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Korrosionsschutz bekennt Farbe - Schnelltest auf Korrosionsgefahr bei nicht rostenden Stählen
(2017)
In Chemieanlagen ist die Passivschicht von Rohrsystemen und Behältern aus nichtrostendem Stahl nicht nur durch den rauen Produktionsalltag gefährdet. Auch im Neuzustand können Schäden entstehen, bspw. durch Schleifvorgänge oder eine unvollständige Entfernung von Anlauffarben nach dem Schweißen. TÜV SÜD Chemie Service beteiligte sich an der Prüfung eines von der Bundesanstalt für Materialforschung und -prüfung (BAM) entwickelten Korrosionsschnelltests. KorroPads liefern in nur 15 Minuten eine valide Aussage zum Zustand der Passivschicht auf den Werkstoffoberflächen.
In this review we present new concepts and recent progress in the application of semiconductur quantum dots (QD) as labels in two important areas of biology, bioimaging and biosensing. We analyze the biologically relevant properties of QDs focusing on the following topics: QD surface treatment and stability labeling of cellular structures and receptors with QDs, incorporation of QDs in living cells, cytotoxicity of QDs and influence of the biolocical environment on the biological and optical properties of QDs. Initially, we consider utilization of QDs as agants in high-resolution bioimaging techniques that can provide information at the molecular levels. The deverse range of modern live-cell QD-based imaging techniques with resolution far beyond the diffraction limit of light is examined. In each technique, we discuss the pros and cons of QD use and deliberate how QDs can be further engineered to facilitate their application in the respective imaging techniques and to produce significant improvements in resolution. Then we review QD-based point-of-care bioassays, bioprobes, and biosensors designed in different formats ranging from analytic biochemistry assays and ELISA, to novel point-of-care smartphone integrated QD-based biotests. Here, a wide range of QD-based fluorescence bioassays with optical transduction, electrochemiluminescence and photoelectrochemical assays are discussedc. Finally, this review provides an analysis of the prospects of application of QDs in selected important Areas of biology.
The performance of grating interferometers coming up now for Imaging interfaces within materials depends on the efficiency (visibility) of their main component, namely the phase grating. Therefore, experiments with monochromatic synchrotron radiation and corresponding simulations are carried out. The visibility of a Phase grating is optimized by different photon energies, varying detector to grating distances and continuous rotation of the phase grating about the grid lines. Such kind of rotation changes the projected grating shapes, and thereby the distribution profiles of phase shifts. This yields higher visibilities than derived from ideal rectangular shapes. By continuous grating rotation and variation of the propagation distance, we achieve 2D visibility maps. Such maps provide the visibility for a certain combination of grating orientation and detector position. Optimum visibilities occur at considerably smaller distances than in the standard setup.
In the present study, we applied a regularized inversion method to extract the particle size, magnetic moment and relaxation-time distribution of magnetic nanoparticles from small-angle x-ray scattering (SAXS), DC magnetization (DCM) and AC susceptibility (ACS) measurements. For the measurements the particles were colloidally dispersed in water. At first approximation the particles could be assumed to be spherically shaped and homogeneously magnetized single-domain particles. As model functions for the inversion, we used the particle form factor of a sphere (SAXS), the Langevin function (DCM) and the Debye model (ACS). The extracted distributions exhibited features/peaks that could be distinctly attributed to the individually dispersed and non-interacting nanoparticles. Further analysis of these peaks enabled, in combination with a prior characterization of the particle ensemble by electron microscopy and dynamic light scattering, a detailed structural and magnetic characterization of the particles. Additionally, all three extracted distributions featured peaks, which indicated deviations of the scattering (SAXS), magnetization (DCM) or relaxation (ACS) behavior from the one expected for individually dispersed, homogeneously magnetized nanoparticles. These deviations could be mainly attributed to partial agglomeration (SAXS, DCM, ACS), uncorrelated surface spins (DCM) and/or intra-well relaxation processes (ACS). The main advantage of the numerical inversion method is that no ad hoc assumptions regarding the line shape of the extracted distribution functions are required, which enabled the detection of these contributions. We highlighted this by comparing the results with the results obtained by standard model fits, where the functional form of the distributions was a priori assumed to be log-normal shaped.
The evolution of the internal strains during in situ tension and compression tests has been
measured in an MgY2Zn1 alloy containing long-period stacking ordered (LPSO) phase using
neutron diffraction. The alloy was extruded at two different temperatures to study the influence
of the microstructure and texture of the magnesium and the LPSO phases on the deformation
mechanisms. The alloy extruded at 623 K (350 °C) exhibits a strong fiber texture with the basal
plane parallel to the extrusion direction due to the presence of areas of coarse non-recrystallised
grains. However, at 723 K (450 °C), the magnesium phase is fully recrystallised with grains
randomly oriented. On the other hand, at the two extrusion temperatures, the LPSO phase
orients their basal plane parallel to the extrusion direction. Yield stress is always slightly higher
in compression than in tension. Independently on the stress sign and the extrusion temperature,
the beginning of plasticity is controlled by the activation of the basal slip system in the dynamic
recrystallized grains. Therefore, the elongated fiber-shaped LPSO phase which behaves as the
reinforcement in a metal matrix composite is responsible for this tension–compression asymmetry.
Using the novel optical measurement technique together with the optical flow algorithm, a twodimensional deformation analysis during welding has been conducted. This technique provides for the first time a measurement of the strain field locally in the immediate vicinity of the assumed solidification front. The described procedure of the opticalmeasurement allows to determine the real martial-dependent values of critical strain and strain rate characterising transition to the hot cracking during laser welding processes. The local critical strain that obtained in the assumed solidification showed that the local critical strain decreases as the strain rate increases. Moreover, this phenomenon has also been shown with results from the CTW-test, since the global strain decreases with an increase in the external strain rate.
The process of laser cladding has become more important during recent years because of its broad application for cladding, repair or additive manufacturing. In the field of mechanical engineering, one use is the repair of turbine blades. For high quality and reliability of the repaired components, it is necessary to adjust the weld bead geometry to the specific repair task. The bead geometry influences the metallurgical bonding and the degree of dilution as well as the formation of defects like pores or cracks. Therefore, it is important to know the effects of the different parameters on the welding bead. A valuable tool to meet this industrial challenge is the design of experiments (DoE). In this context, the user can choose between a huge number of test plans. Greater Profit of information is expected by a larger test range. In order to confirm the acceptance, a five-step full factorial test plan is compared to a central composite design in this paper. Moreover, the limits of the experimental range are indicated and restrictions can be derived. As the results show, the essential effects are detected with a full factorial test plan as well as with a central composite design. Merely the effect strength could not always be specified unambiguously. On this account and in consideration of cost efficiency, the use of central compound design is recommended in industrial applications.
The elucidation of mechanisms underlying the cellular uptake of nanoparticles (NPs) is an important topic in nanotoxicological research. Most studies dealing with silver NP uptake provide only qualitative data about internalization efficiency and do not consider NP-specific dosimetry. Therefore, we performed a comprehensive comparison of the cellular uptake of differently coated silver NPs of comparable size in different human intestinal Caco-2 cell-derived models to cover also the influence of the intestinal mucus barrier and uptake-specialized M-cells. We used a combination of the Transwell system, transmission electron microscopy, atomic absorption spectroscopy, and ion beam microscopy techniques. The computational in vitro sedimentation, diffusion, and dosimetry (ISDD) model was used to determine the effective dose of the particles in vitro based on their individual physicochemical characteristics. Data indicate that silver NPs with a similar size and shape show coating-dependent differences in their uptake into Caco-2 cells. The internalization of silver NPs was enhanced in uptake-specialized M-cells while the mucus did not provide a substantial barrier for NP internalization. ISDD modeling revealed a fivefold underestimation of dose–response relationships of NPs in in vitro assays. In summary, the present study provides dosimetry-adjusted quantitative data about the influence of NP coating materials in cellular uptake into human intestinal cells. Underestimation of particle effects in vitro might be prevented by using dosimetry models and by considering cell models with greater proximity to the in vivo situation, such as the M-cell model.
Environmental and sustainable economical concerns are generating a growing interest in biofuels predominantly produced from biomass. It would be ideal if an energy conversion device could directly extract energy from a sustainable energy resource such as biomass. Unfortunately, up to now, such a direct conversion device produces insufficient power to meet the demand of practical applications. To realize the future of biofuel-fed fuel cells as a green energy conversion device, efforts have been devoted to the development of carbon-based nanomaterials with tunable electronic and surface characteristics to act as efficient metal-free electrocatalysts and/or as supporting matrix for metal-based electrocatalysts. We present here a mini review on the recent advances in carbon-based catalysts for each type of biofuel-fed/biofuel cells that directly/indirectly extract energy from biomass resources, and discuss the challenges and perspectives in this developing field
Ectoine plays an important role in protecting biomolecules and entire cells against environmental stressors such as salinity, freezing, drying and high temperatures. Recent studies revealed that ectoine also provides effective protection for human skin cells from damage caused by UV-A radiation. These protective properties make ectoine a valuable compound and it is applied as an active ingredient in numerous pharmaceutical devices and cosmetics. Interestingly, the underlying mechanism resulting in protecting cells from radiation is not yet fully understood. Here we present a study on ectoine and its protective influence on DNA during electron irradiation. Applying gel electrophoresis and atomic force microscopy, we demonstrate for the first time that ectoine prevents DNA strand breaks caused by ionizing electron radiation. The results presented here point to future applications of ectoine for instance in cancer radiation therapy.
