Ingenieurwissenschaften und zugeordnete Tätigkeiten
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Eingeladener Vortrag
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Interlaboratory comparison: optical property classification of carbon-based films by ellipsometry
(2017)
The paper addresses the “INTERLABORATORY COMPARISON: OPTICAL PROPERTY CLASSIFICATION OF CARBON-BASED FILMS BY ELLIPSOMETRY” and the following points are discussed in more detail: Established classification for mechanical properties, Complementary classification for optical properties, Ellipsometry for determination of optical constants n-k plane as material fingerprint, Samples, participants & set-ups (samples: Japan, participants: Japan, Germany, France, set-ups: Japan, Germany, USA) and Results of interlaboratory comparison: thickness, n & k.
Easy to handle and stretchable polymer optical fibres for sensor applications
Basic idea of stimulated Brillouin scattering
Brillouin threshold for PMMA-POF and PFGI-POF in comparison
Sensorial behavior of Brillouin scattering in PFGI-POF and silica SMF
Basics and classification of distributed Brillouin sensing methods
Basic idea of dynamic Brillouin sensing
The reinforcement of concrete with polymer fibers provides resistance to crack formation. The orientation distribution of these fibers has a significant influence on the mechanical behavior of the material. To optimize material performance, micromechanical models that are capable of making accurate predictions of the mechanical behavior of composite materials are needed. These models must be calibrated using experimental results from microstructural characterization. For the fiber orientation distribution analysis in the present study, computed tomography (CT) data were used to evaluate the properties of a fiber-reinforced cement mortar. The results have indicated that the fibers in this material have highly anisotropic orientation characteristics and that there is a clear tendency for the polymer fibers to agglomerate during mixing and casting. The incorporation of this experimental data into micromechanical models will increase the accuracy of those models for material simulation and optimization.
Shock tube systems are non-electric explosive fuses employed in blasting and demolition applications to trigger the detonation of explosive charges. Their working principle is based on the explosive reaction of a fine powder on the tubing´s inner surface, generating a percussive wave travelling at a velocity of 2,100 m/s along the length of the tube, without destroying it. One of the key aspects of the manufacturing process of these shock tubes is the size and morphology of the explosive powder grains and their distribution on the inner wall of the tube, in order to propagate the shockwave efficiently and reliably. For the first time, synchrotron X-ray computed tomography has been used to characterize non-destructively the explosive powder grains, typically Al/HMX between 10 and 20 μm in size, in terms of morphology and 3D distribution but also to characterise the presence and location of defects within the shock tube walls.
Photoluminescence techniques are amongst the most widely used tools in the life sciences, with new and exciting applications in medical diagnostics and molecular imaging continuously emerging. Advantages include their comparative ease of use, unique sensitivity, non-invasive character, and potential for multiplexing, remote sensing, and miniaturization. General drawbacks are, however, signals, that contain unwanted wavelength- and polarization contributions from instrument-dependent effects, which are also time-dependent due to aging of instrument-components, and difficulties to measure absolute fluorescence intensities. Moreover, scattering systems require special measurement geometries and the interest in new optical reporters with emission > 1000 nm strategies for reliable measurements in the second diagnostic for the comparison of material performance and the rational design of new fluorophores with improved properties.
Here, we present strategies to versatile method-adaptable liquid and solid fluorescence standards for different fluorescence parameters including traceable instrument calibration procedures and the design of integrating sphere setups for the absolute measurement of emission spectra and quantum yields in the wavelength region of 350 to 1600 nm. Examples are multi-emitter glasses, spectral fluorescence standards, and quantum yield standards for the UV/vis/NIR
Lanthanide-doped up-converting nanoparticles (UCNPs) are promising reporters for medical diagnostics and bioimaging, which are excited in the near infrared (NIR) by multiphoton absorption processes, and show multiple narrow emission bands in the visible (vis) and NIR, long luminescence lifetimes in the μs range, and excellent photostability. Current limitations present their relative low absorption cross sections and low fluorescence efficiencies, with the latter being affected by particle size, surface chemistry, and microenvironment, particularly water.
Here, we present results from systematic studies of the excitation power density dependent upconversion luminescence spectra, intensities/intensity ratios of the individual emission bands, slope factors, and quantum yields of UCNPs of varying size, dopant concentration, and surface chemistry in different microenvironments as well as the up- and downconversion luminescence decay kinetics of the different emission bands. Moreover, first studies of the energy transfer from UCNPs to surface-bound organic dyes acting as fluorescence acceptors are shown. Based upon these measurements, fluorescence deactivation channels are identified and spectroscopic parameters for the screening of material performance are derived.
Lanthanide-doped up-converting nanoparticles (UCNPs) are promising reporters for medical diagnostics and bioimaging. Current limitations present their relative low absorption cross sections and low fluorescence efficiencies, with the latter being affected by particle size, surface chemistry, and microenvironment, particularly water.
Here, we present results from systematic studies of the excitation power density dependent upconversion luminescence spectra, intensities/intensity ratios of the individual emission bands, slope factors, and quantum yields of UCNPs of varying size, dopant concentration, and surface chemistry in different microenvironments as well as the up- and downconversion luminescence decay kinetics of the different emission bands. Moreover, first studies of the energy transfer from UCNPs to surface-bound organic dyes acting as fluorescence acceptors are shown. Based upon these measurements, fluorescence deactivation channels are identified and spectroscopic parameters for the screening of material performance are derived.
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.
Synchrotron Radiation with its high intensity and the opportunity to tune the wavelength offers unique possibilities to investigate real catalysts, even under industry-like conditions.
A good example is a XAFS study performed at supported Ni catalysts used for the dimerization of butene at elevated temperature and pressure. Another example are investigations at titania supported Pd based catalyst elucidating the role of co-components (e.g. Sb, Co, Mn and Au) which are necessary to get the desired promising performance in the gas phase acetoxylation of toluene to benzyl acetate, an environmentally benign alternative for the conventional process using chlorine.
Furthermore, investigations about the redox properties of different Cu catalysts will be presented. It could be shown that the redox properties of Cu have a great impact on the performance of such catalysts, not only in some gas phase reactions, but also in photocatalytic applications, e.g. water splitting.
The work aims at addressing the modelling and implementation of criteria for multiple crack propagation, including interaction and coalescence, for a more reliable fracture mechanics-based prediction of stress-life curves for weldments.
A large experimental work is presented in which micro-cracks have been made visible by heat-tinting at successive stages of fatigue life of the welded specimens. Here the correlation between the number of initiation sites and the applied stress level has been also investigated.
The criteria have been implemented in in-house software, which allows multiple fatigue crack propagation, and validated against selected experimental tests. The results have shown that the modelling of multiple crack propagation and interaction is crucial for the prediction of the fatigue strength of weldments, both in finite and infinite life regime.
Borosilicate glass has a wide range of technical applications due to its high chemical durability and thermal-shock resistivity. Here the effect of H2O on 16 Na2O, 10 B2O3,74 SiO2 glass is studied over a wide range of water contents from 0 to 8 wt.%. MIR spectra give evidence for the coexistence of strongly and weakly H-bonded hydrous species. Evaluation of NIR bands at 5200 cm-1 (molecular H2O), 4700 cm-1 (B-OH), and 4500 cm-1 (Si-OH) reveal that OH groups dominate up to ~6 wt.% H2O, with B-OH/Si-OH of ≈ 0.8. The incorporation of low amounts of H2O has strong impact on structure. NMR spectra of nominally dry glasses indicate a significant fraction (12 %) of 3-coordinated boron, but almost all boron is 4-coordinated after addition of 3 wt.% H2O. Raman spectra show that hydration results preferentially in transformation of Q4 to Q2 while Q3 remain unchanged, probably stabilized by bonding to BO4 tetrahedra. Viscosity measurements and differential thermal analysis give consistent results, confirming strong decrease of the glass transition temperature with addition of water from 849 K (dry) to 540 K (5 wt% H2O). An additional relaxation mechanism in hydrous glasses is inferred from dynamic mechanical analysis and is assigned to cooperative processes involving hydrous species. It is postulated that this relaxation mechanism plays an important role in crack growth kinetics.
