internen Projektes PolyComp untersucht wird, künstlich bewittert. Hierzu wurde ein Fluoreszenzlampengerät mit UV-A 340 nm Leuchtstoffröhren verwendet, in dessen Probenraum durch zusätzliche Kammern die gleichzeitige Bewitterung unter drei unterschiedlichen Feuchte-Varianten realisiert wurde (bei konstanter Temperatur):
- UV und trocken
- UV und hohe Luftfeuchte
- UV und stehende Nässe.
Das gleichzeitige Einwirken der einzelnen Einflussfaktoren kann dabei konkurrierende oder aufeinander folgende chemische Reaktionen und physikalische Prozesse und somit ein anderes Ergebnis bewirken, als wenn sie isoliert nacheinander auf eine Probe eingewirkt hätten.
Über die erwähnten Varianten hinaus kann auch noch der spezifische Einfluss der UV-Strahlung mit untersucht werden, weil die Proben im Bereich ihrer Befestigung verdeckt sind.
Die Methodik und erste Ergebnisse dieser Untersuchung werden präsentiert.
Examinations of the mechanical properties of the BAM drop hammer and the BAM friction test were done recently. In order to validate the correct functioning of both tests, usually Round-Robin tests are done with selected test substances. A relatively large spread of the results including some outliers is usually accepted and attributed to the nature of the tests. The author asked, however, in how much the mere mechanical properties could already differ between different institutes, even when no substance is involved (dry runs). A thorough inter-laboratory study was done for the drop test, and results for the friction test are on its way. The current state of these investigations will be presented.
Controlling the hazards in explosives manufacture has been addressed ever since such substances have entered industrial processing. The rigour of exercising such control appears to vary in different fields of application (fireworks versus blasting explosives) and in different countries worldwide. Nonetheless, each tradition has developed a set of standard tests addressing sensitivity and other aspects of behaviour of explosives. With a full system of workers protection in place in most countries nowadays, the control of hazards in explosives manufacture has become much more formalised. The paper aims to show the common parts of process hazard analysis and the consequential steps involving either a risk based approach or a prescriptive approach. The paper aims to stimulate discussions about recent developments.
This presentation shall outline the regulatory tools for explosives manufacture in force in Germany and emphasize the benefits of a codified approach. Those in the need of applying safety measures find a given set of prescriptions, which do not need to be determined through a case by case study. While a process hazard analysis is usually required, it is not necessary to perform a risk analysis.
The system is likely to be more conservative than others, because it generalizes the application cases and needs to be valid for all variations within the description. It is also conservative in that respect that, from learning from previous accidents, for each case a conclusion improving safety entered the code. The more recent history of events shows that the system provides excellent protection of workers in this field. In addition it gives all operators a safe backup for their activity, since following the code generates the "presumption of conformity" and makes juridical judgement more straight forward.
A joint Round Robin test was initiated by the "explosives testing user group" involving all renowned test institutions of the USA plus The Netherlands (TNO) and Germany (BAM). Aim of the Round Robin test was not only to align results with regard to the friction sensitivity of a given powder sample, but also to study the variations of GO and NO-GO reactions by high speed camera recordings.
Bei der Betrachtung der Rechtmäßigkeit von Explosivstoffen und pyrotechnischen Gegenständen mit CE-Zeichen auf dem Gemeinschaftsmarkt der EU wird oft der Baumusterprüfung und der "Baumusterprüfberscheinigung" große Aufmerksamkeit geschenkt. Bei pyrotechnischen Gegenständen kommt hier noch die Registriernummer als überprüfbares Merkmal hinzu. In der Phase der Baumusterprüfung werden die anwendungstechnischen Eigenschaften und Anforderungen der harmonisierten Normen geprüft, wofür eine der prüfenden benannten Stellen der EU die Verantwortung hat.
Für die sichere Funktion und Leistung von Explosivstoffen und pyrotechnischen Gegenständen ist jedoch die in der, oder im Anschluss an die, Fertigung stattfindende Qualitätssicherung (QS) mindestens ebenso wichtig. Ohne Einhaltung eines der Qualitätssicherungsmodule findet keine rechtmäßige Abgabe auf den Gemeinschaftsmarkt statt. Unkorrekte Anwendung der QS führt i. d. R. auch zu Fehlern an den Produkten mit mehr oder weniger auffälligen Problemen.
In der Vergangenheit konnte die Marktüberwachung aus dem Anzeigeverfahren für die erstmalige Verwendung von Explosivstoffen und pyrotechnischen Gegenständen und den dabei geführten Listen Anhaltspunkte bzgl. der Rechtmäßigkeit gewinnen und ggf. bei der BAM weiterführende Informationen abfragen. Mit dem Wegfall der Anzeigepflicht nach § 6 der 1. SprengV und dem Wegfall dieser Informationsquelle muss sich die Überprüfung von Explosivstoffen und pyrotechnischen Gegenständen auf dem Markt und in Lagern auf die begleitenden QS nach einem der Module der jeweiligen Richtline konzentrieren.
In dem Beitrag werden Kennzeichnungsmerkmale und Möglichkeiten der Überprüfung der QS an Explosivstoffen und pyrotechnischen Gegenständen aufgezeigt. Teilnehmer der Marktüberwachung und anderer Aufsicht führenden Stellen sollen sensibilisiert werden und mit Informationen ausgestattet werden, die ihnen ein Handeln auf diesem Gebiet ermöglichen.