Many engineering structures are nowadays made of composite materials or metal foam. These modern engineering materials contain very complex inner geometry. To simulate the deformational behaviour of these structures often requires a high number of discretisation elements. This in turn yields a very large system of linear equations that are extremely time and memory consuming or practically impossible to solve. It is therefore desirable to find an approach to overcome this obstacle. In this paper a numerical method is proposed to find an approximate substitute model for geometrical complex structures.
Efficient water oxidation catalysts are required for the development of water splitting technologies. Herein, the synthesis of layered hybrid NiFephenylphosphonate compounds from metal acetylacetonate precursors and phenylphosphonic acid in benzyl alcohol, and their Oxygen evolution reaction performance in alkaline medium, are reported. The hybrid particles are formed by inorganic layers of NiO6 and FeO6 distorted octahedra separated by bilayers of the organic group, and template the Formation in situ of NiFe hydroxide nanosheets of sizes between 5 and 25 nm and thicknesses between 3 and 10 nm. X-ray absorption spectroscopy measurements suggest that the hybrid also acts as a template for the local structure of the metal sites in the active catalyst, which remain distorted after the transformation. Optimum electrocatalytic activity is achieved with the hybrid compound with a Fe content of 16%. The combination of the synergistic effect between Ni and Fe with the structural properties of the hybrid results in an efficient catalyst that generates a current density of 10 mA cm−2 at an overpotential of 240 mV, and also in a stable catalyst that operates continuously at low overpotentials for 160 h.
Miniaturized pacemakers with a surface consisting of a Ti alloy may have to be removed after several years from their implantation site in the heart and shall, therefore, not be completely overgrown by cells or tissue. A method to avoid this may be to create at the surface by laser-ablation self-organized sharp conical spikes, which provide too little surface for cells (i.e., fibroblasts) to grow on. For this purpose, Ti-alloy substrates were irradiated in the air by 790 nm Ti:sapphire femtosecond laser pulses at fluences above the ablation threshold. The laser irradiation resulted in pronounced microstructure formation with hierarchical surface morphologies. Murine fibroblasts were seeded onto the laser-patterned surface and the coverage by cells was evaluated after 3–21 days of cultivation by means of scanning electron microscopy. Compared to flat surfaces, the cell density on the microstructures was significantly lower, the coverage was incomplete, and the cells had a clearly different morphology. The best results regarding suppression of cell growth were obtained on spike structures which were additionally electrochemically oxidized under acidic conditions. Cell cultivation with additional shear stress could reduce further the number of adherent cells.
Oberflächendetektive im Praxiseinsatz - Schnelltest auf Korrosionsgefahr an nichtrostenden Stählen
(2017)
Die Passivschicht von Behältern und Rohrsystemen aus nichtrostendem Stahl ist nicht nur durch den rauen Industriealltag gefährdet. Schon im Neuzustand können Schäden entstehen, etwa durch Schleifvorgänge oder ungenügende Entfernung von Anlauffarben. TÜV SÜD Chemie Service beteiligte sich an der Prüfung eines von der BAM entwickelten Schnelltests. Das Korropad-Verfahren liefert in nur 15 Minuten eine verlässliche Aussage zum Zustand der Passivschicht.
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 flourescence entensities. 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 designg of new flourophores with improved properties.
Here, we present strategies to versatile method-adaptable liquid and solid flourescence Standards for different flourescence paramters including traceable Instrument calibration procedures and the design of integrating spere setups for the absolute measurements of emission spectra and Quantum yields in the wavelength Region of 350 to 1600 nm. Examples are multi-Emitter glasses, spectral flourescence Standards, and quantum yield Standards for the UV/vis/NIR.
One of the fundamental principles of the UN-GHS (Globally Harmonized System of Classification and Labelling of Chemicals) is that all hazards of a chemical should be assigned and communicated. There is no general prioritization of hazards in the sense that certain hazard classes are not applicable if another one has been assigned. In contrast to health and environmental hazards, there are physical or chemical factors which preclude certain combinations of physical hazard classes. So far, there is no common understanding as to which combinations are relevant and which not. For example, should a pyrophoric liquid be classified as flammable liquid in addition, or is this redundant and unnecessary? In the course of the implementation of the GHS by countries or sectors and the actual application by industry all over the world, such questions become more and more important.
This publication systematically discusses all combinations of the UN-GHS physical hazard classes and assesses them with regard to the relevance of possible simultaneous assignment to a chemical. For many of the combinations an unambiguous decision based on theGHS alone is not possible, thus confirming that the question which physical hazard classes might be assigned simultaneously to a chemical is not trivial. As one more milestone on the path to a globally harmonized system for the classification of hazardous chemicals, this should be discussed and ultimately solved on a global basis. It is the hope that this publication might serve as an impetus for such discussions.
In this study, thickness related changes of the optical properties of doped tin oxide were studied. Two different sets of samples were prepared. The first set was doped with iron or nickel on silicon substrate with thicknesses of 29–56 nm, the second was iron doped on gold/glass substrate with 1.6–6.3 nm. The optical constants were determined by using spectral ellipsometry (SE) followed by modelling of the dielectric function with an oscillator model using Gaussian peaks. The analysis of the optical constants shows a dependence of the refraction and the absorption on the thickness of the doped tin oxide coating. In addition to the tin oxide absorption in the UV, one additional absorption peak was found in the near-IR/red which is related to plasmonic effects due to the doping. This peak shifts from the near-IR to the red part of the visible spectrum and becomes stronger by reducing the thickness, probably due to the formation of metal nanoparticles in this layer. These results were found for two different sets of samples by using the same optical model. Afterwards the second sample set was tested in the Surface Plasmon Resonance Enhanced Ellipsometric (SPREE) gas measurement with CO gas. It was found that the thickness has significant influence on the sensitivity and thus the adsorption of the CO gas. By increasing the thickness from 1.6 nm to 5.1 nm, the sensing ability is enhanced due to a higher coverage of the surface with the over coating. This is explained by the high affinity of CO molecules to the incorporated Fe-nanoparticles in the tin oxide coating. By increasing the thickness further to 6.3 nm, the sensing ability drops because the layer disturbs the SPR sensing effect too much.
The breadth of applications of nanoparticles and the access to food-associated consumer products containing nanosized materials lead to oral human exposure to such particles. In biological fluids nanoparticles dynamically interact with biomolecules and form a protein corona. Knowledge about the protein corona is of great interest for understanding the molecular effects of particles as well as their fate inside the human body. We used a mass spectrometry-based toxicoproteomics approach to elucidate mechanisms of toxicity of silver nanoparticles and to comprehensively characterize the protein corona formed around silver nanoparticles in Caco-2 human intestinal epithelial cells. Results were compared with respect to the cellular function of proteins either affected by exposure to nanoparticles or present in the protein corona. A transcriptomic data set was included in the analyses in order to obtain a combined multiomics view of nanoparticle-affected cellular processes. A relationship between corona proteins and the proteomic or transcriptomic responses was revealed, showing that differentially regulated proteins or transcripts were engaged in the same cellular signaling pathways. Protein corona analyses of nanoparticles in cells might therefore help in obtaining information about the molecular consequences of nanoparticle treatment.
The nucleophilic thiol–ene (thia-Michael) reaction between molecular rods bearing terminal thiols and bis-maleimides was investigated. The molecular rods have oligospiroketal (OSK) and oligospirothioketal (OSTK) backbones. Contrary to the expectations, cyclic oligomers were always obtained instead of linear rigid-rod polymers. Replacing the OS(T)K rods with a flexible chain yielded polymeric products, suggesting that the OS(T)K structure is responsible for the formation of cyclic products. The reason for the preferred formation of cyclic products is due to the presence of folded conformations, which have already been described for articulated rods.
Unraveling the Dynamics of Nanoscopically Confined PVME in Thin Films of a Miscible PVME/PS Blend
(2017)
Broadband dielectric spectroscopy (BDS) was employed to investigate the glassy dynamics of thin films (7−200 nm) of a poly(vinyl methyl ether) (PVME)/polystyrene (PS) blend (50:50 wt %). For BDS measurements, nanostructured capacitors (NSCs) were employed, where films are allowed a free surface. This method was applied for film thicknesses up to 36 nm. For thicker films, samples were prepared between crossed electrode capacitors (CECs). The relaxation spectra of the films showed multiple processes. The first process was assigned to the α-relaxation of a bulklike layer. For films measured by NSCs, the rates of α-relaxation were higher compared to those of the bulk blend. This behavior was related to the PVME-rich free surface layer at the polymer/air interface. The second process was observed for all films measured by CECs (process X) and the 36 nm film measured by NSCs (process X2). This process was assigned to fluctuations of constraint PVME segments by PS. Its activation energy was found to be thickness-dependent because of the evidenced thickness dependency of the compositional heterogeneity. Finally, a third process with an activated temperature dependence was observed for all films measured by NSCs (process X1). It resembled the molecular fluctuations in an adsorbed layer found for thin films of pure PVME, and thus, it is assigned accordingly. This process undergoes an extra confinement because of frozen adsorbed PS segments at the polymer/substrate interface. To our knowledge, this is the first example where confinement-induced changes were observed by BDS for blend thin films
L-Lactide is polymerized in bulk at 160 8C either with dibutyltin bis(benzylmercaptide) (SnSBzl), dibutyltin bis(benzothiazole 2-mercaptide) (SnMBT), or with dibutyltin bis(pentafluorothiophenolate) (SnSPF) as catalysts. SnSBzl yields linear polylactides having benzylthio-ester end groups in addition to cyclic polylactides, whereas SnMBT and SnSPF mainly or exclusively yield cyclic polylactides. This finding, together with model reactions, indicates that the SnS catalysts promote a combined ring-opening polymerization and polycondensation process including end-to-end cyclization. SnMBT caused slight racemization (3%–5%), when used at 160 8C. With SnSPF optically pure cyclic poly(L-lactide)s with high-molecular weights can be prepared at 160 8C.