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.
Borosilicate glass has a wide range of technical applications due to its high chemical durability and thermal-shock resistivity. Here the effect of H2O on 16 Na2O, 10 B2O3,74 SiO2 glass is studied over a wide range of water contents from 0 to 8 wt.%. MIR spectra give evidence for the coexistence of strongly and weakly H-bonded hydrous species. Evaluation of NIR bands at 5200 cm-1 (molecular H2O), 4700 cm-1 (B-OH), and 4500 cm-1 (Si-OH) reveal that OH groups dominate up to ~6 wt.% H2O, with B-OH/Si-OH of ≈ 0.8. The incorporation of low amounts of H2O has strong impact on structure. NMR spectra of nominally dry glasses indicate a significant fraction (12 %) of 3-coordinated boron, but almost all boron is 4-coordinated after addition of 3 wt.% H2O. Raman spectra show that hydration results preferentially in transformation of Q4 to Q2 while Q3 remain unchanged, probably stabilized by bonding to BO4 tetrahedra. Viscosity measurements and differential thermal analysis give consistent results, confirming strong decrease of the glass transition temperature with addition of water from 849 K (dry) to 540 K (5 wt% H2O). An additional relaxation mechanism in hydrous glasses is inferred from dynamic mechanical analysis and is assigned to cooperative processes involving hydrous species. It is postulated that this relaxation mechanism plays an important role in crack growth kinetics.
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.
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.
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.
185 cracks were initiated in a soda-lime-silica glass by Vickers indentation and grown under controlled dry nitrogen atmosphere. Direct observation of subcritical crack growth (SCCG) upon indentation was performed using a video camera with an image acquisition rate of 3 ms. The results show that the validity of K(c) relations used to determine the indentation fracture toughness from a single imprint is questionable. It seems that correlation of crack length to stress intensity necessitate the use of statistical significant data of multiple crack events.
Hydrous silicate and borate glasses of up to 8 wt% water were prepared using wet condition of melting under external pressure. Rheological experiments were conducted to determine the effect of the total water content on viscous flow and kinetic fragility. The findings indicate that dissolved water acts as a strong fluxing agent in both glass types. Water decreases particularly viscosity at the glass transition range, makes the viscosity-temperature curve "longer" and thus decreases kinetic fragility. Recent IR and NMR data are presented to link the dynamics of hydrous silicate and borate glasses with their structure particularly with regard to changes in the water-, silicon- and boron-speciation.
Up to now, the mechanisms of surface nucleation and surface-induced texture formation are far from being understood. Corresponding phenomena are discussed hypothetically or even controversial, and related studies are restricted to very few glasses. As a main drawback, the vast majority of previous work on oriented growth of surface crystals do not consider the possible effects of glass surface treatments (like polishing defects, adhered particles and cracks, …) or ambient annealing conditions (vacuum or atmospheric pressure) which both can influence crystal nucleation and growth. Moreover, very few observations of crystal orientation related to surface crystallization were focused on separately growing crystals. In conclusion, up to now, no systematic studies on initially oriented crystal growth or nucleation from defined active nucleation sites have been pursued.
Therefore, the main objective of the proposed project is to gain a basic understanding of the mechanisms of surface-induced microstructure formation in glass ceramics. We shall answer the question whether preferred orientation of surface crystals is the result of oriented nucleation or caused by other orientation selection mechanisms acting during early crystal growth. In both cases, crystal orientation may be caused by the orientation of the glass surface itself or the anisotropy and orientation of active surface nucleation defects.
New techniques of experimental characterization of surface-crystallized glasses shall be applied to find answers to the questions posed above. Based on a controlled preparation and annealing of the glass sample surfaces, that includes the defined creation of active nucleation defects, and followed by the microstructural characterization especially during the very early growth stages of separated surface crystals, the orientation relations between defect and initiated surface crystal will be analyzed. In order to gain new insights, a couple of entirely new microstructure diagnostics techniques, including chemically contrasted XRM, laser-based sample preparation for XRM, and 3D electron backscatter diffraction shall be developed or applied.
This way, using X-ray microscopy as a pivotal technique for the non-destructive 3D characterization of relatively large samples at superior spatial resolution (but also complemented by other microstructure diagnostics techniques, e.g. TEM elemental mappings at cross-sectioned samples) unprecedented insights into the microstructure evolution upon surface crystallization of model glasses will be gained.
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.
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.
Presentation of the work of division 9.4 with focus on the Key aspects of component welding applying higher-strength fine-grained structural steels. The increased application of higher-strength steels and filler materials necessitates a more profound understanding of the interactions between the welding process, the heat input, the cooling conditions and the resulting metallurgical processes in the weld and its surroundings. Strategies, which help to improve the strength properties and life-time of welded structures to such an extent that the utilisation of higher-strength materials can be justified and their lightweight construction potential can thus be exploited to the full, can only be derived from the interaction between all the influencing factors. Examples of a few investigations on welded joints between higher-strength fine-grained structural steels with regard to the interactions between the main variables influencing the cold cracking are presented.
Laser metal deposition is described with its applications for additive manufacturing. The necessary process chain is discussed, with regard to weld bead dimensions and 3D build-up strategy. Metallurgical cross sections, x-ray and tensile tests are conducted. As demonstrative components, a gas turbine burner and a turbine blade are shown
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.
The presentation focuses on the current state of the optical spectroscopic studies on plasmon enhanced upconversion luminescent processes of silica-metal core-shell nanocomposites. A general introduction of the upconversion process, the theoretical basis of plasmonic enhancement, the theoretical requirements in regard to NP architecture for plasmon enhanced UC will be outlined. The first proof-of-concept measurements show the difficulty in realization the theoretical measurement parameters in laboratory conditions and underline the need for shifting the experiments to single particle level.“
Advanced spray drying process by controlled slurry destabilization and ultrasonic atomization
(2017)
Spray drying of ceramic slurries aims for soft and free-flowing granules with homogenous microstructure suitable for uniaxial and isostatic pressing. A stable and continuous spray drying process of slurries with maximized solids content is a further development target, since a reduction of the energy intensive drying procedure is desirable.
First part of the investigation focuses on the development of an appropriate zirconia slurry for spray drying with optimized organic additive contents (dispersant + binder + pressing and lubricating agents). Characterization and improvement of slurries are based on zeta potential measurements and investigations of the sedimentation behavior in an optical centrifuge. Therefor the slurries were spray dried with a conventional spray dryer with a two stream nozzle run in fountain mode. The controlled destabilization of the slurries was introduced, since the unwanted formation of hard granules with donut-like shape could be circumvented. Spray drying of such modified slurries resulted in soft granules without voids and finally leaded to sintered bodies with improved microstructure, density and bending strength.
Expectedly, the destabilization process causes a significant increase in viscosity of the ceramic slurry. Hence, an alternative spraying concept utilizing an ultrasonic nozzle was tested. Indeed, the ultrasonic nozzle seems able to atomize slurries with viscosities beyond the capability of the regular two stream nozzles due to the slurry’s shear thinning behavior. In second part of the investigation the integration of the ultrasonic nozzle in a commercial spray dryer is shown and first results of the spraying tests are discussed. Continuous spraying processes of highly viscous alumina, zirconia and ZTA slurries were realized over an extended production period.
Corrosion Resistance of the Super-Austenitic Stainless Steel UNS S31266 for Geothermal Applications
(2017)
Super-austenitic stainless steels cover grades with high chromium (20 to 27 %), high nickel (18 to 31 %) and high molybdenum (4 to 6 %) contents. Within this family, the 6%Mo high nitrogen grade S31266 was developed to combine the beneficial influence of chromium, tungsten, molybdenum and nitrogen on its mechanical and corrosion properties. Due to 22 % nickel, 24 % chromium and 0.4 % nitrogen additions, this alloy exhibits a very stable microstructure, being less prone to intermetallic phase precipitation than the other highly alloyed super-austenitic stainless steels.