Sol-gel synthesis was used to prepare nanoparticles of MgF2 and CaF2. These nanoparticles were tested for their application in wood protection. In comparison to control samples, wood specimens treated with MgF2 and CaF2 showed lower mass loss under exposure to termites and fungi. Samples treated with MgF2 performed better at protecting wood from cellulose degradation when exposed to termites. Conversely, in the presence of fungi, mass loss in treated samples was similar irrespective of the chemical composition (MgF2 and CaF2) of the treatment. A possible explanation for this difference in results between termites and fungi could be their different mechanism of cellulose hydrolysis. Thus, future wood preservatives would need to be customized according to their specific application.
An extraction of silica from natural sands of Bancar has been conducted by means of alkali fusion route using NaOH and mechanical alloying using planetary ball milling. The PANI/SiO2 Composite system has been coated in steel surfaces using spraying method. This study was designed to obtain PANI/SiO2 as an anti-corrosion coating material. The filler materials in the composite System consist of micro- and nano-SiO2. The structure of synthesized SiO2 be characterized using XRD and TEM. Corrosion of PANI/SiO2 composite has been tested using immersion method in synthetic geothermal atmosphere (Nord Deutsche Becken/NDB solution). The surface morphology after corrosion was observed by using SEM/EDX. XRD-Patterns and TEM show that the size of produced SiO2 is micro and nano. The size and composition of filler have influenced to surface degradation in geothermal atmosphere significantly. The addition of nano-SiO2 in the PANI matrix influenced corrosion resistance better than micro-SiO2 filler qualitatively. The nano-SiO2 has a high potential as an anti-corrosion material in geothermal atmosphere. The product of corrosion is mainly Fe2O3 and the corrosion process is identified as a pitting corrosion.
Proben mit einer Mittelkerbe aus Polyamid 66 mit 35% Gewichtsan-teil an Kurzglasfaser (PA-GF35) wurden im Spritzgießverfahren hergestellt und in einem ungeschädigten und durch Schwingbeanspruch geschädigten Zustand mittels Röntgenverfahren charakterisiert. Sowohl die Faserorientierungsverteilung als auch die Riss-/Mikrorissbildung wurden mit der Röntgenrefraktionstopographie in einem SAXS-Aufbau und dem Diffraction-Enhanced-Imaging am Synchrotron (BESSY II) analysiert. Beide Verfahren spiegeln in guter Übereinstimmung die Charakteristiken dieser Werkstoffklasse in Bezug auf die Fertigungsqualität und die Schädigungsme-chanismen wider.
SAXS for the determination of the size distribution of nanoparticles: Application in catalysis
(2017)
The open source software packages SASfit1 and McSAS2 are widely used to determine the size distribution of nanoparticles. SASfit is based on classical curve fitting. The type of size distribution needs to be provided as constraint for analysis. Very often the lognormal size distribution is useful as shown for the characterization of single- and multimodal magnetic iron oxide particles. The use of SASfit is part of efforts to standardize analyzing methods for magnetic nanoparticles within the EU project NanoMag (www.nanomag-project.eu). In contrast to SASfit, it is not necessary to provide the type of size distribution when using the program McSAS. Both programs provide tools that allow the user to estimate uncertainties of the derived size distributions. Such is helpful in the development of nanoscale reference materials for environmental, health and safety measurements. As an example, a detailed study on using SAXS in the characterization of ultra-small-silver nanoparticles is presented. These particles are useful in the catalytic reduction of 4-nitrophenol and display an adjustable activity (see Figure).
Figure. Core-shell silver nanoparticles catalyze the reduction of 4-nitrophenol and display an increasing catalytic activity when stabilized with different ligands in the line bovine serum albumin (BSA), glutathione (GSH) and polyacrylic acid (PAA).5
Ermittlung eines allgemeingültigen Erstarrungsrisskennwerts durch Abstraktion gängiger Heißrisstests
(2017)
Ergebnisse von Untersuchungen zur Heißrissanfälligkeit metallischer Werkstoffe, die aus gängigen Heißrisstests gewonnen wurden, sind i.A. schlecht mit Ergebnissen aus anderen Testverfahren vergleichbar. Darüber hinaus ist die Fehlererkennungsgenauigkeit der etablierten Testverfahren mitunter dürftig. Auch die Übertragbarkeit der rein Werkstoff-orientieren Testergebnisse auf reale Bauteile gestaltet sich schwierig. Insgesamt ist das Phänomen der Heißrissbildung nicht ausreichend erforscht und verstanden, als dass es in Konstruktion und/oder Bauteilfertigung vorhergesagt werden könnte.
Die vorliegende Arbeit befasst sich mit der Abstraktion gängiger Testverfahren, um verfahrensspezifische Einflüsse möglichst zu eliminieren, sodass eine universellere Beurteilung von Werkstoffen vorgenommen werden kann. Die gewonnenen Ergebnisse können so besser für Simulationen bzw. Vorhersagen der Heißrissanfälligkeit realer Bauteile herangezogen werden.
Ermittlung eines allgemeingültigen Erstarrungsrisskennwerts durch Abstraktion gängiger Heißrisstests
(2017)
Ergebnisse von Untersuchungen zur Heißrissanfälligkeit metallischer Werkstoffe, die aus gängigen Heißrisstests gewonnen wurden, sind i.A. schlecht mit Ergebnissen aus anderen Testverfahren vergleichbar. Darüber hinaus ist die Fehlererkennungsgenauigkeit der etablierten Testverfahren mitunter dürftig.