Nanocomposites based on poly(L-lactide) (PLA) and organically modified Ni/Al layered double hydroxides (NiAl/LDHs) are prepared by melt blending and investigated by a combination of size exclusion chromatography, differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), wide-angle X-ray scattering, and broadband dielectric spectroscopy. A detailed comparison to the behavior of the corresponding MgAl/LDH–PLA nanocomposites is made. SAXS investigations show that the morphology of the NiAl/LDH–PLA nanocomposites is more intercalated compared to the MgAl/LDH based PLA nanocomposite, which is more exfoliated. The DSC investigation gives a different dependence of the degree of crystallization on the concentration of LDH for NiAl/LDH–PLA than for MgAl/LDH–PLA nanocomposite system. These differences are discussed taking the differences of the morphologies of both systems into account. Broadband dielectric spectroscopy reveals information about the molecular dynamics where essential differences are observed for all relaxation processes taking place in both systems which were related to the different morphologies.
The quantum yield is a critically important parameter in the development of lanthanide-based upconverting nanoparticles (UCNPs) for use as novel contrast agents in biological imaging and optical reporters in assays. The present work focuses on the influence of the beam Profile in measuring the quantum yield (f) of nonscattering dispersions of nonlinear upconverting probes, by establishing a relation between f and excitation light power density from a rate equation analysis. A resulting 60% correction in the measured f due to the beam profile utilized for excitation underlines the significance of the beam profile in such measurements, and its impact when comparing results from different Setups and groups across the world.
In concrete elements, simultaneously subjected to cyclic loadings and external alkalis, the risk for damage caused by or under participation of an alkali-silica reaction (ASR) is particularly high. This is of particular concern for concrete pavements due to the increasing heavy vehicle traffic and the application of sodium chloride (NaCl) de-icer during winter. Since 2004, the climate simulation concrete prism test (CS-CPT) has been used successfully to evaluate job mixtures for pavements by considering the impact of alkali-containing de-icers. However, the role of mechanical predamage on ASR is largely unclear. In a joint research project, the CS-CPT has been used to investigate the influence of preexisting microcracks on ASR. It was evident that an ASR initiated earlier in the predamaged concrete prisms due to the more rapid ingress of NaCl solution through the microcracks.
Approximation of the crack driving force for cracks at notches under static and cyclic loading
(2017)
The work deals with the efficient calculation of the elastic-plastic crack driving force (J-integral for monotonic loading andΔJ-integral under cyclic loading) for short cracks at notches as essential parameter for the reliable static and fatigue assessment of notched structures. The J- or ΔJ-integral is calculated based on analytical solutions for stress intensity factors, estimated by means of well-known weight function solutions in the case of cracks under power-law stress distributions. A plasticity-correction function is applied to the stress intensity factors to obtain the final expression of the crack driving force. The comparison between analytical solutions and finite element calculations in case of cracks at the weld toe in welded joints shows good agreement.
One of the great strengths of X-ray computed tomography over conventional inspection methods (ultrasound, thermography, radiography) is that it can image damage in 3D. However for curved ordeformed composite panels it can be difficult to automatically ascribe the damage to specific plies or inter-ply interfaces. An X-ray computed tomography (CT) data processing methodology is developed to extract the through-thickness distribution of damage in curved or deformed composite panels. The method is applied to [(0°/90°)2]s carbon fibre reinforced polymer (CFRP) panels subjected low velocity impact damage (5 J up to 20 J) providing 3D ply-by-ply damage visualisation and analysis. Our distance transform approach allows slices to be taken that approximately follow the composite curvature allowing the impact damage to be separated, visualised and quantified in 3D on a ply-by-ply basis. In this way the interply delaminations have been mapped, showing characteristic peanut shaped delaminations with the major axis oriented with the fibres in the ply below the interface. This registry to the profile of the panel constitutes a significant improvement in our ability to characterise impact damage in composite laminates and extract relevant measurements from X-ray CT datasets.
The 7th International Conference on Spectroscopic Ellipsometry (ICSE-7) was held in Berlin in June 2016, jointly organised by ICSE and BAM. The publication of the proceedings special issue in Applied Surface Science follows this event. In the special issue, about 100 articles on current topics of optics and surface science related to ellipsometry, polarimetry, and similar techniques are presented, underpinning the high significance of these techniques for many fields of materials science.
If fracture mechanics shall be applied to the total lifetime respectively the fatigue limit of components (within the meaning of the S-N curve approach) it has to address four challenges:
(a) It has to adequately describe so-called short crack propagation, which cannot be based on the common long crack concepts for principle reasons. Since the crack size is in the order of the plastic zone size, the modelling of short crack propagation cannot be based on the common linear elastic Delta K concept. Instead, an elastic-plastic parameter such as the cyclic J integral has to be applied. A second point is that the crack closure concept has to be modified in that the crack opening stress is not a constant, crack size- independent parameter but shows a transient behaviour with increasing short crack size.
(b) It has to provide a meaningful definition of the initial crack dimensions as the starting point for an S-N curve relevant (residual) lifetime analysis. This can be based either on the (statistical) size of material defects which can be treated as cracks or by the size of the crack which would arrest subsequent to early crack propagation, whatever is larger.
(c) It has to cope with the problem of multiple cracks for load levels higher than the fatigue limit such as it occurs in many applications in the absence of very large initial defects.
(d) This requires consequent statistical treatment taking into account variations in the local geometry of the area where crack initiation has to be expected as well as the scatter in the initial crack size and in the material data used for the analyses.
The unparalleled excited-state potential-energy landscape of the chromium(III)-based dye [1]3+ ([Cr(ddpd)2]3+; ddpd=N,N’-dimethyl-N,N’-dipyridin-2-ylpyridin-2,6-diamine) enables a strong dual emission in the near infrared region. The temperature dependence of this dual emission allows the use of [1]3+ as an unprecedented molecular ratiometric thermometer in the 210–373 K temperature range in organic and in aqueous media. Incorporation of [1]3+ in biocompatible nanocarriers, such as 100 nm-sized polystyrene nanoparticles and solutol micelles, provides nanodimensional thermometers operating under physiological conditions.
The mechanochemical Knoevenagel condensation of malononitrile with p-nitrobenzaldehyde was studied in situ using a tandem approach. X-ray diffraction and Raman spectroscopy were combined to yield time-resolved information on the milling process. Under solvent-free conditions, the reaction leads to a quantitative conversion to p-nitrobenzylidenemalononitrile within 50 minutes. The in situ data indicate that the process is fast and proceeds under a direct conversion. After stopping the milling process, the reaction continues until complete conversion. The continuous and the stopped milling process both result in crystalline products suitable for single crystal X-ray diffraction.
The practical performance of surface coatings in applications like catalysis, water splitting or batteries depends critically on the coating materials’ porosity. Determining the porosity in a fast and nondestructive way is still an unsolved problem for industrial thin-films technology. As a contribution to calibrated, non-destructive, optical layer characterisation, we present a multi-method comparison study on porous TiO2 films deposited by sol-gel synthesis on Si wafers. The ellipsometric data were collected on a range of samples with different TiO2 layer thickness and different porosity values. These samples were produced by templated sol-gel synthesis resulting in layers with a well-defined pore size and pore density. The ellipsometry measurement data were analysed by means of a Bruggeman effective medium approximation (BEMA), with the aim to determine the mixture ratio of void and matrix material by a multi-sample analysis strategy. This analysis yielded porosities and layer thicknesses for all samples as well as the dielectric function for the matrix material. Following the idea of multi-method techniques in metrology, the data was referenced to imaging by electron microscopy (SEM) and to a new EPMA (electron probe microanalysis) porosity approach for thin film analysis. This work might lead to a better metrological understanding of optical porosimetry and also to better-qualified characterisation methods for nano-porous layer systems.
1. IntroductionPorous materials, especially porous thin films play an importantrole in chemical and physical technology in every case where thecontact area between two media has to be maximised. From cataly-sis to photochemistry and photovoltaics, the applications of porouslayer materials are diverse and numerous [1–6].The accurate and non-destructive characterisation of porousfilms for layered systems poses a challenge. This applies especiallyfor the key parameter of porous films, their porosity, i.e. the mix-ing ratio between the Matrix of the film (host material) and thepore volume which is empty or filled with a fluid medium (inclu-sions). This parameter influences most of the physical and chemicalproperties of a porous thin film and is therefore essential for theunderstanding as well as the optimisation of this class of materials.