This paper deals with the corrosion resistance of S31266 in artificial geothermal water with moderate salinity and low pH. Long-term static exposures and electrochemical tests were conducted at various temperatures to evaluate the pitting, crevice and stress corrosion cracking resistance of this material.
The results show that S31266 is resistant up to 220 °C. As a consequence, it can be a good candidate material for geothermal applications involving a highly corrosive environment, especially salinity and low pH.
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.
The purpose of the work presented in this paper is to analyze locally (at the element level) the contact behavior of a soil-pile contact problem. Therefore, a 2D shear test is modeled using the Finite Element Method. The formulation of a 4 nodded zero-thickness Interface element of Beer is chosen with a linear interpolation function. Four constitutive contact models adapted for contact problems have been implemented. The Mohr-Coulomb and Clough and Duncan models were chosen initially, due to the ease of implementation and few number of parameters needed. After, more complicated models in the framework of
elasto-plasticity such as: Lashkari and Mortara were implemented for the first time into the finite element code of the shear test problem. They include other phenomena such as:
relative density of soil, the stress level and sand dilatancy. From the results the relation between shear displacement and shear stress has been deduced. Finally, a discussion of the advantages and the drawbacks during computation of each model is given at the end.
UCST-type thermoresponsive polymers (i.e. that phase separate from solution upon cooling) present a tremendous potential not only in aqueous media where they can be used in drug delivery, diagnostic and microfluidic applications, but also in water/alcohol mixtures, where they can be used for instance in sensing systems for alcohol-soluble drugs. However, only a few thermoresponsive polymers have been reported that present an UCST in a relevant temperature range and “green” solvents such as water or ethanol.
In this context, acrylamide-based monomers can be very useful building blocks for designing novel non-ionic UCST-type polymers because of their hydrophilic nature (with the appropriate side chain) and propensity to form hydrogen bonds. We will present our latest results on the UCST-type thermoresponsive behaviour of acrylamide- and 2,6-diaminopyridine-based homopolymers and copolymers in water or water/alcohol mixtures, and give some insights about the rational design of UCST polymers relying on H-bonding.
Semiconductor nanocrystals with a spherical (QDs) core and a spherical or a rod-shaped Shell, u.a., so-called Quantum dot-Quantum rods (QDQRs) are increasingly used as fluorescent Reporters or optically active components in the life and material science, e.g., in solid state lightening including Plasma Displays. (1,2) Morever, there is an increasing interest in materials with emission >800 nm for bioanalysis, medical diagnostics, and safety barcodes. Prerequisites for the mechanistic understanding of nonradiativ decay channels needed for the rational design of improved nanomaterials and the comparison of material Performance are reliable fluorescence measurements and validated methods for the assessment of their surface chemistry. (3,4) The latter is of particular importance for nanocrystalline Emitters, where surface states and the accessibility of emissive states by quenchers largely control photoluminescence properties. (5) Here, we present results from systematic spectroscopic studies including absolutely measured photolumunescence Quantum yields of different vissible and NIR emisisve QD and QDQRs Systems of varying particle architecture size and surface chemistries in Dispersion and embedded in salt crystals. (6,7)
Non-Destructive Testing (NDT) is routinely used in aerospace, nuclear, railway and automotive industries. The most common use of NDT is to find flaws in components. In dynamically loaded components, flaws grow, and if they are not detected in time and no corrective measures are taken they can reach critical sizes. When a flaw reaches a critical size, it endangers the structural integrity of the component and will likely cause the component to fail. To detect flaws before they reach a critical size, components are inspected in fixed time intervals with non-destructive testing systems. In order to determine the amount of time between inspections, three variables are necessary: the critical size of the flaw, the flaw propagation speed and the size of the flaw that can be reliably detected by NDT. All three variables are, to a certain extent, stochastic. The critical size of the flaw and flaw propagation speed are questions of fracture mechanics. The size of the flaw that can be reliably detected by NDT is predicted by POD curves. The POD is determined for a given inspection scenario. The inspection scenario includes the NDT system, the component geometry and the type of the flaw. If one of these changes, the POD will also change and needs to be recalculated. As a result, the design of a dynamically loaded safety-relevant components is an iterative process in which a geometry is sought that provides an optimum between structural integrity and inspectability. A model that describes the iterative process for the design of the safe components with examples from praxis will be presented.
Polymer-based nanocomposites attracted recently a lot of attention from both the applicative and fundamental point of research. While the former point of view is due to the properties improvement compared to the corresponding matrix polymers the latter aspect is related to interaction of polymers with solid surfaces and confinement effects.
Here, nanocomposites based on poly(L-lactide) (PLA), which is a semi-crystalline polymer, and organically modified Layered Double Hydroxides (LDH) were prepared by melt blending, and investigated by a combination of Differential Scanning Calorimetry (DSC), Small- and Wide-Angle X-ray Scattering (SAXS, WAXS), and dielectric spectroscopy (BDS). Two different LDH materials were considered, which results in different morphologies of the nanocomposites. The influence of these different morphologies on the properties of the nanocomposites especially on the molecular mobility is discussed in detail.
In general the structure of semi-crystalline polymers has to be described by a three phase model, consisting of a mobile amorphous (MAF), a crystalline (CF), and a rigid amorphous fraction (RAF). For nanocomposites based on semi-crystalline polymers the RAF is due to both the crystallites (RAFcrystal) and the filler (RAFfiller). The considered nanocomposites were further investigated by hyper and temperature modulated differential scanning calorimetry. For the first time the different phase fractions CF, MAF, RAFcrystal, and RAFfiller could be estimated independently from each other.
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.
Polymerizing Substances
(2017)
Polymerizing substances are classified in different classes of the UN Recommendations on the Transport of Dangerous Goods. Based on incidents a new division 4.1 for polymerizing substances, which are not meet the criteria of the Classes 1-8, was implemented in the regulations. In the lecture, the criteria and the determination of the SAPT (self-accelerating polymerization temperature are discussed.
- Impact tests of concrete blocks
- High energy facility for laminographic testing
- Laminographic arrangement
- Cross-Laminography
- Measurement range extension by detector tiling
- Reconstruction methods
- Fast “shift averaging” method “next to base plane”
- reconstruction --> Removal of reinforcement indications
- 3D-Data analysis
- Crack-Segmentation by „Template Matching“
The detection and characterization of surface breaking cracks in steel prior to damage is a technologically as well as economically important task especially for safety-relevant structures. Detection of small cracks already during the steel production process might significantly reduce the risk of failure and reduce production costs due to an obsolete post-processing.
However, the hostile environmental conditions (high temperature specimens) together with very strict requirements in current steel production (production speeds, in-line testing and evaluation) are challenging and render many well-established NDE techniques hardly applicable.
We present an approach to use laser thermographic testing as a fast, remote and contactless NDE method, that addresses these challenges and might ultimately allow for online crack detection.
The basic idea of laser thermographic testing, introduced by Kubiak in 1968, is the monitoring of the heat flow as induced by local heating. Disturbances within the heat flow generated by the presence of surface cracks can then be analyzed by image processing algorithms, as we have shown in previous work.
The aim of the presented work is to advance laser thermographic testing to be applicable to the specific conditions of steel production environments. This purpose was met by the development of a laboratory setup that allows us to simulate production conditions, as rolling speed, specimen temperature, laser heating power and study their influence on crack detection performance. This parametric study enabled us to develop and improve data processing and crack detection algorithms with the final goal of providing optimized in-line crack detection. The studies were accompanied by comprehensive FEM simulations to intensify the understanding of the contrast formation as well as the crucial parameters influencing the performance of the method.
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.
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.
In order to study damage in concrete exposed to fire, a series of continuous X-ray computed tomography (CT) measurements were performed on a concrete sample heated, in-situ, on one side. The water migration relative to time and 3D space and, in particular, the dynamic condensation and vaporization of water droplets in the pores was quantified. This approach shows significant potential for further investigation of fire-related concrete damage.