Nach der Konzeption eines neuartigen, geeigneten Verfahrens zur Bestimmung der Erstarrungsrissneigung weitestgehend unabhängig von Prozesseinflüssen, fasst dieser Vortrag nun die Validierung der experimentellen Vorgehensweise zusammen.
Die Schicht-für-Schicht additive Fertigung (AM) in Form des selektiven Laser- bzw. Elektronenstrahlschmelzens (SLM und EBM) bietet einerseits Vorteile bezüglich des Probendesigns, andererseits sind strukturelle Abweichungen von der nominellen Morphologie unvermeidbar. Beispielsweise führt das Abkühlen des fertigen Bauteils zu verringerten Abmessungen und angeschmolzene Pulverpartikel sorgen für unregelmäßige Oberflächen mit nicht vernachlässigbaren Rauigkeiten.
Im Fokus dieser Arbeit steht die computertomographische (CT) Untersuchung von IN625 Pulver und den daraus SLM-gefertigten Streben, Einheitszellen und Gitterstrukturen.
Mit Hilfe von Synchrotron – CT konnte das IN625 Pulver mit einer Voxelgröße von 0,5µm untersucht werden. Für die Untersuchung der daraus gefertigten verschiedenen Probengemetrien wurde Labor CT genutzt.
6 mm lange Streben variierten im Aufbauwinkel von 40° bis 90°. Der Unterschied zwischen Unter- und Oberseite während der Fertigung wird sowohl bei Porenverteilung als auch bei der Oberflächenrauigkeit deutlich. Ein Vergleich der Strebenabmessungen für die nominalen Durchmesser von 0,5 mm bis 3 mm zwischen CT and GOM zeigte keine signifikanten Differenzen.
Vier dieser Streben wurden zu einer bbc Einheitszelle zusammengefügt, welche sich wiederum zu den Gitterstrukturen ergänzen.
An einem Gitterwürfel (3x3x3 Einheitszellen) wurden In-Situ (Druck) CT bis 5kN durchgeführt. Mit einer Kraft von etwa 3kN erreichen wir den plastischen Bereich und beobachten zudem Strebenverzug.
Außerdem wurde ein Vergleich zu den CAD-Files wurde genutzt um einen möglichen Verzug während der Fertigung beurteilen zu können. Dafür wurden 4x4x4 cm³ Gitterstrukturen gebaut und evaluiert.
Mit diesen CT Messungen bestätigen wir eine signifikante Schrumpfung, die Bereits während der Fertigung berücksichtigt werden muss.
Die Schicht-für-Schicht additive Fertigung (AM) in Form des selektiven Laser- bzw. Elektronenstrahlschmelzens (SLM und EBM) bietet einerseits Vorteile bezüglich des Probendesigns, andererseits sind strukturelle Abweichungen von der nominellen Morphologie unvermeidbar. Beispielsweise führt das Abkühlen des fertigen Bauteils zu verringerten Abmessungen und angeschmolzene Pulverpartikel sorgen für unregelmäßige Oberflächen mit nicht vernachlässigbaren Rauigkeiten.
Im Fokus dieser Arbeit steht die computertomographische (CT) Untersuchung von IN625 Pulver und den daraus SLM-gefertigten Streben, Einheitszellen und Gitterstrukturen.
Mit Hilfe von Synchrotron – CT konnte das IN625 Pulver mit einer Voxelgröße von 0,5µm untersucht werden. Für die Untersuchung der daraus gefertigten verschiedenen Probengemetrien wurde Labor CT genutzt.
6 mm lange Streben variierten im Aufbauwinkel von 40° bis 90°. Der Unterschied zwischen Unter- und Oberseite während der Fertigung wird sowohl bei Porenverteilung als auch bei der Oberflächenrauigkeit deutlich. Ein Vergleich der Strebenabmessungen für die nominalen Durchmesser von 0,5 mm bis 3 mm zwischen CT and GOM zeigte keine signifikanten Differenzen.
Vier dieser Streben wurden zu einer bbc Einheitszelle zusammengefügt, welche sich wiederum zu den Gitterstrukturen ergänzen.
An einem Gitterwürfel (3x3x3 Einheitszellen) wurden In-Situ (Druck) CT bis 5kN durchgeführt. Mit einer Kraft von etwa 3kN erreichen wir den plastischen Bereich und beobachten zudem Strebenverzug.
Außerdem wurde ein Vergleich zu den CAD-Files wurde genutzt um einen möglichen Verzug während der Fertigung beurteilen zu können. Dafür wurden 4x4x4 cm³ Gitterstrukturen gebaut und evaluiert.
Mit diesen CT Messungen bestätigen wir eine signifikante Schrumpfung, die Bereits während der Fertigung berücksichtigt werden muss.
Der Einfluss der Probenabtrennung von der Bauplatte auf den Eigenspannungszustand in SLM IN718
(2017)
Die Schicht-für-Schicht additive Fertigung (AM) in Form des selektiven Laserschmelzens (SLM) bietet einerseits Vorteile bezüglich des Probendesigns, andererseits sind thermische Eigenspannungen (ES) aufgrund des hohen Temperaturgradienten unvermeidbar. Diese Eigenspannungen wurden in zwei SLM-gefertigten Proben aus IN718 zerstörungsfrei mit Neutronenstreuung hinsichtlich der folgenden zwei Einflüsse analysiert: der Einfluss der Hatch-Länge und das Abtrennen des Werkstücks von der Bauplatte. Begleitet wurden die Messungen der Eigenspannungen durch optische Mikroskopie und die taktile Vermessung der Oberfläche. Eine Korrelation zwischen den Eigenspannungen und der Hatch-Länge konnte beobachtet und erklärt werden.