Multiple timescales in the photoswitching kinetics of crystalline thin films of azobenzene-trimers
(2017)
Functional materials that exhibit photoinduced structural phase transitions are highly interesting for applications in optomechanics and mechanochemistry. It is, however, still not fully understood how photochemical reactions, which are often accompanied by molecular motion, proceed in confined and crystalline environments. Here we show that thin films of azobenzene trimers exhibit high structural order and determine the crystallographic unit cell. We demonstrate that thin film can be switched partially reversibly between a crystalline and an amorphous phase. The time constant of the photoinduced amorphisation as measured with real-time x-ray diffraction ($\approx $ 220 s) lies between the two time constants (120 s and 2870 s) of the ensemble photoisomerisation processes that are measured via optical spectroscopy. Our observation of a photoinduced shrinking of the crystalline domains indicates a cascading process, in which photoisomerisation starts at the surface of the thin film and propagates deeper into the crystalline layer by introducing disorder and generating free volume. This finding is important for the rapidly evolving research field of photoresponsive thin films and smart crystalline materials in general.
The damage mechanisms slow crack growth (SCG) and environmental stress cracking (ESC), relevant for PE-HD materials are characterized based on improved full notch creep testing (FNCT) of two selected typical PE-HD materials for container applications. In this context, a distinction of the failure mechanisms as well as a categorization of involved media is suggested. Employing a novel FNCT device, elongation data were obtained in addition to conventional time-to-failure results of stress-dependent as well as temperature-dependent measurements. Changes in failure behavior, as determined by fracture surface analysis based on light microscopy (LM) and laser scanning microscopy (LSM), are correlated with FNCT results and used to introduce an additional possibility for the identification of brittle/ductile fracture behavior.
Aluminum has gathered toxicological Attention based on relevant human exposure and its suspected hazardous potential. Nanoparticles from food supplements or Food contact materials may reach the human gastrointestinal tract.
Here, we monitored the physicochemical fate of aluminum containing nanoparticles and aluminum ions when passaging an in vitro model of the human gastrointestinal tract. Smallangle X-ray scattering (SAXS), transmission electron microscopy (TEM), ion beam microscopy (IBM), secondary ion beam mass spectrometry (TOF-SIMS), and inductively coupled plasma mass spectrometry (ICP-MS) in the singleparticle mode were employed to characterize two aluminumcontaining nanomaterials with different particle core materials (Al0, γAl2O3) and soluble AlCl3. Particle size and shape remained unchanged in saliva, whereas strong Agglomeration of both aluminum nanoparticle species was observed at low pH in gastric fluid together with an increased ion release. The levels of free aluminum ions decreased in intestinal fluid and the particles deagglomerated, thus liberating primary particles again. Dissolution of nanoparticles was limited and substantial changes of their shape and size were not detected. The amounts of particle-associated phosphorus, chlorine, potassium, and calcium increased in intestinal fluid, as compared to nanoparticles in standard dispersion.
Interestingly, nanoparticles were found in the intestinal fluid after addition of ionic aluminum. We provide a comprehensive characterization of the fate of aluminum nanoparticles in simulated gastrointestinal fluids, demonstrating that orally ingested nanoparticles probably reach the intestinal epithelium. The balance between dissolution and de novo complex formation should be considered when evaluating nanotoxicological experiments.
Two classes of polyesters were prepared by irreversible polycondensations.
The dependence of the dispersities on the experimental parameters such as synthetic method, chemical structure, molecular weight and initial monomer concentration was determined. At first it was demonstrated that it is essential for a correct calculation of Mn and Mw to include all oligomers down to the dimers in the evaluation of SEC curves. Furthermore, it was demonstrated for poly(e-caprolactone)s and polylactides that reversible polycondensations and ring-opening polymerizations with equilibration yield identical products.
Finally, the dependence of the dispersity on various experimental Parameters was determined for equilibrated poly(e-caprolactone)s and polylactides.
Discoloration Effects of High-Dose gamma-Irradiation and Long-Term Thermal Aging of (U) HMW-PE
(2017)
Two polyethylene types with ultra-high (UHMWPE) and high molecular weight (HMW-PE) used as neutron radiation shielding materials in casks for radioactive waste were irradiated with doses up to 600 kGy using a 60Co gammasource. Subsequently, thermal aging at 125∘C was applied for up to one year. Degradation effects in the materials were characterized using colorimetry, UV-Visspectroscopy, IR spectroscopy, and DSC. Both materials exhibited a yellowing upon irradiation.The discoloration of UHMW-PE disappeared again after thermal aging.Therefore, the yellowing is assumed to originate fromannealable color centers in the formof free radicals that are trapped in the crystalline regions of the polymer and recombine at elevated temperatures. For the antioxidantcontaining HMWPE, yellowing was observed after both irradiation and thermal aging. The color change was correlated mainly to decomposition products of the antioxidant in addition to trapped radicals as in UHMW-PE. Additionally, black spots appeared after thermal aging of HMW-PE.
In diesem Beitrag werden zerstörungsfreie Untersuchungen mittels aktiver Thermografie an Probekörpern aus CFK und GFK mit unterschiedlichen künstlichen Fehlstellen vorgestellt. Dabei wird die zeitliche und örtliche Temperaturverteilung nach der Erwärmung mit Blitzlampen oder mit einem Infrarot-Strahler mit einer Infrarot-Kamera erfasst. Zur späteren Rekonstruktion der Messdaten wurde ein numerisches Modell entwickelt. Dazu war die Bestimmung der thermophysikalischen und optischen Materialeigenschaften erforderlich, was in diesem Beitrag ebenfalls beschrieben wird. Die Ergebnisse der numerischen Modellierung werden mit den experimentellen Untersuchungen der aktiven Thermografie verglichen. Weiterhin werden die experimentellen Untersuchungen hinsichtlich der beiden Materialsysteme CFK und GFK und unter Berücksichtigung der Teiltransparenz des GFK-Materials sowie der unterschiedlichen Anregungsquellen bewertet.
This paper presents the first worldwide inter-laboratory comparison of small-angle X-ray scattering (SAXS) for nanoparticle sizing. The measurands in this comparison are the mean particle radius, the width of the size distribution and the particle concentration. The investigated sample consists of dispersed silver nanoparticles, surrounded by a stabilizing polymeric shell of poly(acrylic acid). The silver cores dominate the X-ray scattering pattern, leading to the determination of their radius size distribution using (i) the generalized indirect Fourier transformation method, (ii) classical model fitting using SASfit and (iii) a Monte Carlo fitting approach using McSAS. The application of these three methods to the collected data sets from the various laboratories produces consistent mean number- and volume-weighted core radii of Rn = 2.76 (6) nm and Rv = 3.20 (4) nm, respectively. The corresponding widths of the lognormal radius distribution of the particles were σn = 0.65 (1) nm and σv = 0.71 (1) nm. The particle concentration determined using this method was 3.0 (4) g l−1 or 4.2 (7) × 10−6 mol l−1. These results are affected slightly by the choice of data evaluation procedure, but not by the instruments: the participating laboratories at synchrotron SAXS beamlines, commercial and in-house-designed instruments were all able to provide highly consistent data. This demonstrates that SAXS is a suitable method for revealing particle size distributions in the sub-20 nm region (at minimum), out of reach for most other analytical methods.
The discussions on the nanoconfinement effect on the glass transition and glassy dynamics phenomena have yielded many open questions. Here, the thickness dependence of the thermal glass transition temperature of thin films of a PVME/PS blend is investigated by ellipsometry. Its thickness dependence was compared to that of the dynamic glass transition (measured by specific heat spectroscopy), and the deduced Vogel temperature (T0). While and T0 showed a monotonous increase, with decreasing the film thickness, the dynamic glass transition temperature () measured at a finite frequency showed a non-monotonous dependence that peaks at 30 nm. This was discussed by assuming different cooperativity length scales at these temperatures, which have different sensitivities to composition and thickness. This non-monotonous thickness dependence of disappears for frequencies characteristic for T0. Further analysis of the fragility parameter, showed a change in the glassy dynamics from strong to fragile, with decreasing film thickness.
Two strontium-based dicarboxylate systems [Sr(oBDC-F4)(H2O)2] (1) and [{Sr(oBDC)(H2O)2)·H2O] (2) were synthesized mechanochemically via milling of Sr(OH)2·8H2O with tetrafluorophthalic acid (H2oBDC-F4) or phthalic acid (H2oBDC), respectively. The new structures were determined ab initio from the powder X-ray diffraction (PXRD) data. Both compounds 1 and 2 crystallize in the monoclinic space group P21 /c as two-dimensional coordination polymers (2D-CPs). The determined structures were validated by extended X-ray absorption (EXAFS) data. Compounds 1 and 2 show different thermal stabilities. The fluorinated CP 1 is decomposed at 300 °C while the nonfluorinated CP 2 transforms into a new phase after thermal treatment at 400 °C. The two hydrated CPs exhibit small surface areas which increase after the thermal posttreatment for 1 but remains unchanged for the dehydrated sample of 2. Dynamic vapor sorption (DVS) experiments indicate that both the dehydrated and hydrated samples of 2 depict no significant differences in their adsorption isotherms. The DVS of water indicates that the phase transition after thermal posttreatment of 2 is irreversible.