Applications of femtosecond laser processed surfaces are reviewed. This includes the colorization of technical surfaces, the control of surface wetting, the tailoring of surface colonization by bacterial biofilms, the reduction of cell adhesion on novel pacemakers, and the improvement of the tribological performance of nanostructured metal surfaces.
Ellipsometry is a valuable surface analysis tool with an unmatched sensitivity towards surface layer properties. In this presentation, an initiative is discussed to make ellipsometry also a metrological tool. This is usually seen as very difficult due to the model-based nature of the analysis process. By establishing standardisation and reference materials, ellipsometry can be made traceable and can also become a valuable part of the traceable thin film metrology landscape. This is important because this technique has much potential to determine complex material parameters much needed in the production of high-tech products.
Chemical and electrochemical interaction mechanisms of metal-reducing bacteria with gold surfaces
(2017)
The ubiquity of biofilms is accompanied by significant health and safety risks. Clarifying the interaction mechanisms of sessile bacteria with metal and metal oxide surfaces is of great interest to advance the development of new control strategies and novel anti-fouling surfaces which mitigate the detrimental effects of bio-fouling.
The Shewanella genus is a faculatively aerobic, Gram-negative, exoelectrogenic bacterium known to demonstrate exceptional adaptability in respiratory capacities. Shewanella is often found in microbial communities within aquatic and sedimentary settings. During aerobic conditions, Shewanella utilizes oxygen as a terminal electron acceptor. During anaerobic conditions, respiration occurs via reduction of alternative terminal electron acceptors such as oxidized metals via extracellular electron transfer mechanisms involving electron shuttle molecules released by the bacteria.
The purpose of this work is to investigate the mechanisms of bacterial attachment and subsequent biofilm formation on metallic surfaces. Using Shewanella sp. model biofilms, surface enhanced Raman spectroscopy (SERS) complemented with electrochemical techniques have been utilized to study this dynamic interaction. Additionally, to study the process of diffusion of extracellular electron shuttles, a model system comprised of calcium cross-linked alginate to mimic the architecture of bacterial extracellular polymeric substances has been used. Inert model substrates with consistent uniformity and high surface enhancement factor have been fabricated via the deposition of gold nano-islands on thin glass slides. Moreover, it has permitted modification of the surface chemistry and surface energy via surface functionalization using organothiol self-assembled monolayers. The presentation will summarize our results on the interplay between the initial settlement rate and biofilm formation kinetics of bacteria on metallic substrates with variable environmental conditions such as electrolyte composition, pH, in addition to surface characteristics such as hydrophobicity/hydrophilicity and external polarization.
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.
Electrochemically active bacteria such as iron oxidizing bacteria (IOB) or iron reducing bacteria (IRB) accelerate the corrosion of stainless steel via the oxidation and reduction of iron oxides in the passive layer. The exposure to medium containing IOB and IRB leads to pitting corrosion with deep pits on stainless steel surfaces. Improving corrosion control via a better understanding of localized corrosion processes is highly relevant especially for reasons of safety or environmental protection since advancing pitting corrosion can easily lead to unpredictable material failure. Classic electrochemical methods however, provide insufficient information about the spatial heterogeneity of a corroding sample and fall short in detecting localized corrosion.
The aim of this work is to develop methods for the analysis of localized corrosion, on stainless steel surfaces induced by IRB and IOB biofilms. It is quite challenging to address the complexity of the variations in the passive layer composition and microstructure as well as the biofilm’s complexity with its local differential aeration cells and electrochemical parameters both at the same time. Thus in this study, agarose artificial biofilms mimicking the physical properties of a natural biofilm have been used as model systems to be able to differentiate between individual effects. This artificial biofilm is applied on a multi-electrode stainless steel sample to identify local anodic sites during exposure experiments. For more detailed analysis of active sites, a scanning electrochemical microscopy (SECM) has been applied. Using the SECM as an amperometric sensor, we have investigated concentration gradients of iron ions or oxygen within the biofilm and its immediate vicinity on actively corroding electrodes.
The presented analytical approach delivers promising results in clarifying how localized corrosion of stainless steels develops chronologically and spatially in the presence of IRBs and IOBs. Our results on model systems do also provide the basis for the investigation of natural biofilms in the future.
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.
Nanotechnology at BAM
(2017)
Nowadays the Instrumented Indentation Testing (IIT), in the nano range often named as nano indention, is one of the most commonly used methods to determine the mechanical properties of materials in the micro and nano range. This method is already extensive standardized in DIN EN ISO 14577 part 1-4. In the past, the application of this standard in testing praxis shows that the established values have an excellent precision. On the other side, the trueness as comparability of obtained results with reference values is not so good. To improve accuracy of IIT the use of a variable ε and the consideration of the lateral displacement during indentation became normative requirements during the last revision of ISO 14577.
Starting with the beginning of instrumented indentation testing in 1898 the historical background and the main assumption of the Oliver and Pharr method will be explained and critical discussed. It will be shown how to apply the use of a variable ε and the consideration of the lateral displacement during indentation in the daily testing work to improve accuracy of IIT.
Finally, ongoing standardization projects in the field of IIT will be briefly presented.
The draft of part 5 of ISO 14577 specifies verification and calibration of testing machines for carrying out the measurement of the dynamic material response when an oscillatory force or displacement, with amplitudes small in comparison to the prescribed target values, is imparted to the indenter while the indenter is continuously loaded to a prescribed target load or target depth or while the load or displacement is held constant at a prescribed target value. In case of a material showing plastic-elastic behavior, the measured dynamic response is used for continuous evaluation of the dynamic stiffness of the contact as a function of depth and frequency. Using the dynamic stiffness of the contact a reduced dynamic modulus will be calculated. In case of a material showing visco-elastic behavior from the measured dynamic response also the dynamic contact damping coefficient as function of depth and frequency is evaluated continuously. Using dynamic contact stiffness and dynamic contact damping coefficient reduced lost and storage modulus for visco-elastic materials will be calculated. The main normative requirements of the draft are discussed and their applications are illustrated by examples from daily experimental praxis.
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.
In this study, series of coatings with the goal of sensitising gold SPR sensors towards CO, NH4, etc. were prepared. To better understand the mechanism behind the sensitizing effect and to enable the targeted production of optimized layers, the wide range of coatings was studied by multiple methods from spectroscopic ellipsometry for their dielectric function, by XPS for chemical composition and SEM, TEM to determine their microscopic structure. The coatings were deposited at inert Ar gas and reactive Ar/O2 gas mixture by RF magnetron sputtering or DC pulsed magnetron sputtering with settable RF bias on the substrates. The plasma processes were monitors by mass spectrometry.
The metal oxide coatings in SPR sensors have to be prepared reproducible with thickness about 5 nm therefore lower deposition rate conditions were advantages.
Due to the increasing demand for utilization and improvement of energy efficient materials, especially concerning requirements in lightweight construction and design, polyolefin materials are used extensively and in an increasingly broad range of applications.
Although loaded with stresses under yield stress, preformed voids, inhomogeneities or notches can possibly lead to damage and unexpected failure induced by liquid media in polyolefin materials. For PE-HD, slow crack growth (SCG) as well as environmental stress cracking (ESC) are relevant mechanisms of damage. SCG appears without influence of a surrounding medium or in “inert” media whereas ESC occurs in “active” media, which have decisive influence on damage mechanism and time to failure. To characterize the intrinsic resistance of the material against those damage mechanisms, the Full-Notch Creep Test (FNCT) is widely used and of paramount importance particularly for the assessment of pipe and blow molding types of PE-HD.
In this study, the FNCT – usually applied as a standardized testing method (ISO 16770) using a few universal model liquid media – is extended by investigations of selected relevant PE-HD materials with a variety of properties also in real media. Mainly topical fuels, customary in the market such as diesel and biodiesel are examined. Especially the influence of temperature, and the ESC behavior of PE-HD in media that are sorbed to a significant extent, are addressed. The underlying diffusion-controlled sorption process was assessed before comparing non-saturated specimens with samples previously saturated with sorbing media.