The effects of UV radiation and humidity condition on the frictional properties of TPU materials are presented in this paper.
Photooxidative degradation of polymer leads to deterioration of physical and mechanical properties, which affect its tribological behavior significantly.
Unfilled TPUs lose their anti-slip properties.
A laser induced breakdown spectroscopy (LIBS) system was combined with the Gas Tungsten Arc (TIG) Welding process for the in situ monitoring of chemical compositions in austenitic stainless steels during welding. The purpose of this project is to develop a prototype of an online chemical composition control system for welding applications. One of the use cases of this new LIBS-based measurement system can be the controlling of potentially dangerous emissions during the welding process in order to improve the working safety conditions.
The Tungsten Inert Gas (TIG) welding process was combined with a Laser-Induced Breakdown Spectroscopy (LIBS) system for the in situ measurement of chemical compositions in austenitic stainless steels. The main aim of this project was the development of a prototype for a real-time chemical composition analysis system for welding applications. In principle, the measurement of the weld pool composition allows governing the weld pool solidification behaviour by controlling the welding parameters. This control loop allows avoiding weld defects.
Chemical compositions of the weld seam is from a metallurgical point of view the most critical parameter for the occurrence of weld defects. Additionally, this new LIBS-based measurement system can be used for the monitoring and controlling of potentially dangerous emissions during the welding process in order to improve the working safety conditions. Preliminary investigations show that the chemical composition measurement of welds with LIBS is possible during and after welding.
Elastomer seals are widely used as barrier seals in containers for low and intermediate level radioactive waste. In addition, they are also used in waste fuel storage and transportation casks as auxiliary seals. Depending on the area of use, the rubber materials have to demonstrate proper sealing performance with respect to mechanical, thermal and environmental conditions as well as irradiation during the entire operation period. A fundamental understanding of the structure property relationship and their changes during aging can help to evaluate the long-term sealing performance.
In the present study, specific materials are investigated to study the structure-property and seal performance-correlation. Fluoro-elastomer (FKM), silicone rubber (VMQ) and ethylene propylene diene rubber (EPDM) were chosen as base rubbers. Comparable mechanical properties for these seals, especially in terms of a comparable compression behavior were achieved by careful control of base rubber formulation, i.e., by opting for the right filler and its concentration, amount of crosslinking chemicals, and with the assistance of process oils. Moreover, with the same rubber, similar mechanical properties were achieved by varying the filler concentration and crosslinking degree, which shall enable to correlate the particular influence on the structure property dependency of the seals in detail. The materials are investigated under pristine and aged conditions to evaluate the influence of aging, e.g. on the stress relaxation or recovery behavior. These values appear to be suitable parameters to judge the expected sealing performance.
Due to the electrically conducting nature of some fillers used to reinforce rubbers (such as carbon blacks, carbon nanotubes (CNTs), Graphene, etc.) it is possible to obtain current information about mechanical and visco-elastic properties by monitoring the electrical conductivity or resistivity. A simple relation that relates electrical resistance with mechanical stress was derived and the stress values were theoretically predicted from the electrical resistance values, which showed good correlation with experimental results.
Building materials consist of cement, water and chemical admixtures, which adjust cement paste properties. They can act beyond their aimed functions causing changes in hydration course. The mechanisms are still under investigation. We investigate cement hydration in levitated droplets using an ultrasonic levitator. Hydrate phase formation is followed in situ by synchrotron XRD. The data allows detailed conclusions about the mechanisms of the admixture action in the ongoing hydration reactions.
Chemical admixtures are widely used to adjust properties of the cementitious mixtures. Different superplasticizers (SP) are typically added to improve the flowability of the fresh cement paste. Their working period is the initial stage of the cement hydration from its beginning until stiffening. Currently, polycarboxylate-based SP (PCE-SP) are the most effective ones. They can act beyond their aimed function causing changes in the hydration course, e. g. retardation effects. The exact mechanisms and influencing factors are still under investigation. However, the occurrence of the retardation effect indicates the involvement of PCE in the hydration reactions. Some observations indicate, that the retardation depends on the type, molecular structure and concentration of PCE, and the presence of other admixtures (stabiliser, ST). These factors influence further the working time of admixture and its amount related efficacy in the flow improvement.
We investigate the cement hydration process in situ in levitated droplets. High resolution synchrotron X-ray diffraction allows gathering temporal course of the hydration reactions. The measurement setup is based on an ultrasonic levitator allowing in situ investigation of the temporal changes of the phase composition in the hydrating cementitious system. Further, the hydration can be followed ab initio avoiding the time loss for the sample preparation and filling in the sample holder. The collected data allows to conclude about the mechanisms of the admixture action and their involvement into the ongoing hydration process.