Influence of weathering on the leaching behaviour of zinc and PAH from synthetic sports surfaces
(2017)
Synthetic materials used for outdoor sports grounds consist of a mix of inorganic, organic and polymeric compounds that show ageing due to weathering and a complex leaching behaviour by percolation of rainwater, which can limit its lifetime. Additionally, weathering exposure induces degradation processes in the polymers, which leads to the formation of new surfaces allowing water to access additional reservoirs of leachable compounds. A laboratory test comprising artificial weathering, ozonisation and subsequent leaching was developed to investigate this behaviour in a reproducible and controllable way. The experiments showed a general decline of Zn, polycyclic aromatic hydrocarbons (PAH) and total organic carbon (TOC) concentrations after an initial increase. Within this general trend, the course of concentration over exposure duration is very specific for individual sample materials and the analyte under investigation. The results indicate that weathering and degradation behaviour cannot be predicted from initial material conditions. Thus, weathering experiments are recommended to fill this gap of knowledge.
Carbon nanotube-grafted carbon fiber polymer composites: Damage characterization on the micro scale
(2017)
Multiwall carbon nanotubes (CNTs) e carbon fibers (CFs)hybrid materials were produced by directly growing CNTs on CFs by means of chemical vapor deposition. For the latter, the oxidative dehydrogenation reaction of C2H2 and CO2 was applied, which allows growing CNTs without damaging the CF surface. Uni-directional nano-engineered carbon fiber reinforced composites (nFRCs) were fabricated by impregnating these hybrid materials with epoxy. The nFRCs subjected to single fiber push-out tests revealed a decrease of the interfacial shear strength (IFSS) of about 36% compared to the carbon fiber composites without CNTs. By means of transverse three-point bending tests performed on pre-notched composite beams inside a scanning electron microscope, the fracturing behavior parallel to the fibers was studied in-situ. The nFRCs showed significantly reduced fiber/matrix debonding while CNTs pull-out, CNTs bridging as well as matrix failure occurred. These results demonstrate that the presence of CNTs in nFRCs affects the stress distribution and consequently the damage Initiation as well as the damage propagation. The presence of CNTs suppresses the stress concentration at the fiber/Matrix interface and reduces the debonding of CFs from the matrix. However, our results indicate that the stress concentration shifts towards the CNTs' ends/matrix interface and causes promoted matrix failure leading to lower IFSS.
Periodic self-organization of matter beyond the diffraction limit is a puzzling phenomenon, typical both for surface and bulk ultrashort laser processing. Here we compare the mechanisms of periodic nanostructure formation on the surface and in the bulk of fused silica. We show that volume nanogratings and surface nanoripples having subwavelength periodicity and oriented perpendicular to the laser polarization share the same electromagnetic origin. The nanostructure orientation is defined by the near-field local enhancement in the vicinity of the inhomogeneous scattering centers. The periodicity is attributed to the coherent superposition of the waves scattered at inhomogeneities. Numerical calculations also support the multipulse accumulation nature of nanogratings formation on the surface and inside fused silica. Laser surface processing by multiple laser pulses promotes the transition from the high spatial frequency perpendicularly oriented nanoripples to the low spatial frequency ripples, parallel or perpendicular to the laser polarization. The latter structures also share the electromagnetic origin, but are related to the incident field interference with the scattered far-field of rough non-metallic or transiently metallic surfaces. The characteristic ripple appearances are predicted by combined electromagnetic and thermo-mechanical approaches and supported by SEM images of the final surface morphology and by time-resolved pump-probe diffraction measurements.
The objective of this research was to determine the resistance of frequently used sealing materials such as fluorocarbon rubber (FKM), fluorosilicone rubber (FVMQ), silicone rubber (VMQ), ethylene-propylene-diene rubber (EPDM), chloroprene rub-ber (CR), chlorosulfonated polyethylene (CSM), butyl rubber (IIR), acrylonitrile buta-diene rubber (NBR), polyester urethane rubber (PUR) and polyamide (PA) in non-aged/aged biodiesel and heating oil with 10 % biodiesel at 20 °C, 40 °C and 70 °C. Mass, tensile properties and Shore hardness A/D (for polyamide) of the test speci-mens were determined before and after the exposure for 84/42 days in the aged and non-aged fuels of different age.
Biodiesel fuels are easily oxidized and contain acids and water. The sealing materi-als: acrylonitrile butadiene rubber, butyl rubber, chloroprene rubber, chlorosulfonated polyethylene and ethylene-propylene-diene rubber and were generally not resistant to biodiesel and heating oil with 10 % biodiesel. Fluorocarbon rubber, fluorosilicone rubber and polyamide were the most resistant materials in all tested fuels up to 70 °C. The degree of damage to the sealing materials increased with higher test temperatures and the age of the fuels.
The effect of electrochemical charging of hydrogen on the structure of a lean duplex stainless steel LDX 2101® (EN 1.4162, UNS S32101) was examined by both Time-of-Flight secondary ion mass spectrometry and electron back-scatter diffraction. The goal is to correlate hydrogen concentration and induced structural changes. Chemical and structural characterizations were done for the same region at the sample's surface with sub-micron spatial resolution. Regions of interest were varying in size between 50 × 50 μm and 100 × 100 μm. The results show a phase transformation of austenite to mainly a defect-rich BCC and scarcely a HCP phase. The phase transformation occurred in deuterium rich regions in the austenite.
Advanced structural characterisation techniques which are rapid to use, non-destructive and structurally definitive on the nanoscale are in demand, especially for a detailed understanding of extended-defects and their influence on the properties of materials. We have applied the electron
backscatter diffraction (EBSD) technique in a scanning electron microscope to non-destructively
characterise and quantify antiphase domains (APDs) in GaP thin films grown on different (001)Si substrates with different offcuts. We were able to image and quantify APDs by relating the asymmetrical intensity distributions observed in the EBSD patterns acquired experimentally and comparing the same with the dynamical electron diffraction simulations. Additionally mean angular error maps were also plotted using automated cross-correlation based approaches to image APDs.
Samples grown on substrates with a 4° offcut from the [110] do not show any APDs, whereas samples grown on the exactly oriented substrates contain APDs. The procedures described in our work can be
adopted for characterising a wide range of other material systems possessing non-centrosymmetric point groups.
A combined methodical approach is tested with respect to the characterization of the inner structure of porous TiO2 layers as typically used in modern dye sensitized solar cells (DSSC). Their performance is directly linked to the surface area of the pore network. The micrometer thick layer employed was manufactured by screen-printing of a starting TiO2 powder constituted of shape-controlled, bipyramidal anatase nanoparticles on FTO/glass substrates. The analytical methods exploited in our study are Focused Ion Beam (FIB) slicing followed by 3D reconstruction as well as the new approach transmission Kikuchi diffraction (TKD) technology in the scanning electron microscope (SEM). Size and shape distribution of the TiO2 NPs within the layer can be extracted. SEM in transmission mode and atomic force microscopy (AFM) have been used to verify the dimensional data obtained by the new combined methodical approach. Its analytical benefits but also the challenges and limitations are highlighted.
Ultrasonic echo testing is widely used in non-destructive testing in civil engineering to investigate concrete structures, to measure thickness, and to locate and characterise built-in components or inhomogeneities. Currently, synthetic aperture focusing techniques are mostly used for imaging. These algorithms are highly developed but have some limitations. For example, it is not possible to image the lower boundary of built-in components like tendon ducts or vertical reflectors. We adopted reverse time migration for non-destructive testing in civil engineering in order to improve the imaging of complicated structures in concrete. By using the entire wavefield, including waves reflected more than once, there are fewer limitations compared to synthetic aperture focusing technique algorithms. As a drawback, the required computation is significantly higher than that for the techniques currently used.
Simulations for polyamide and concrete structures showed the potential for non-destructive testing. The simulations were followed by experiments at a polyamide specimen. Here, having acquired almost noise-free measurement data to test the algorithm, we were able to determine the shape and size of boreholes with sufficient accuracy. After these successful tests, we performed experiments at a reinforced concrete foundation slab. We obtained information from the data by reverse time migration, which was not accessible by traditional imaging. The imaging of the location and structure of the lower boundary of the concrete foundation slab was improved. Furthermore, vertical reflectors inside the slab were imaged clearly, and more flaws were found. It has been shown that reverse time migration is a step forward in ultrasonic testing in civil engineering.
Eine Passivschicht schützt die Oberfläche nichtrostender Stähle vor Materialauflösung. Sie darf nicht unvollständig oder beschädigt sein. Sonst drohen Schadensfälle durch Korrosion an Rohrsystemen und Behältern. TÜV SÜD Chemie Service zeigt ein von der Bundesanstalt für Materialforschung und -prüfung (BAM) entwickeltes Verfahren zur Überprüfung der Passivschicht. Der Test nimmt nur 15 Minuten in Anspruch.
The chemical characteristics of two different types of laser-induced periodic surface structures (LIPSS), so-called high and low spatial frequency LIPSS (HSFL and LSFL), formed upon irradiation of titanium surfaces by multiple femtosecond laser pulses in air (30 fs, 790 nm, 1 kHz), are analyzed by various optical and electron beam based surface analytical techniques, including micro-Raman spectroscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The latter method was employed in a high-resolution mode being capable of spatially resolving even the smallest HSFL structures featuring spatial periods below 100 nm. In combination with an ion sputtering technique, depths-resolved chemical information of superficial oxidation processes was obtained, revealing characteristic differences between the two different types of LIPSS. Our results indicate that a few tens of nanometer shallow HSFL are formed on top of a ∼150 nm thick graded superficial oxide layer without sharp interfaces, consisting of amorphous TiO2 and partially crystallized Ti2O3. The larger LSFL structures with periods close to the irradiation wavelength originate from the laser-interaction with metallic titanium. They are covered by a ∼200 nm thick amorphous oxide layer, which consists mainly of TiO2 (at the surface) and other titanium oxide species of lower oxidation states underneath.