The investigations were performed using a novel FNCT-device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
In addition to acquired results concerning time to failure and elongation behavior, imaging techniques, such as light microscopy (LM), laser scanning microscopy (LSM) and X-ray computed tomography (CT scan) were utilized to obtain data concerning crack propagation and media migration. Fracture surface analysis (LM, LSM) and quasi in-situ imaging (CT scan) via measurement in different load stages are considered explicitly. Correlations of elongation behavior and data derived from imaging analysis such as fracture plane roughness and height of areas of ductile deformation were obtained.
Due to the increasing demand for utilization and improvement of energy efficient materials, especially concerning requirements in lightweight construction and design, polyolefin materials are used extensively and in an increasingly broad range of applications.
Although loaded with stresses under yield stress, preformed voids, inhomogeneities or notches can possibly lead to damage and unexpected failure induced by liquid media in polyolefin materials. For PE-HD, slow crack growth (SCG) as well as environmental stress cracking (ESC) are relevant damage mechanisms. SCG appears without influence of a surrounding medium or in “inert” media whereas ESC occurs in “active” media, which have decisive influence on damage mechanism and time to failure. To characterize the inherent resistance of the material against those damage mechanisms, the Full-Notch Creep Test (FNCT) is widely used. Therefore, the FNCT is of paramount importance particularly for the assessment of pipe and blow molding types of PE-HD – especially in the field of polymer development and improvement for high-performance applications.
In this study, the FNCT – usually applied as a standardized testing method (ISO 16770) using a few universal model liquid media – is extended by investigation of selected relevant PE-HD materials with a variety of properties also in real media. Mainly topical fuels, customary in the market such as diesel and biodiesel are examined. Especially the influence of temperature, and the ESC behavior of PE-HD in media that are sorbed to a significant extent, are addressed.
The investigations were performed using a novel FNCT-device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
Additional to acquired results concerning time to failure and elongation behavior, imaging techniques, such as light microscopy (LM), laser scanning microscopy (LSM) and X-ray computed tomography (CT scan) were utilized to obtain data concerning crack propagation and media migration. Correlations of elongation behavior and data derived from imaging analysis were obtained.
Damage of PE-HD induced by liquid media - Full Notch Creep Testing (FNCT) and Imaging analysis
(2017)
Due to the increasing demand for utilization and improvement of energy efficient materials, especially concerning requirements in lightweight construction and design, polyolefin materials are used extensively and in an increasingly broad range of applications.
Although loaded with stresses under yield stress, preformed voids, inhomogeneities or notches can possibly lead to damage and unexpected failure induced by liquid media in polyolefin materials. For PE-HD, slow crack growth (SCG) as well as environmental stress cracking (ESC) are relevant damage mechanisms. SCG appears without influence of a surrounding medium or in “inert” media whereas ESC occurs in “active” media, which have decisive influence on damage mechanism and time to failure.
To characterize the inherent resistance of the material against those damage mechanisms, the Full-Notch Creep Test (FNCT) is widely used. Therefore, the FNCT is of paramount importance particularly for the assessment of pipe and blow molding types of PE-HD – especially for automotive but also for most other high-performance applications.
In this study, the FNCT – usually applied as a standardized testing method (ISO 16770) using a few universal model liquid media – is extended by investigations of selected relevant PE-HD materials with a variety of properties also in real media. Mainly topical fuels, customary in the market such as diesel and biodiesel are examined. Especially the influence of temperature, and the ESC behavior of PE-HD in media that are sorbed to a significant extent, are addressed.
The investigations were performed using a novel FNCT-device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
Additional to acquired results concerning time to failure and elongation behavior, imaging techniques, such as light microscopy (LM), laser scanning microscopy (LSM) and X-ray computed tomography (CT scan) were utilized to obtain data concerning crack propagation and media migration. Correlations of elongation behavior and data derived from imaging analysis such as fracture plane roughness were obtained.
Due to their unique physical properties, particularly their electronic and luminescent properties, graphene quantum dots (GQDs) are expected to be suitable for a wide range of applications in bioimaging, electro-optical and photonic materials or energy harvesting among others.1 Tuning the surface chemistry provides an efficient approach to modulate the fluorescence and distinct electronic properties of GQDs.2 Nevertheless, the role of surface chemistry on the electronic structure of GQDs remains poorly understood. In this presentation, we will compare systematically the electronic and chemical structures of GQDs functionalized with carboxylic and aminated groups to those of non-functionalized GQDs, combining theoretical and experimental approaches, here various photon-based spectroscopies. First, the electronic structure of GQDs was characterized by soft X-ray absorption (XA) and X-ray emission (XE) spectroscopies, probing unoccupied and occupied electronic states, respectively, at the carbon K edge for the first time. The interpretation of the XA/XE spectra was done based on theoretical calculations. Then, the chemical structure of the GQDs was characterized in situ by ATR-FTIR in water, thereby accounting for the importance of the interface between GQDs and water believed to play a central role in the chemical reactivity and the optical properties. We previously demonstrated that monitoring the OH vibrations of water molecules during exposure to humid air was a powerful method to probe H-bonding environment around carbon nanomaterials.3 For GQDs, clear surface-dependent water adsorption profiles are observed and discussed. Finally, UV/Vis absorption and photoluminescence measurements were done to characterize the optical properties of these GQDs. Our results suggest that the surface chemistry of the GQDs affects significantly their electronic structure and optical properties. These findings will contribute to an improved understanding of the structure–activity relationship of GQDs and other carbon nanomaterials with surface modifications.
Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals.1 The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms.2,3 We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In this contribution, I will discuss our recent results investigating the formation of (polymorphic) cocrystals and metal phosphonates.4 First investigations of a mechanochemical synthesis under controlled temperature which allow determining the activation barrier are presented. Furthermore, in situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases as a result of the reaction heat.5 Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemically synthesized compounds.
Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals.1,2 The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms.3,4 We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy (Fig.1a) The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In this talk I will discuss our recent results investigating the formation of (polymorphic) cocrystals.6-7 First investigations of a mechanochemical synthesis under controlled temperature (Fig 2a) which allow determining the activation barrier are presented.8 Furthermore, in situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases as a result of the reaction heat.
Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals.1,2 The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms.3,4 We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy (Fig.1a) The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In this talk I will discuss our recent results investigating the formation of (polymorphic) cocrystals.
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
Welding Technology
(2017)
Geothermal brine is considered to be an aggressive
environment as it contains various dissolved salts.
Even though carbon steel is commonly used as a
construction material due to its machinability and
economical reason, it is susceptible to uniform and
localized corrosion in a high temperature and high
pressure system. Therefore, a coating system is
introduced to protect the carbon steel against
corrosion in such environment.
1. Carbon steel is susceptible to uniform corrosion in presence of oxygen, with corrosion rate of immersion at 150 °C of 0.39 mm/a.
2. Exposure test of carbon steel at 150°C and 10 bar (pressurized by Ar) results in pitting corrosion with depth of 19 µm and width 4 µm on average.
3. OCP measurement shows that the stability of measurement is reached after 40 hours of immersion in the solution.
4. EIS measurement is useful to observe the effect of temperature, immersion time, and coating composition on the corrosion processes of coated metals for use in geothermal application.
Copolymer structure elucidation by multidimensional techniques with focus on UPLC x ESI-TOF-MS
(2017)
Structure elucidation of complex synthetic copolymers still represents a challenge. An one-dimensional separation technique cannot give the answer to the question: What are the molar mass distribution (MMD), the functionality distribution (FTD), the chemical composition distribution (CCD), the monomer sequence distribution (MSD), the topology differences within a single broad distributed polymer sample?
Since the first LC/ ESI-MS experiment of the Nobel prize winner John B. Fenn in 1984, the coupling of liquid chromatographic to mass spectrometric techniques gained a continuous rapid development.
Often the deficiencies of stand-alone methods can be bridged. LC, blind to structural information needs mass spectrometry as one of the most powerful detectors able to give detailed information on e.g. the repeat units, functionalization or copolymer composition of the chromatographic separated constituents. A separation prior to MS reduces radical the dispersity which is one of the reasons for failing of MS. Also problems with different ionization probabilities in complex mixtures can partly be overcame.