Wasserstoff kann in Überlagerung mit Beanspruchungen zu einem unerwarteten Werkstoffversagen in höherfesten Stählen führen (wasserstoffunterstützte Schädigung von Metallen, starke Abnahme des Verformungsvermögens). In der Schweißtechnik besteht die Gefahr der wasserstoffunterstützten Kaltrissbildung. Die Aufnahme von Wasserstoff während des Schweißens lässt sich gänzlich nicht verhindern. Höherfeste Feinkornbaustähle um 700 MPa werden zunehmend mit unterschiedlichen Legierungskonzepten und Herstellungsrouten produziert. Diese Unterschiede erzeugen ein differentes Gefüge und Aussscheidungscharakteristik bei nominell ähnlichen Festigkeiten. Wichtige Vertreter sind der S690QL und der S700MC. Die Ergebnisse zeigen zum einen eine deutliche Abnahme der mechanisch-technologischen Gütewerte, zum anderen eine differente Degradation durch Wasserstoff. Signifikant ist die Abnahme der wahren Bruchdehnung bei bereits geringen Wasserstoffkonzentrationen unterhalb 4 ppm. Weiterhin wurde das Wasserstoffbindungsverhalten (Trapping) im Grundwerkstoff und im schweißsimulierten Gefüge untersucht. Die Ergebnisse zeigen Unterschiede hinsichtlich der Bindungsenergie und des Fallencharakters. Die Resultate belegen, dass eine Reduzierung des eingebrachten Wasserstoffs unabdingbar ist für einen sicheren Betrieb geschweißter Komponenten aus höherfestem Feinkornbaustahl.
The ageing of Fe-Cr model alloys in 0.5 % SO2 and 99.5 % Ar atmosphere was investigated to aim in a fundamental and systematic analysis of the combined oxidation and sulfidation mechanism. The crystallization and reaction paths for oxide and sulfide formation were followed in-situ by energy dispersive X-ray diffraction (EDXRD) in an early stage of corrosion (30 s – 24 h). For this technique, high energetic white synchrotron X-ray radiation (10-100 keV) was used as radiation source. Diffraction pattern were collected continuously in an early stage of corrosion up to 24 h during the complete ageing experiment.
The crystalline phases, growing on top of the coupons, were identified directly via their specific dhkl values. The evolution of the extracted integral intensities of specific reflections of the corrosion products as a function of time access direct information about the kinetics of the nucleation and growth. The results presented here show for iron with 2 wt% Cr wuestite formation first. Wuestite vanishes after 10 min of reaction only and magnetite and hematite appear. Magnetite formation proceeds simultaneously with sulfide formation. Sulfides growth proceeds after an incubation time, which differs for low alloyed (2 wt% Cr) and high alloyed (9 wt% Cr) material.
Materials are subject to environmental constraints that include biological, chemical and physical factors. To gain confidence about durability and long-term performance of any material, environmental resistance testing procedures have to be amended with modern simulation procedures that include biological components. In fact, any environmentally exposed surface at temperatures lower than 121 °C will be home to microbial growth, even at high salt concentrations, extreme pH, environmental pollution, low water potential, and intense irradiation – everywhere where water is liquid and available. As a consequence, complex microbial ecosystems called biofilms are self-sufficient and found on almost all solid-air-water interfaces. Obviously, environmental changes perturb biofilm development but over a number of seasons, these changes result in relatively stable microbial communities peculiar and adapted to a particular niche and material. Certain microbial settlers are indicative of, and in a real sense mark, a particular biofilm and can, thus, be considered as “reference organisms”. Characteristic reference organisms’ peculiar to specific material-inhabiting communities can be isolated, identified, characterised and used in standard test procedures as well as research into materials science (materials improvement). In this presentation classical microbiological, genetic and molecular methods for studying reference organisms and their roles in materials deterioration will be presented. We will present a set of different reference organisms that are currently in focus of our research and testing development.
Unilateral thermal exposure of concrete building components induces moisture transport processes that have a significant influence on the spalling behaviour of dense high-strength concrete (HSC). These transport processes are based on evaporation and condensation mechanisms of liquid and gaseous water in the pores as well as the chemically bound water within the concrete. The low permeability of HSC and the formation of a saturated zone within building components (also known as a moisture clog) leads to high water-vapour pressures, which contributes to explosive spalling. The formation of these pressures has already been verified by means of pore-pressure measurement techniques. In addition, the redistribution of the moisture within concrete specimens subject to unilateral thermal exposure has been demonstrated on fractured surfaces. Investigations by means of the nuclear magnetic resonance (NMR) relaxometry technique and neutron radiography have shown one-dimensional changes in moisture distribution during thermal exposure.
However, none of these methods has been able to depict the moisture distribution in three dimensions (3D), so the link between pore size, concrete micro-structure and moisture content is missing. The research project presented in this paper aims to fill this gap by developing a new multi-level test methodology to characterise non-destructively the temporal course of spatial moisture distribution during unilateral thermal exposure. The procedure used during this programme included the collection of X-ray 3D-computed tomography (CT) measurements using a miniaturised specimen subjected to in-situ thermal exposure and the comparison of those CT results with the results of one-dimensional NMR-relaxometry before and after the heating process.
In the first step, a mobile heating device was developed, built and tested. To simulate a unilaterally-heated construction component, a cylindrical specimen made of HSC (Ø = 40 mm, L = 100 mm) was cast into an impermeable glass ceramic shell. The ceramic shell ensured a one-dimensional moisture flux and limited the thermal expansion of the concrete. An additional high-temperature wool (HTW) insulating shell ensured a one-dimensional heat flux. The heating device, which operated using infrared radiation (IR), allowed the unilateral heating of the specimens up to 300 °C using variable heating regimes.
In the second step, the mobile heating device was integrated into the CT-scanner, which enabled the collection of measurements before, during and after heating. By subtraction of successive 3D-CT images, X-ray attenuation differences could be resolved three-dimensionally in the specimen and interpreted as changes in the moisture content.