Materials used in military applications have to withstand multiple threats like ballistics and explosions. Thus, high-strength low alloyed (HSLA) steels are used. The main joining technique for metals is welding. Therefore, analysing the dynamic impact behaviour of high-strength welds is very important to fulfil these demands.
Investigation of welds at high strain rates has rarely been conducted in the past. To determine the dynamic impact behaviour of hybrid laser-arc welds, the Split Hopkinson Pressure Bar (SHPB) technique was used. The base material was a quenched and tempered fine-grained armour steel with yield strength of 1100 MPa.
First, a full hybrid laser-arc weld was investigated by extracting specimens consisting of weld metal and heat affected base material. The influence of two variables, the cooling time between 800 °C and 500 °C (t8/5) and strength of filler material, on the impact behaviour was studied. The cooling time t8/5 was varied by preheating to influence the microstructure in the HAZ and to analyse the effect on the hardness and dynamic compressive strength.
Subsequent analysis to detail the original Investigation was carried out by dilatometer heat treatment of specimens to create homogenous subzones of the weld. These specimens have a homogenous microstructure of HAZ and were tested by SHPB to determine the stress-strain characteristics for the different microstructures of HAZ.
The results of the weld specimen showed the effect of preheating and filler material strength on the dynamic compressive behaviour. The analysis of the different microstructures of the HAZ indicated that especially the tempered microstructure caused a reduction in dynamic compressive strength.
The full-notch creep test (FNCT) is widely used to characterize the slow crack growth (SCG) behavior of polyolefin materials in “inert” media as well as effects of environmental stress cracking (ESC) in which the medium has decisive influence on damage mechanism and time to failure. The test is of greatest importance for pipe and blow molding types of polyethylene, high density (PE-HD). Usually the full-notch creep test is applied as a standardized testing method (ISO 16770) using a few universal liquid media, such as solutions of Arkopal N 100. In our study, selected relevant polyethylene, high density materials are investigated also in real media – practical formulations as well as representative pure chemicals – and influences of temperature and geometry of specimen and notch are explicitly addressed. Furthermore, the investigations comprise also the environmental stress cracking behavior of polyethylene, high density in media that are sorbed to a significant extent – examples are diesel and biodiesel – based on comparison with samples previously saturated with those media. Thus, also the underlying diffusion controlled sorption process has to be assessed before. The investigations were performed using a full-notch creep testing device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
Several cylindrical specimens and dental implants, presenting diagonal lattice structures with different cell sizes (600, 900 and 1200 µm) were additively manufactured by selective laser melting process. Then they were implanted for two months in a sheep. After removal, they were studied by Archimedes’ method as well as X-ray computed tomography in order to assess the penetration of bone into the lattice. We observed that the additive manufactured parts were geometrically conform to the theoretical specifications. However, several particles were left adhering to the surface of the lattice, thereby partly or entirely obstructing the cells. Nevertheless, bone penetration was clearly visible. We conclude that the 900 µm lattice cell size is more favourable to bone penetration than the 1200 µm lattice cell size, as the bone penetration is 84 % for 900 µm against 54 % for 1200 µm cell structures. The lower bone penetration value for the 1200 µm lattice cell could possibly be attributed to the short residence time in the sheep. Our results lead to the conclusion that lattice implants additively manufactured by selective laser melting enable better bone integration.
Potential of martensitic stainless steel X5CrNiCuNb 16-4 as pipe steel in corrosive CCS environment
(2017)
Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site (heat, pressure, salinity of the aquifer, CO2-partial pressure). X5CrNiCuNb16-4 has been proven to be sufficient resistant in corrosive environments, but shows rather unusual corrosion behaviour in CCS environment. Therefore differently heat treated coupons of 1.4542 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in an a) water saturated supercritical CO2 and b) CO2-saturated synthetic aquifer environment similar to on-shore CCS-sites in the Northern German Basin. Additionally fatigue tests were performed via push-pull tests with a series of 30 specimens was tested at stress amplitudes between 150 MPa and 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ~ 30 Hz). Best corrosion resistance in the liquid phase is achieved via normalizing prior to exposure and hardening+tempering at 670 °C leads to lowest corrosion rates in the supercritical phase. With no regard to atmosphere discontinuously ellipsoidal surface corrosion regions appear after exposure of 4000 h and more. The endurance limit of X5CrNiCuNb16-4 measured in air is reduced by more than 50% when exposed to CCS environment (maximum number of cycles (10 x 106) at a stress amplitude of 150 MPa) The scatter range TN = 1:34 is disproportionately large contributing to an overall unusual corrosion behaviour.
Unusual Corrosion Behavior of 1.4542 Exposed a Laboratory Saline Aquifer Water CCS-Environment
(2017)
Differently heat treated coupons of 1.4542 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in an a) water saturated supercritical CO2 and b) CO2-saturated synthetic aquifer environment similar to on-shore CCS-sites in the Northern German Basin. Surface corrosion layers are homogeneous but unusually discontinuously ellipsoidal. After 8000 h at 100 bar maximum corrosion rate in the liquid phase is approximately 0.014 mm/year, with normalizing providing best corrosion resistance and approximately 0.003 mm/year in the supercritical phase where hardening+tempering at 670 °C leads to lowest corrosion rates.
Catalytic C–F bond activation reactions of mono- and polyfluoroalkanes at Lewis acidic amorphous aluminum chlorofluoride (ACF) are presented. The hydrogen sources Et3GeH or Et3SiH control the selectivity of the conversions. The immobilization of Et3GeH at ACF resulted in catalytic dehydrohalogenation reactions to yield olefins under very mild conditions. In contrast, if Et3SiH is immobilized at ACF, C–C coupling occured and the formation of Friedel–Crafts products was observed. MAS NMR spectroscopic studies revealed information about the surface binding of the substrates.
Die Entwicklung von leistungsfähigen Fließmitteln in den letzten Jahrzehnten ermöglicht die Herstellung von Beton mit sehr geringem w/z-Wert, bei gleichzeitig guter Verarbeitbar-keit. Die Reduzierung des w/z-Wertes geht dabei mit einer Erhöhung der Festigkeit und einer Verdichtung der Gefü-gestruktur einher. Aufgrund der hohen Druckfestigkeit finden diese Hochleistungsbetone vermehrten Einsatz im Hoch-, Brücken-, und Tunnelbau. Unter Brandbeanspruchung neigen diese Hochleistungsbetone allerdings zu explosionsartigen Abplatzungen. Diese werden nach derzeitigem Stand auf thermomechanische und thermohydraulische Prozesse zurückgeführt. Letztere beruhen auf der Generierung hoher Wasserdampfdrücke in einseitig brandbeanspruchten Beton-bauteilen, die zum einen auf die geringe Permeabilität des Hochleistungsbetons und zum anderen auf die Bildung einer wassergesättigten Zone, der sogenannten „moisture clog“ zurückzuführen sind. Dabei spielen Verdampfungs- und Kondensationsvorgänge sowie der vorhandene Temperatur-gradient eine wichtige Rolle. Die Interaktion des Feuchtetra-nsportes mit den Gefügeveränderungen während der thermi-schen Beanspruchung soll im Rahmen weiterer Versuche eingehend untersucht werden.
Zur Analyse des Feuchtetransports während der thermischen Beanspruchung wurden miniaturisierte Prüfkörper aus Hoch-leistungsbeton hergestellt, die mit Hilfe eines elektrischen Heizelements einseitig erwärmt wurden. Zur Sicherstellung eines eindimensionalen Wärme- und Feuchtetransportes ist der Betonprüfkörper mit einer speziellen Glaskeramik und einer Hochtemperaturwolle ummantelt. Simultan zur Erwär-mung werden eine Reihe röntgentomographischer Aufnah-men durchgeführt. Durch Differenzbildung aufeinanderfol-gender Aufnahmen können Dichteveränderungen lokal und zeitlich aufgelöst werden. Diese lassen Rückschlüsse auf Än-derungen der Feuchteverteilung im Prüfkörper während der Erwärmung zu. Parallel dazu werden Untersuchungen mittels NMR-Relaxometrie (nuclear magnetic resonance) vor und nach der thermischen Beanspruchung durchgeführt. Diese Prüfmethodologie ermöglicht es erstmals, die Veränderungen der Feuchteverteilung infolge thermischer Beanspruchung im Hochleistungsbeton von den Gelporen bis hin zu vorhande-nen Verdichtungsporen abzubilden. So zeigen erste Ergebnis-se, dass die gewählten Untersuchungsmethoden Veränderun-gen der Feuchteverteilung im Prüfkörper räumlich und zeitlich auflösen können.
The phase behavior of a dendritic amphiphile containing a Newkome-type dendron as the hydrophilic moiety and a cholesterol unit as the hydrophobic segment is investigated at the air–liquid interface. The amphiphile forms stable monomolecular films at the air–liquid interface on different subphases. Furthermore, the mineralization of calcium Phosphate beneath the monolayer at different calcium and phosphate concentrations versus mineralization time shows that at low calcium and Phosphate concentrations needles form, whereas flakes and spheres dominate at higher concentrations. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and electron diffraction confirm the formation of calcium phosphate. High-resolution transmission electron microscopy and electron diffraction confirm the predominant formation of octacalcium phosphate and hydroxyapatite.