Different LC separation techniques as size exclusion chromatography (SEC), liquid adsorption chromatography (LAC), liquid chromatography at critical conditions (LCCC) and gradient elution liquid chromatography (GELC) combined with Matrix assisted Laser Desorption Ionization (MALDI) respectively Electrospray Ionization (ESI) Time of Flight (TOF) mass spectrometry are able to give information which otherwise are completely inaccessible. In some cases CID tandem mass spectrometry is applied. Fragmentation of suitable precursor ions resulted in typical fragment ion patterns. This technique enables an additional information on e.g. sequences, structural defects and topology of complex polymer mixtures.
Herein a new approach is demonstrated to provide evidence of different functionalities and short block sequences in statistical EO-PO copolymers. Furthermore silsesquioxane mixtures and Polyglycerols are investigated concerning occurring topology effects.
The novel heat treatment concept of “Quenching and Partitioning” (Q&P) enables producing low alloyed martensitic steels with high strength and formability. Therefore austenite, retaining from a quenching temperature between Mf and Ms, is stabilised by carbon diffusion. This stabilised austenite transforms in martensite (TRIP effect) under mechanical loading. Current investigations on the Q&P heat treatment of martensitic stainless steels reveal a further enhancement of mechanical properties due to higher amounts of austenite. Thus a tensile strength of 1.800 MPa and a maximum elongation of 20 % are possible, while mechanical properties under compression are much higher due to a distinct SD effect.
The presentation aims to gain a further understanding of the Q&P heat treatment and the resulting mechanical properties for the steel X46Cr13, especially the mechanical behaviour under dynamic mechanical loading condition. Results of drop work and Split Hopkinson Pressure Bar test confirms the findings of quasi static compression test. Furthermore, Charpy impact tests show higher impact toughness compared to the common heat treatment of quenching and tempering (Q&T). Complementary investigations indicate a higher corrosion resistance of Q&P compared to Q&T.
In the present study, Ti-6Al-4V bridge-like specimens were manufactured additively by selective laser melting (SLM) under different laser scanning speed conditions in order to compare the effect of process energy density on the residual stress state. Subsurface residual stress analysis was conducted by means of synchrotron diffraction in energy dispersive mode for three conditions: as-built on base plate, released from base plate, and after heat treatment on the base plate. The quantitative residual stress characterization shows a correlation with the qualitative bridge curvature method. Computed tomography (CT) was carried out to ensure that no stress relief took place owing to the presence of porosity. CT allows obtaining spatial and size pores distribution which helps in optimization of the SLM process.
High tensile residual stresses were found at the lateral surface for samples in the as-built conditions. We observed that higher laser energy density during fabrication leads to lower residual stresses. Samples in released condition showed redistribution of the stresses due to distortion. A method for the calculation of the stress associated to distortion of the parts after cutting from base plate is proposed. The distortion measurements were used as input for FEM simulations.
Atomic force microscopy based Infrared spectroscopy (AFM-IR) is a quickly evolving technique that provides chemical analysis and compositional mapping with spatial resolution far below conventional optical diffraction limits. This is possible since the detection method is based on a very sharp AFM tip which starts to oscillate when the sample starts to thermally expand (the changed is caused by the absorption of IR wavelength) where the thermal expansion is related to the IR absorption. This presentation briefly described the application of that new technique from polymer characterization and utilization of AFM-IR in material research, up to life science applications.
THz time domain spectroscopy (TDS) operates with short electromagnetic pulses. The sensitivity of the pulses to optical material property changes makes THz-TDS attractive for the detection of flaws in dielectric materials. Unfortunately, the X-ray computed tomography (CT) model holds only for THz-TDS reconstruction if minor refraction index differences between the inhomogeneities and the surrounding material matrix exist. A Time Domain SAFT algorithm has been developed to overcome the restrictions. THz time domain measurement on representative sample sets with inherent artefacts were performed to use them for the image reconstructions. The results will be presented and compared with optical surface images of the used test objects to evaluate the SAFT algorithm in relation to the reconstruction quality.
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.
There is an increasing interest in optical reporters like semiconductor and lanthanide-based nanocrystals with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, 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 for upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable 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 as well as by the lack of 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 densitydependent measurements of emission spectra and quantum yields in the wavelength region of 650 to 1650 nm
including calibration strategies and first candidates for potential fluorescence standards. Subsequently, the photoluminescence properties of different types of nanocrystals are presented and discussed including absolute photoluminescence measurements of upconversion and down conversion emission in different solvents.
There is an increasing interest in molecular and nanoscale 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, the photoluminescence properties of different types of nanocrystals are presented including the upconversion and downconversion emission of differently sized and surface functionalized lanthanide-doped nanoparticles and photoluminescence quenching effects are quantified.
Comparison of fluorescence measurements performed on different fluorescence instruments, analyte quantification from fluorescence intensities as well as the determination of fluorescence quantum yields require instrument calibration and consideration of the wavelength-dependent instrument-specific quantities spectral photon flux reaching the sample and spectral responsivity. Here, we present guidelines and recommendations for the qualification of fluorescence instruments and introduce suitable chromophore-based reference materials. Moreover, the design concepts of the different BAM fluorescence standards are discussed.
Mandatory for the comparison of different emitter classes and the rational design of the next generation of molecular and nanoscale reporters are reliable and quantitative photoluminescence measurements. This is of special relevance for all fluorescence applications in the life and material sciences. In the following, proccedures for the determination of this spectroscopic key parameter are presented including material-specific effects related to certain emitters
Upconversion nanoparticles (UCNPs) offer new strategies for luminescence-based sensing and imaging. One of the best studied materials are ..-NaYF4 UCNPs doped with 20 % Yb3+ and 2 % Er3+, which efficiently convert 976 nm light to photons emitted at 540 nm, 655 nm, and 845 nm, respectively, reveal long luminescence lifetimes (> 100 µs), are photostable and chemically inert. Their upconversion (UC) luminescence (UCL) properties are, however, strongly influenced by particle size, surface chemistry, and microenvironment. In addition, the multiphotonic absorption processes responsible for UCL render UCL excitation power density (..) dependent. This makes quantitative UCL measurements as well as the determination of UC quantum yields (.UC) very challenging.
The rational design of brighter UCNPs particle architectures and the interest in identifying optimum particle architectures for FRET-based sensing and imaging schemes, which often rely on core-only UCNPs to minimize donor-acceptor distances, encouraged us to assess the influence of particle size and P on UCL. Here, we present the photophysical properties of a series of hexagonal NaYF4 UCNPs with sizes from 10 to 43 nm with different surface ligands dispersed in organic solvents and water studied by steady state and time-resolved fluorometry as well as quantitatively by integrating sphere spectrometry with P varied over about three orders of magnitude. Our results underline the need for really quantitative luminescence studies for mechanistic insights and the potential of high P to compensate for UCL quenching due to high energy phonons and surface effects.
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.
The technological importance, the regularity of the microstructure and the complexity of the mechanical behavior of single crystal superalloys have motivated the development of a large number of mathematical models of the mechanical behavior of these alloys in the last two decades. While crystal viscoplasticity has proven to be an efficient framework to account for their anisotropy, several issues are still challenging. Indeed, most models consider that octahedral and cubic slip systems contribute to the largest part of the plastic deformation. However, the exact nature of cubic slip is still controversial and the precipitates can be sheared by <112> slip systems at intermediate temperatures, which largely influence the dependence of the flow rate on the orientation under creep conditions. Due to the different strengths of the matrix and the precipitates and the large volume fraction of the precipitate phase, a complex distribution of internal stresses exists, which can difficultly be captured by the conventional back stress models of plasticity. In addition, at high temperature, the microstructure degrades and the residual mechanical strength is reduced. The driving force for this microstructure degradation is intimately connected to the distribution of the internal stresses. As a result of this complexity, a large number of tests are usually required to fully characterize the mechanical behavior of single crystal superalloys. This in turn largely impedes the implementation of inelastic modeling in the industrial praxis.