Initial results show that this test methodology can monitor the 3D changes of moisture content inside the specimen during thermal exposure. It enables the researcher to visualise areas with moisture accumulation as well as dehydrated areas inside the specimen. Comparative one-dimensional NMR-relaxometry measurements confirm the results of the CT image analysis.
Die Entwicklung von leistungsfähigen Fließmitteln in den letzten Jahrzehnten ermöglicht die Herstellung von Beton mit sehr geringem w/z-Wert, bei gleichzeitig guter Verarbeitbarkeit. Die Reduzierung des w/z-Wertes führt zu einer Erhöhung der Festigkeit und zu einer Verdichtung der Gefügestruktur. Aufgrund der hohen Druckfestigkeit finden Hochleistungsbetone vermehrten Einsatz im Hoch-, Brücken-, und Tunnelbau. Allerdings neigen diese Hochleistungsbetone unter Brandbeanspruchung zu explosionsartigen Abplatzungen, die nach derzeitigem Stand auf thermomechanische und thermohydraulische Prozesse zurückgeführt werden. Letztere beruhen auf der Generierung hoher Wasserdampfdrücke in einseitig brandbeanspruchten Betonbauteilen, die zum einen auf die geringe Permeabilität des Hochleistungsbetons und zum anderen auf die Bildung einer wassergesättigten Zone, der sogenannten „moisture clog“ zurückzuführen sind. Dabei spielen Verdampfungs- und Kondensationsvorgänge sowie der vorhandene Temperaturgradient eine wichtige Rolle. Die Interaktion des Feuchtetransportes mit den Gefügeveränderungen während der thermischen Beanspruchung soll im Rahmen weiterer Versuche eingehend untersucht werden.
Zur Analyse des Feuchtetransports während der thermischen Beanspruchung werden miniaturisierte Prüfkörper aus Hochleistungsbeton hergestellt, die mit Hilfe eines elektrischen Heizelements einseitig erwärmt werden. Zur Sicherstellung eines eindimensionalen Wärme- und Feuchtetransportes ist der Betonprüfkörper mit einer speziellen Glaskeramik und einer Hochtemperaturwolle ummantelt. Simultan zur Erwärmung werden eine Reihe röntgentomografischer Aufnahmen durchgeführt. Durch Differenzbildung aufeinanderfolgender Aufnahmen können Dichteveränderungen lokal und zeitlich werden, die Rückschlüsse auf Änderungen der Feuchteverteilung im Prüfkörper während der Erwärmung zulassen. Parallel dazu werden Untersuchungen mittels NMR-Relaxometrie (nuclear magnetic resonance) vor und nach der thermischen Beanspruchung durchgeführt. Die entwickelte Prüfmethodologie ermöglicht es, Veränderungen der Feuchteverteilung infolge thermischer Beanspruchung im Hochleistungsbeton von den Gelporen bis hin zu vorhandenen Verdichtungsporen abzubilden. Erste Ergebnisse zeigen, dass die gewählten Untersuchungsmethoden Veränderungen der Feuchteverteilung im Prüfkörper räumlich und zeitlich auflösen können.
Improved wear resistant ceramics of metal incorporated NbC processed with gas pressure sintering
(2017)
Tungsten carbide (WC) dominates wear protection and machining since more than 90 years due to its hardness with an associated good toughness and high melting point.
It was recently demonstrated that Niobium Carbides are wear resistant and show a better performing under cutting than WC grades. In order to profit of the good properties of Niobium Carbide, specific processing techniques need to be developed. The density of NbC is half of WC and offers colloidal processing for perfectly mixing NbC with metallic binder (up to 15 vol.-% Ni) and secondary carbide-particles. The used NbC-powder has an average particle size d50 of 3 micron measured by laser granulometry analysis. The true density was 7.68 g/cm3. An Oxygen content of the used NbC of 0.4 % is caused by residual slag content.
It is possible to increase the stability of the NbC-suspensions and to reduce their viscosity by adding a specific dispersing agent.
This surface-modified NbC powders (containing Ni)were uniaxially pressed and then gas pressure sintered in vacuum or Argon atmosphere. All samples reached more then 98 % of there theoretical density. The micrographs showed a homogenius distribution of the Ni-binder in the product. The tribological behaviour under dry sliding and oscillating up to 600 °C and the mechanical properties were studied.
Die mechanische Spannung ist ein maßgeblicher Parameter ferromagnetischer Materialien. Wird ein solches Material unter die Curie Temperatur abgekühlt, zerfällt es spontan in nahezu selbstgesättigte magnetische Domänen. Diese Magnetisierung führt gleichzeitig zu einer Verformung der mit ihr gekoppelten Kristallgitter. Ein Effekt der auch reziprok gilt: wird die Gitterverformung durch eine Spannung behindert ändert sich zwangsweise der magnetische Zustand.
Man kann annehmen, dass zwischen unterschiedlichen, für sich aber homogen verspannten Werkstoffbereichen, lokale magnetische Streufelder auftreten, weil magneto-mechanische Effekte eine Inkompatibilität der Domänenstruktur induzieren. Bekanntlich bilden sich Spannungsgradienten nach Schweißprozessen durch ungleichmäßigen Wärmeeintrag, thermischer Dehnung, und unterschiedlichen Abkühlraten aus.