The data also indicate that the final products form via a complex multistep reaction, including an association step, where nano-needles aggregate into larger flake-like objects.
The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes) and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be used to obtain dendritic-based macromolecules, thereby showing their structural versatility. We put our focus on amphiphilic Janus dendrimers and amphiphilic dumbbells that form vesicles in water but we also encompass vesicles formed thereof in organic solvents. The second part of this review deals with the production methods of these vesicles at the nanoscale but also at the microscale. Furthermore, the influence of various parameters (intrinsic to the amphiphilic JD and extrinsic—from the environment) on the type of vesicle formed will be discussed. In the third part, we will review the numerous biomedical applications of these vesicles of nano- or micron-size.
In situ EDXRD study of MAG-welding using LTT weld filler materials under structural restraint
(2017)
Welding using low transformation temperature (LTT) filler materials is an innovative approach to mitigate detrimental welding residual stresses without cost-intensive post weldtreatments. Due to the local Generation of compressive residual stresses in the weld line by means of a delayed martensite transformation a significant enhancement of the cold cracking resistance of highly stressed welded components can be expected. For the effective usage of These materials a deeper understanding of the microstructural evolution inside the weld material is necessary to determine the complex processes that cause the residual stress formation during welding. Solid-state phase transformation kinetics and the evolution of strain in LTT weld filler materials are monitored in-situ at the instrument ID15A at the ESRF in Grenoble, France. The transferability to real components is implemented by using a realistic MAG welding process under consideration of structural restraint. During welding of multilayer joints, the phase Transformation and phase specific strain evolution of each individual layer is investigated in transmission geometry by means of energy-dispersive X-ray diffraction EDXRD using high energy synchrotron Radiation with a counting rate of 2.5 Hz. The measurement results of a 10% Cr / 10% Ni LTT weld filler are compared to data monitored for the conventional weld filler material G89. The in-situ data clearly indicate a strong effect on the local strain evolution and the formation of compressive strain. This results from the restraint volume expansion during the postponed austenite to martensite transformation of the LTT weld filler, which counteracts the thermal shrinkage. In contrast, for the conventional weld filler material the thermal contraction strains lead to tensile residual strain during welding. Furthermore, the results of in-situ observation during welding Show that the transformation kinetic is dependent on the welding sequence.
Corrosion is the major degradation pathway affecting reinforced concrete structures. In the long-term, the rust layer might become thick and slow down the diffusion of oxygen from the atmosphere to the steel. With this in mind, the mineralogy, microstructure and diffusion properties of an old and thick corrosion product layer were investigated. Despite the presence of macropores, the gas diffusion coefficient was found to be low. The impact of the layer on the oxygen diffusion was evaluated using Fick’s law. The results showed that the layer could reduce the flux of oxygen only in a specific configuration.
A set of highly fluorescent, pH-responsive boron dipyrromethene dyes covering the pH range of 5-12 is presented for broad range pH measurements in mixed aqueous-organic median and polymer matrices. Readout in the intensity Domain with low cost and miniaturized Instrumentation utilizes reversible protonation induced switching ON of their initially completely quenched flourescence mediated by photoinduced electron Transfer. All dyes, rationally designed to reveal closely matching Absorption and Emission properties, are accessible via facile two-step reactions in Overall yields of up to 20%. By modifying the Substitution pattern of the meso-Aryl substiuent, the pKa values could be fine-tuned from 6 to 11. Integration of these molecules into polymeric films by a simple mixing procedure yielded reversible and longterm stable pH sensors for naked eye detection.
Carbon fiber reinforced polymer ropes are gaining in significance in the fields of civil engineering and hoisting applications. Thus, methods of non-destructive testing (NDT) need to be developed and evaluated with respect to new challenges and types of defects. Particularly important is the development of in-service testing solutions which allow the integration in global online monitoring systems. Conventional methods like electrical resistivity or strain measurements using optical fibers are already in use. This study investigates the possibility of using various X-ray techniques to increase the reliability and significance of NDT and their applicability to in-service testing. Conventional film radiography is the most common technique; however, even after image enhancement of the digitized film, this technique lacks contrast sensitivity and dynamic range compared to digital detector array (DDA) radiography. The DDA radiography is a highly sensitive method; yet, the limitation is that it delivers 2D images of 3D objects. By the use of co-planar translational laminography the detectability of planar defects is superior to 2D methods due to multiple projection angles. Apart from this, it can be used on-site due to a rather simple setup and robust equipment. In this work two photon counting detectors (PCD) with different sensor materials (Si and CdTe) were used. The results show that the resolution and defect recognition is lower in case of DDA radiography and laminography using PCDs compared to high-resolution computed tomography. However, the DDA radiography and laminography are sensitive enough to both fiber breakage and delaminations and can be significantly advantageous in terms of measurement time and adaptability for on-site monitoring.
Matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS) is a well-implemented analytical technique for the investigation of complex biological samples. In MS, the sample preparation strategy is decisive for the success of the measurements. Here, sample preparation processes and target materials for the investigation of different pollen grains are compared. A reduced and optimized sample preparation process prior to MALDI-TOF measurement is presented using conductive carbon tape as target. The application of conductive tape yields in enhanced absolute signal intensities and mass spectral pattern information, which leads to a clear separation in subsequent pattern analysis. The results will be used to improve the taxonomic differentiation and identification, and might be useful for the development of a simple routine method to identify pollen based on mass spectrometry.
Poly(l-lactide)s are synthesized and annealed at 120 °C and changes of the molecular weight distribution (MWD) are monitored by matrix-assited laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. For example, benzyl alcohol+SnOct2 causes equilibration of odd- and even-numbered chains and the final goal of the transesterification is the most probable distribution. The underlying intermolecular transesterification is even observed at 100 and 80 °C in the solid state. However, cyclic tin mercaptide catalysts transform the initial most probable distribution into a MWD with maxima, which display a conspicuous fine structure due to a preferential crystallization of certain ring sizes. The optimum ring sizes for the crystallization are provided by ring-ring equilibration. The gradual formation of a special morphology shifts the melting temperature to values up to 187 °C. Annealing of commercial poly(l-lactide) with a cyclic tin catalyst also yields a distribution of mass peaks with a maximum showing the characteristic fine structure.
Lanthanide-doped photon-upconversion nanoparticles (UCNPs) have been the Focus of many Research activities in materials and life sciences in the last 15 years because of their potential to convert light between different spectral regions and their unique photophysical properties. To fully exploit the application potential of These facinating nanomaterials, a number of challenges have to be overcome, such as the low brightness, particularly of small UCNPs, and the reliable quantification of the excitation-power-density-dependent upconversion luminescence. In this series of critical Reviews, recent developments in the design, Synthesis, optical-spectroscopic characterization, and application of UCNPs are presented with Special Focus on bioanalysis and the life sciences. Here we guide the reader from the Synthesis of UCNPs to different concepts to enhance their luminescence, including the required optical-spectroscopic assessment to quantify material Performance; surface modification strategies and bioanalytical applications as well as selected examples of the use of UCNPs as reporters in different Assay formats are addressed in part II. Future Trends and challenges in the field of upconversion are discussed with Special emphasis on UCNP Synthesis and material characterization, particularly quantitative luminescence studies.
In the present study, samples fabricated by varying the deposition hatch length during selective laser melting of nickel based superalloy Inconel 718 were investigated. Microstructure and texture of these samples was characterized using scanning electron microscopy, combined with electron back-scattered diffraction, and residual stress assessment, using neutron diffraction method. Textured columnar grains oriented along the sample building direction were observed in the shorter hatch length processed sample. A ten-fold increase in the hatch length reduced the texture intensity by a factor of two attributed to the formation of finer grains in the longer hatch length sample. Larger gradients of transverse residual stress in the longer hatch length sample were also observed. Along the build direction, compressive stresses in the shorter hatch length and negligible stresses for the longer hatch length specimen were observed. Changes to the temperature gradient (G) in response to the hatch length variation, influenced the G to growth rate (R) ratio and the product G × R, in agreement with the microstructures and textures formed. For the residual stress development, geometry of the part also played an important role. In summary, tailored isotropy could be induced in Inconel 718 by a careful selection of parameters during selective laser melting.
Structural health monitoring contributes to early damage detection in the built infrastructure. During the last two decades, sensor networks transferred from wired to wireless sensor networks. Several methods exist to measure moisture in building materials. Most of the introduced commercial moisture measurement methods provide information about the local or near surface moisture. A feasibility study is presented to demonstrate, how the Received Signal Strength Indicator (RSSI) of a Bluetooth Low Energy (BLE) signal, transmitted from the BLE-module embedded in building materials, correlate with changing moisture content. The feasibility of this influence was investigated in the presented study. The maximum and minimum RSSI were systematically recorded and analysed.
The vast experience with the automated, ultrasonic system for the inspection of hollow railway axles used by Deutsche Bahn shows that much smaller flaws are detectable than required. This results in a number of false calls. False calls lead to unnecessary demounting and disassembling of wheelsets, which generates unnecessary additional costs. In order to adjust the sensitivity of the inspection system to reduce the number of false calls without compromising safety, the capability of the system to detect cracks needs to be comprehensively established. This capability can be quantified by using probability of detection (POD) curves for the system. The multi-parameter POD model makes it possible to include several factors that influence the crack detection in the analysis. The analysis presented in this paper shows that crack position, orientation, depth extension, and shape as well as the geometry of the axle all have influence on the ultrasonic response amplitude. For future work, calculation of the POD using multi-parameter POD model with these parameters is planned.