The lecture summarizes the principal types of constitutive models for single crystal superalloys and reviews some recent advances in this area. In particular, it is shown how simulations at the microstructure scale level combined with conventional testing and microscopic analysis helped to improve our understanding of the mechanical behavior of single crystal superalloys. Directional coarsening, the importance of internal stresses, orientation dependency and the corresponding modeling issues are discussed. Also open questions are highlighted.
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.
This presentation gives an overview on the activities and actions of the members of the forum of notified bodies for pyrotechnics under the European Directive 2013/29/EU. It comprises information on the recent members of the forum, details on conformity assessment procedures (e.g. module G), labelling of pyrotechnics, round robin tests and specific category depending Q&A.
Over the last couple of years a lot of effort was put into the development of internationally recognized standards for fireworks. The work is globally organized within the ISO/TC 264 “Fireworks”. This technical committee consists of five working groups (WGs), set up for the development of criteria for safety requirements, test methods and labelling of fireworks articles:
WG1: Terminology
WG2: Safety requirements and labelling
WG3: Categories and types
WG4: Test methods
WG5: Fireworks display
The Bundesanstalt für Materialforschung und -prüfung (BAM) was from the beginning part of the entire standardization activities and participated actively with experts in all WGs, project leadership and provided the chairman for the ISO/TC 264-WG2 “Safety requirements and labelling”. This paper aims at giving an overview about the meetings, the philosophy behind the chosen standardization approaches and selected information on safety requirements, test methods and labelling aspects.
The phase transformation under various cooling rates and in different HAZ regions for high strength armour steel was analysed by dilatometry. To develop a Continuous Colling Transformation (CCT) diagram, the samples were heated up to a peak temperature of 1250 °C to achieve a coarse grained microstructure and then cooled down with a cooling time t8/5 varying from 3 s to 240 s. Analysis of dilatation curves revealed the austenite decomposition process, during which transformation temperatures were determined. The results showed martensitic transformations for all welding relevant cooling times.
Furthermore, to analyse different heat affected subzones of the weld, the peak temperature was varied between 550 °C and 1250 °C at a constant cooling time t8/5 of 6 s. The simulated coarse grained heat affected zone (CGHAZ) and fine grained heat affected zone (FGHAZ) showed only martensitic transformations with transformation temperatures below 400 °C. The steel exhibited an inhomogeneous hardness with hardening in the CGHAZ and FGHAZ and softening in the intercritical and subcritical HAZ. The physically simulated microstructure was validated by a real hybrid laser-arc weld microstructure.
The sources of human error
(2017)
Perfect flawless performance does not exist. Yet we expect people in organisations with high safety and reliability demand to perform at their best so that the systems designed, operated and maintained by people do not fail. Still, even the best guarded systems fail. The goal of the study of human factors is avoiding the negative effects of the interaction between humans and technology as well as decreasing them to increase the well-being of people, functioning of the systems, and safety. This is achieved by identifying human performance problems, by applying human knowledge to the design of the system, and by utilizing gained knowledge to other similar situations that exist currently or will occur in the future.
This presentation will outline the definition, classification and misconceptions about human error and discuss the differences between traditional and contemporary understanding and prevention of human error. Practical examples from own research, highlighting the importance of identifying risks and appropriately dealing with them, will be given.
The demand for high-performance materials has strongly increased over the last decade. One way to improve their performance is to introduce material gradients as found in Nature (for example squid beaks, spider fangs, mussel byssal threads).
One path towards the achievement of such material gradients is the synthesis of hybrid (gradient) copolymers, for instance based on silane and organic monomers. Since not all gradient copolymers can be synthesized by utilising the reactivity ratios of the monomers, forced gradients have to be used. However, in order to obtain gradient copolymers at high conversions, living or pseudo-living copolymerizations have to be performed and so far only few hybrid (organic / inorganic) gradient copolymers have been reported. In this contribution we will present the synthesis of a novel organic / inorganic hybrid copolymer via controlled radical polymerization.
Influence of solid-state-synthesis conditions on properties of oxide thermoelectric materials
(2017)
Calcium cobaltite and calcium manganate are promising oxide thermoelectric materials for applications between 600 °C and 900 °C in air to convert waste heat directly into electrical power. The solid state reaction, well known for large scale powder synthesis of functional materials, is used for the production of thermoelectric oxides. As a high temperature process, the powder synthesis consumes a lot of energy. In different studies, different synthesis conditions were used for the preparation of calcium cobaltite and calcium manganate powder. To the author’s knowledge, a systematic study of the synthesis conditions of calcium cobaltite and calcium manganate has not yet been published.
Therefore, the synthesis conditions for calcium cobaltite (temperature, dwell time, and particle size of raw materials) were studied with a statistical design of experiments (2³) and investigated regarding phase composition (XRD), densification and thermoelectric properties. The gained knowledge was used to optimize the solid state reaction of calcium manganate.
This study showed that a higher energy input (elevated temperatures, longer dwell times, or repeated calcinations) during powder synthesis does not improve but deteriorate the thermoelectric properties of calcium cobaltite. The same correlation was determined for the densification. As a higher energy input during powder synthesis leads to a larger grain size and therefore to a reduced sinter activity the densification at a given sinter profile is minimize as well as the thermoelectric properties. These results can be used to minimize the energy demand for the powder synthesis of oxide thermoelectric materials.
The talk addresses layer-based sensors for monitoring applications. In particular, sensor principles surface plasmon resonance (SPR), air-coupled ultrasonic, and magneto-optical coupling are discussed. Optical sensors on planar substrates are prepared by sol-gel, CVD- and PVD deposition techniques, ultrasonic sensors on planar and curved substrates are made by means of PVD processes, and magnetostrictive coatings for magneto-optical sensors are deposited on fibre-based Bragg gratings (FBGs) using PVD and ECD techniques. For all kinds of sensors design and function are explained and discussed, i.e. regarding sensitivity. It is shown that a) SPR enhanced ellipsometry is a promising tool for gas monitoring of hazardous gases, that b) thermos-acoustic and piezo-electric pulse-echo techniques are relevant for damage inspection of hidden volume defects of CFRPs, and that c) magnetostrictive-optical sensors with self-calibrating (magnetic reference field) function are useful for structural health monitoring in terms of strain sensors.
The wetting behavior of material surfaces can be controlled by surface structures. We functionalized case-hardened alloyed carbon steel to modify the wetting behavior using ultrashort laser pulses (fs- to ps-range). The laser processing was performed by scanning the laser beam across the surface of initially polished flat sample material. An experimental study of the laser processing parameters (peak fluence, scan velocity, line overlap) rendered an assignment of different regimes associated with characteristic surface morphologies (laser-induced periodic surface structures, grooves, micro cones, etc.) possible. Analyzing the surface using optical as well as scanning electron microscopy allowed the identification of morphologies providing the optimum similarity to the natural skin of non-moisture havesting lizards. For mimicking skin structures of moisture-harvesting lizards, additionally a two-step laser processing strategy was established for realizing hierarchical microstructures. In this approach, micrometer-scaled capillaries (step 1) were superimposed by a laser-generated regular array of small dimples (step 2). Optical focus variation imaging measurements finally revealed the three dimensional topography of the laser processed surfaces derived from lizard skin structures. The functionality of these surfaces was analyzed in view of wetting and directional fluid transport properties. The results suggest possible applications of the laser-structured surfaces.
Characterisation of degradation and determination of end-of-lifetime criterion for O-ring seals
(2017)
The ageing of polymers, including elastomers, is an undesirable but inevitable process leading to a limited lifetime of rubber products such as seals. Independent of the application, as e.g. automotive, piping or container applications, a long lifetime or at least a timely exchange of a seal before occurence of critical failure is desired.