Unter dieser Prämisse untersuchen wir Wolfram-Inertgas geschweißte Blindnahtproben (250x100x4,8 mm^3) aus einem hypereutektoiden Baustahl.
Der Spannungszustand der Proben wurde anhand von Neutronendiffraktometrie (ND) am Instrument E3 am Reaktor BERII (Helmholzzentrum Berlin, HZB) charakterisiert. ND ist ein Referenzverfahren für die quantitative Bestimmung von elastischen Dehnungen in kristallinen Materialien, deren Gitter selbst der Messmaßstab ist. Die Auswertung zeigt hohe Längsspannungen mit lokalen Maxima in Größenordnung von 600 MPa, die von umgebenen Druckspannungszonen kompensiert werden.
Zur Detektion der magnetischen Kleinststreufelder verwenden wir speziell designte GMR-Sensorik (GMR - Giant Magneto Resistance), die aufgrund der geringen Größe ihrer aktiven Sensorelemente hohe Ortsauflösung mit Sensitivität vereint. Die Visualisierung der Messergebnisse lässt eine klare magnetische Mikrostruktur der Schweißnähte erkennen, in der die Streufelder lateral in Größenordnung des Erdmagnetfeldes variieren (~50 µT).
Wir zeigen durch einen Vergleich beider Messverfahren, dass lokale magnetische Streufeldmaxima in hohem Maße mit den Spannungsgradienten übereinstimmen.
In einer Vielzahl technischer Anwendungen spielt die Aufrechterhaltung eines definierten Reibungs- und Verschleißverhaltens zwischen bewegten Oberflächen für die Sicherheit und Funktionalität eine ent-scheidende 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 Oberflächenstrukturierun-gen breite Möglichkeiten zur Beeinflussung des Schmierungszustandes bzw. der Kontaktbedingungen. Neben immateriellen Strukturen bieten ebenfalls erhabene Mikrostrukturen großes Potenzial zur Beein-flussung des tribologischen Verhaltens. Ihr Einsatz ist aufgrund der Verschleißproblematik erhabener Strukturen, sowie verschiedener technischer als auch wirtschaftlicher Problemstellungen, bei ihrer Her-stellung momentan limitiert.
In diesem Beitrag wurde das Verfahren der Laserimplantation angewandt, um ebendiese Problemstellun-gen zu überwinden. Das Verfahren basiert auf einem lokalisierten Dispergieren von Hartstoffpartikeln, wodurch erhabene und separierte Oberflächenstrukturen hoher Verschleißfestigkeit in einem Fertigungs-schritt erzeugbar sind. Hierfür wurde erstmalig ein gepulster Faserlaser mit hoher Strahlqualität, zur Er-zeugung punkt- und linienförmiger Mikrostrukturen, angewandt. Versuche wurden auf dem Kalt-arbeitsstahl X153CrMoV12, unter Anwendung von Titandiborid als Hartstoff, durchgeführt. Anhand von Härtemessungen konnte gezeigt werden, dass sowohl punkt- als auch linienförmige Strukturen mit Här-ten über 1000 HV1 und einer feinkörnigen Mikrostruktur mit feinverteilten Hartstoffpartikeln herstellbar sind. Des Weiteren war es möglich die Implantgeometrien, welche an Querschliffen und durch Weißlicht-interferometeraufnahmen erfasst wurden, durch die Pulsleistung und Pulsdauer zu steuern.
Oberflächenstrukturierung mittels Laserimplantation ist anwendbar zur Positivstrukturierung mit TiB2, führt zu signifikanter Härtesteigerung und Verschleißfestigkeit an verschleißgefährdeten Werkzeugen.
Die Steuerung der Implantgeometrie ist durch die Prozessparameter möglich.
Die flexible Anordnung implantierter Bereiche ermöglicht die Erzeugung komplexer Muster zur Beeinflussung des tribologischen Verhaltens.
The cause and type of solid particle erosion varies across different industries and locations in plants, for instance the particles could be volcanic ash in aero-engines, fly ash in boilers, exfoliated scale in steam turbines or mineral matter in oil excavation. In all cases the durability of materials can be improved through better surface engineering and coatings, but the development of these is restricted also due to lack of generic models. In this respect, the simulation of a single impact with finite element methods using 100.000 knots would take about 15 minutes. In order to simulate an entire particle erosion experiment, up to one billion of such impacts would have to be considered. In order to simulate an entire particle erosion experiment, the current work presents an alternative approach capable of calculating about half a billion impacts on a substrate in less than six hours on a standard PC. The predictions of the simulation will be compared to a steel sample at 600°C eroded by aluminum oxide particles with a velocity around 210 m/s.
It is widely known that the magnetic domain structure of stress-sensitive ferromagnetic materials may be altered by external or internal mechanical stresses due to magnetoelastic effects. In this contribution, localized magnetic domain changes arising from inhomogeneous deformation and multiaxial loading conditions are imaged by the Bitter method for the first time. It is demonstrated that these domain changes provide deformation-related information and thus, allow for the visualization of macroscopic strain gradients in fine-grained polycrystalline steels, while keeping a sufficient spatial resolution.
This approach has been developed within the framework of BAM-MI-project “MICRONET”.