In order to investigate the degradation of material properties and to determine the lifetime of elastomers used as seals, an ageing programme was started with hydrogenated acrylonitrile butadiene rubber (HNBR), ethylene propylene diene rubber (EPDM) and fluorocarbon rubber (FKM) [1-3]. Both O-ring seals (uncompressed and compressed by 25 %) with a cord diameter of 10 mm as well as sheets with a thickness of 2 mm were aged at 75 °C, 100 °C, 125 °C and 150 °C for up to two years. The changes of material properties during ageing were characterised for each material using the sheets by means of e.g. dynamic-mechanical analysis and tensile tests, while sealing properties such as compression stress relaxation (CSR), compression set (CS) and leakage rate were determined on O-rings. The experimental results indicate that while material properties, CSR and CS show considerable degradation effects, the static leakage rate stays constant or even decreases before failure occurs quite suddenly at advanced degradation levels. This reveals that static leakage rate has only limited sensitivity for the degradation of the seal material.
Our approach to determine a suitable end of lifetime criterion, which involves a partial decompression of the seal during the leakage test, is presented and discussed.
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.
In order to satisfy the growing requirements towards lightweight design and resource efficiency in modern steel constructions, e.g. mobile cranes and bridges, high-strength steels with typical yield strength ≥ 690 MPa are coming into use to an increasing extent. However, these steels require special treatment in welding. The susceptibility for degradation of the mechanical properties in presence of hydrogen increases significantly with increasing yield strength. In case of missing knowledge about how and which amount of hydrogen is uptaken during welding, hydrogen assisted cracking can be a negative consequence. Moreover, modern weld technology like the modified spray arc process enables welding of narrower weld seams. In this context, a reduced number of weld beads, volume and total heat input are technical and economic benefits. This work presents the influence of welding parameters on the diffusible hydrogen content in both (1) single-pass and (2) multi-layer welds. Different hydrogen concentrations were detected by varied contact tube distance, wire feed speed, arc length as well as varied arc type (transitional arc and modified spray arc). The results showed, that all welding parameters had significant influence on the diffusible hydrogen concentration in the single-pass welds. By increasing the number of weld beads in case of multi-layer welding, the hydrogen concentration have been substantially reduced. Whereby, differences in hydrogen concentrations between both arc types are present.
Introduction on BAM developments in the project “Microbially Induced Corrosion” (MIC) for new analytical tool, surface modifications and bacterial biofilm developments in the course of the ICBM-Colloquia at the Institut für Chemie und Biologie des Meeres (ICBM) of the Carl-von-Ossietzky-University in Oldenburg.
Presentation of the MIC-project (Microbially Induced Corrosion) within the focus area Materials of the BAM. Strategies, developments and innovations in the area of analytical tools, surface modifications, polymer stability and biofilm-enhanced deteriorations of materials in the context of microbially induced corrosion processes.
Microbially induced corrosion (MIC) is a severe cost and risk factor for the oil and gas industry, water heat- and cooling systems, waste water management, and infrastructural constructions. The industrial preventions management of MIC focuses on eliminating present microorganisms, which leads to the repeated and time-consuming application of biocides. However, biocides are often only minor effective for microorganisms that live protected from these agents in a biofilm matrix formed on material surfaces. In recent years, microbiologist have renewed our vision on the electrochemical processes underlying material corrosion induced by sulfate reducing bacteria, but the knowledge at the level of multispecies biofilm formation and the effects of material’s properties are still rather scarce.
Therefore, an interdisciplinary team of material scientists, chemists and microbiologists, established a MIC-research platform at the Federal Institute for Materials Research and Testing (BAM) to study the effects of material’s properties and biofilm formation on MIC. Using femtosecond laser pulse technology steel surfaces with defined nanostructures were manufactured. The test pieces were incubated using a flow-through chambers setup with different organisms relevant for biofilm studies. Our studies showed, that nanoscale structures severely affect the biofilm thickness and, hence, growth for health threatening organisms like E. coli and S. aureus, but also for MIC-relevant bacteria such as Fe(III)-reducing Shewanella spec.
Another aspect of the biofilm matrix is the establishment of microscale environments with conditions, such as anaerobic or acidic microenvironments, which promotes a diverse multispecies community. However, the detection and visualization of such small-scale microenvironments is rather challenging. Further, it could directly indicate the activity of microorganism influencing or inducing corrosion processes. Therefore, dye-stained nanoscale particles, bearing pH-responsive fluorophores at the surface, were developed to measure the pH at the biofilm’s surface and within the matrix using confocal laser scanning microcopy. The particles will be further advanced to measure other environmentally relevant parameters, including oxygen concentration, and concentrations of selected metal ions indicative of corrosion of e.g., materials used for water pipelines. In the future, our platform and its analytical tools will be employed to study the formation of biofilms in dependency of the respective support material, its surface properties like roughness, and the microbial community.
Trapping in T24 steel weld joints – Effects on activation energy for hydrogen diffusion during TDA
(2017)
Failure cases in the past decade exhibited severe cracking in T24 welds and showed that generally hydrogen-assisted cracking (HAC) occurring up to 200°C cannot be excluded. A basic understanding is necessary on how hydrogen diffusion is influenced by the weld process. In this regard, both weld microstructures HAZ and weld metal have particular influence on hydrogen diffusion compared to the base material. In general, hydrogen diffusion at a certain temperature is described by diffusion coefficients representing an effective value of combined lattice diffusion and effects of reversible hydrogen traps. Those traps are typically precipitates, interstitials, grain boundaries and so on. A common approach to describe the trap character and its effect on diffusion is the determination of so-called activation energy. This can be done by respective thermal desorption analysis (TDA) with linear heating. In the present study, different T24 as-welded microstructures (BM, HAZ, WM) were investigated. For that purpose, electrochemically hydrogen charged specimens were analyzed by TDA with linear heating using a mass spectrometer for detection of ultra-low hydrogen amounts. The results showed that typically the as-welded HAZ had higher energy traps than the tempered base material. Nonetheless two important effects were ascertained: (1) it is strictly necessary to monitor the sample temperature due to its great impact on the hydrogen desorption peak temperature and (2) the real heating rate in the specimen vs. the applied heating rate has to be considered. Both influence the calculated activation energy, i.e. the assigned hydrogen trap character (moderate or strong trap), which changed up to a factor of two in terms of the calculated activation energy. This effect can be much more important compared to the microstructure effect itself. Hence, suitable experimental boundary conditions should be mandatory for the determination of hydrogen trap kinetics.
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.
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.
The aim of this study was to develop a lightweight composite façade element for refurbishment of existing façades. It was crucial to minimize the thermal bridges and to undercut the thermal requirement of the system existing façade new element. The awareness of the environmental impact of the building sector is increasing. In this context, ultra-high performance concrete (UHPC) materials are shown to be promising alternatives with advantages such as lower embodied energy and reduced environmental impact. Predictions suggest that UHPC composite elements for building envelopes could have other benefits such as an increased service life, optimized use of building area due to thinner elements and minimized maintenance due to the absence of reinforcement or use of non-corrosive reinforcing materials such as carbon fibers. In this framework, composite elements have been developed combining an autoclaved aerated concrete insulation layer with an external UHPC supporting layer. The results show that the lightweight composite element has a good performance in term of thermal transmittance and minimization of thermal bridges.
Development of durable transparent enamel colors for the manufacture of decorate glass panels
(2017)
Today glass is broadly used in modern architecture. For applications indoor it is possible to produce decor glass by using enamel colors and glass painting techniques without any problems. However, this is more limited for applications outdoor. Humidity and environmental pollution attack the surface of the coating and damage it strongly. There are only few colors on the market which are resistant towards acids and bases until now. Additionally, most of those colors are opaque. In order to extend the color palette, chemically resistant colored glasses are being developed which are transparent, relatively low melting and intensively toned even in thin coat thickness. To achieve such ambitious aim, many parameters have to match which act in complex manner. Metal oxides were used to color the glasses. A lead-free glass composition was developed to avoid an exposition of heavy metals to the environment. The glasses were characterized, in particular in terms of their thermal properties, their crystallization behavior and their chemical durability. Different practical applications will be shown.