The use of duplex stainless steels (DSS) in energy related applications is well known. Nowadays, DSSs become more favorable than austenitic steels due to the outstanding mechanical properties, the good corrosion resistance and the lower nickel content.However, the use of the duplex grade in acidic environments such as seawater can lead to a severe degradation in the structural integrity of the steel by hydrogen-induced/assisted cracking mechanisms, which can eventually result in premature failure. Hydrogen assisted degradation and cracking of steels remains unclear even though this topic is intensively studied for more than a century. The main gap lies in the validation of the proposed theoretical models at the sub-micron scale. Industrial and the research communities define a need for an accurate method by which it is possible to image the distribution of hydrogen in the microstructure. Among the very few available methods nowadays, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) provides precise mapping of hydrogen in the microstructure. Moreover, the powerful combination of ToF-SIMS with multivariate data analysis (MVA), electron backscattered diffraction (EBSD) for providing a the structural information and the use of data fusion techniques can contribute to a better understanding of the hydrogen induced degradation processes in the material.
In the present work two types of duplex grades were chosen as a case study (standard and lean DSS). The duplex class, consist of equivalent amounts of ferrite and austenite, was investigated by ToF-SIMS and EBSD during and after electrochemical deuterium charging in order to simulate the service of a component in acidic environments. Deuterium is known to act on the steel similarly to hydrogen and therefore was used as a tracer for hydrogen. The results show that the ferrite was affected almost identical in both steels whereas in the austenitic phase significant differences were observed in the lean duplex in comparison to the standard duplex. The advantage of the combined techniques is reflected by the ability to correlate the hydrogen distribution in the microstructure to the resulted structural changes.
The aluminum alloy 2618A is an Al-Cu-Mg alloy with additions of Fe and Ni, which was designed for long-term operation at elevated temperature in transportation and aerospace industries. Typical applications include aircraft parts and structures (sheet material) or engine components such as turbo charger centrifugal compressor wheels (forged material). Such components are subjected to prolonged aging during service, (e.g. 50 000 h) at temperatures which are close to their age hardening temperature (ca. 190 °C). The microstructural evolution was investigated.
Diverse animal species consume toxins, minerals or secondary compounds as an adaptive response to pathogen infection – a process termed self-medication. Recent studies have also shown that macronutrients can play an important role in an individual’s infection response. For instance African army worm caterpillars select a diet rich in protein and low in carbohydrate upon baculovirus infection. Here we investigate whether dietary choice of macronutrients also plays a role in immunity in the omnivorous cockroach: Blatta orientalis. After challenging individual cockroaches with a common entomopathogenic soil bacterium, Pseudomonas entomophila, we conducted food-choice experiments using two artificial diets differing in their relative protein to carbohydrate ratio. We show for the first time that cockroaches are able to self-select a protein-enriched diet as a response to bacterial infection. This is driven by a sharp decline in carbohydrate intake rather than an increase in protein intake. Additionally, infected cockroaches reduced their overall nutrient intake, which is consistent with an illness-induced anorexia-like response. The feeding pattern of bacteria-challenged individuals returned to normality approx 4 days after challenge. We also investigate whether cockroach survival and hemolymph immunity are enhanced in individuals when restricted to a protein-rich vs. carbohydrate-rich diet. Overall, our findings demonstrate that macronutrient preferences follow a general pattern independent of pathogen type. Furthermore, we show that interactions between nutrition and immunity are highly conserved in evolution, highlighted by the fact that caterpillars and cockroaches diverged some 386 million years ago.
Recent studies have shown that host-microbiota interactions can lead to dramatic changes in host phenotype. We investigate the causal drivers of microbe-associated shifts in host phenotype by examining how feeding behaviour is modulated by microbiota interactions in two omnivorous cockroaches: Blatta orientalis and Blatella germanica. We conducted food-choice experiments after challenging hosts with a common entomopathogenic soil bacterium to understand the impact of pathogens on host macronutrient preference. We find that immune challenge by a pathogenic microbe drives a sharp decline in carbohydrate intake and results in a relative increase in the ratio of protein to carbohydrate (P:C) consumed. Additionally, infected cockroaches reduce their overall nutrient intake, which is consistent with an illness-induced anorexia-like response. We show for the first time that cockroach feeding behaviour is dynamically modulated by a pathogen, and examine the influence of modified feeding behaviour on host immunity. We also investigate whether in addition to pathogens, gut commensals are causally responsible for shifts in host behavioural phenotype. Here, we conduct food-choice and immune-challenge experiments in germ-free cockroaches, which have been refaunated with gut microbiota that are experimentally adapted to variable macronutrient (P:C) diets.
Recent studies have shown that host-microbiota interactions can lead to dramatic changes in host phenotype. We investigate the causal drivers of microbe-associated shifts in host phenotype by examining how feeding behaviour is modulated by microbiota interactions in two omnivorous cockroaches: Blatta orientalis and Blatella germanica. We conducted food-choice experiments after challenging hosts with a common entomopathogenic soil bacterium to understand the impact of pathogens on host macronutrient preference. We find that immune challenge by a pathogenic microbe drives a sharp decline in carbohydrate intake and results in a relative increase in the ratio of protein to carbohydrate (P:C) consumed. Additionally, infected cockroaches reduce their Overall nutrient intake, which is consistent with an illness-induced anorexia-like response. We show for the first time that cockroach feeding behaviour is dynamically modulated by a pathogen, and examine the influence of modified feeding behaviour on host immunity. We also investigate whether in Addition to pathogens, gut commensals are causally responsible for shifts in host behavioural phenotype. Here, we conduct food-choice and immune-challenge experiments in germ-free cockroaches, which have been refaunated with gut microbiota that are experimentally adapted to variable macronutrient (P:C) diets.