New fluorinated coordination polymers were prepared mechanochemically by milling the alkaline earth metal hydroxides MII(OH)2·xH2O (MII: Ca, Sr) with tetrafluoroisophthalic acid (H2mBDC-F4). The structures of [{Ca(mBDC-F4)(H2O)2}·H2O] and [{Sr(mBDC-F4)(H2O)2}·H2O] were determined based on ab initio calculations and their powder X-ray diffraction (PXRD) data. The compounds are isomorphous and crystallize in the orthorhombic space group P212121. The determined structures were validated by using extended X-ray absorption (EXAFS) data. The new materials were thoroughly characterized using elemental analysis, thermal analysis, magic angle spinning NMR, and attenuated total reflection-infrared spectroscopy. Further characterization methods such as BET, dynamic vapor sorption, and scanning electron microscopy imaging were also used. Our investigations indicate that mechanochemistry is an efficient method for preparing such materials.
We present a series of remarkable structural transformations for a family of layered metal–organic frameworks (MOFs) in a three-step solid-state reaction cycle. The cycle represents new dynamic behavior of 2D coordination polymers and involves the sequence of reactions: {[Mn2(ina)4(H2O)2]·2EtOH}n (JUK-1) → {(NH4)2[Mn(ina)2(NCS)2]}n·xH2O (JUK-2) → {[Mn2(ina)2(Hina)2(NCS)2]}n (JUK-3) → JUK-1 (Hina = isonicotinic acid), each accompanied by rearrangement of intralayer coordination bonds and each induced by a different external stimulus. In situ investigation of the first step of the cycle by combined synchrotron X-ray diffraction and Raman spectroscopy reveals direct mechanochemical unzipping of JUK-1 bilayers to respective JUK-2 layers with reaction rates dependent on the milling conditions. In contrast, the reverse zipping of JUK-2 layers involves two steps and proceeds through a new MOF (JUK-3) whose structure was elucidated by powder X-ray diffraction. Magnetic measurements confirm conversions of manganese nodes in the reaction cycle. The findings indicate the possibility of developing coordination-based assemblies with large structural responses for use in smart stimuli-responsive systems and sensor technologies.
The mechanochemical synthesis of the zinc N-(phosphonomethyl)glycinate Zn(O₃PCH₂NH₂CH₂CO₂) H₂O is presented. The structure was solved from powder X-ray diffraction (PXRD) data. In the three-dimensional pillared structure, the Zn atoms are coordinated tetrahedrally. In situ investigations of the reaction process with synchrotron PXRD and Raman spectroscopy reveal a two-step process including the formation of an intermediate.
The use of novel multi-scale correlative methods, which involve the coordinated characterisation of matter across a range of length scales, are becoming of increasing value to materials scientists. Here, we describe for the first time how a multi-scale correlative approach can be used to investigate the nature of ductile fracture in metals. Specimens of a nuclear pressure vessel steel, SA508 Grade 3, are examined following ductile fracture using medium and high-resolution 3D X-ray computed tomography (CT) analyses, and a site-specific analysis using a dual beam plasma focused ion beam scanning electron microscope (PFIB-SEM). The methods are employed sequentially to characterise damage by void nucleation and growth in one volume of interest, allowing for the imaging of voids that ranged in size from less than 100 nm to over 100 mm. This enables the examination of voids initiated at carbide particles to be detected, as well as the large voids initiated at inclusions. We demonstrate that this multi-scale correlative approach is a powerful tool, which not only enhances our understanding of ductile failure through detailed characterisation of microstructure, but also provides quantitative information about the size, volume fractions and spatial distributions of voids that can be used to inform models of failure. It isfound that the vast majority of large voids nucleated at MnS inclusions, and that the volume of a void varied according to the volume of its initiating inclusion raised to the power 3/2. The most severe voiding was concentrated within 500 mm of the fracture surface, but measurable damage was found to extend to a depth of at least 3 mm. Microvoids associated with carbides (carbide-initiated voids) were found to be concentrated around larger inclusion-initiated voids at depths of at least 400 mm. Methods for quantifying X-ray CT void data are discussed, and a procedure for using this data to calibrate parameters in the Gurson-Tvergaard Needleman (GTN) model for ductile failure is also introduced.
X-ray tomography characterisation of lattice structures processed by selective electron beam melting
(2017)
Metallic lattice structures intentionally contain open porosity; however, they can also contain unwanted closed porosity within the structural members. The entrained porosity and defects within three different geometries of Ti-6Al-4V lattices, fabricated by Selective Electron Beam Melting (SEBM), is assessed from X-ray computed tomography (CT) scans. The results suggest that horizontal struts that are built upon loose powder show particularly high (~20 x 10⁻³ vol %) levels of pores, as do nodes at which many (in our case 24) struts meet. On the other hand, for struts more closely aligned (0° to 54°) to the build direction, the fraction of porosity appears to be much lower (~0.17 x 10⁻³%) arising mainly from pores contained within the original atomised powder particles.
Evaluating innovative process technologies has become highly important within the last decades. As standard tools different Life Cycle Assessment methods have been established, which are continuously improved. While those are designed for evaluating single processes they run into difficulties when it comes to assessing environmental impacts of process innovations at macroeconomic level. In this paper we develop a multi-step evaluation framework building on multi regional inputeoutput data that allows estimating macroeconomic impacts of new process technologies, considering the network characteristics of the global economy.
Our procedure is as follows: i) we measure differences in material usage of process alternatives, ii) we identify where the standard processes are located within economic networks and virtually replace those by innovative process technologies, iii) we account for changes within economic systems and evaluate impacts on emissions.
Within this paper we exemplarily apply the methodology to two recently developed innovative technologies: longitudinal large diameter steel pipe welding and turning of high-temperature resistant materials. While we find the macroeconomic impacts of very specific process innovations to be small, its conclusions can significantly differ from traditional process based approaches. Furthermore, information gained from the methodology provides relevant additional insights for decision makers extending the picture gained from traditional process life cycle assessment.
Polymeric membranes represent a cost- and energy efficient solution for gas separation. Recently superglassy polymers with high free volume outperform many conventional dense polymers in terms of gas permeability and selectivity. However, such polymers are prone to pronounced physical aging, resulting in a dramatic reduction in the gas permeability. Molecular mobility of polymer segments plays an important role in the physical aging and the gas transport performance of polymeric membranes. Molecular mobility and physical aging of a representative superglassy polynorbornene with very high gas permeability, PTCNSi2g, was monitored by using dielectric spectroscopy with state-of-the-art high-resolution analyzers. This work helps to shed some light on the structure−property relationship of superglassy polymers on a molecular level and to provide practical “design rules” for the development of high performance polymers for gas separation.
Strand breaks and conformational changes of DNA have consequences for the physiological role of DNA. The natural protecting molecule ectoine is beneficial to entire bacterial cells and biomolecules such as proteins by mitigating detrimental effects of environmental stresses. It was postulated that ectoine-like molecules bind to negatively charged spheres that mimic DNA surfaces. We investigated the effect of ectoine on DNA and whether ectoine is able to protect DNA from damages caused by ultraviolet radiation (UV-A). In order to determine different isoforms of DNA, agarose gel electrophoresis and atomic force microscopy experiments were carried out with plasmid pUC19 DNA. Our quantitative results revealed that a prolonged incubation of DNA with ectoine leads to an increase in transitions from supercoiled (undamaged) to open circular (single-strand break) conformation at pH 6.6. The effect is pH dependent and no significant changes were observed at physiological pH of 7.5. After UV-A irradiation in ectoine solution, changes in DNA conformation were even more pronounced and this effect was pH dependent. We hypothesize that ectoine is attracted to the negatively charge surface of DNA at lower pH and therefore fails to act as a stabilizing agent for DNA in our in vitro experiments.
Supercapacitors are an emerging energy-storage system with a wide range of potential applications. In this study, highly porous nickel-cobalt-oxide@reduced graphene oxide (Ni-Co-O@RGO-s) nanosheets were synthesized as an active material for supercapacitors using a surfactant-assisted microwave irradiation technique. The RGO-modified nanocomposite showed a larger specific area, better conductivity, and lower resistivity than the unmodified nanocomposite because the RGO facilitated faster ion diffusion/transport for improved redox activity. The synergistic effect of Ni-Co-O@RGO-s resulted in a high capacitance of 1903 F/g (at 0.8 A/g) in a mixed KOH/redox active K3Fe(CN)6 electrolyte. The asymmetric Ni-Co-O@RGO-s//AC supercapacitor device yielded a high energy density and power density of 39 Wh/kg and 7500 W/kg, respectively. The porous structure and combination of redox couples from both the electrode and electrolyte provided a highly synergistic effect, which improved the performance of the supercapacitor device.
Härte und Korrosionsbeständigkeit sind die wichtigsten Qualitätsmerkmale von Schneidwaren. Diese werden nur durch eine optimal durchgeführte Wärmebehandlung des martensitischen nichtrostenden Stahls 1.4116 (X50CrMoV15) erreicht. In der industriellen Fertigung wird die Korrosionsbeständigkeit von Schneidwaren durch Wechseltauchversuche überprüft, die herstellerübergreifend eine große Schwankung der Korrosionsbeständigkeit belegen. In den letzten Jahren wurden neue elektrochemische Untersuchungsmethoden für die Werkstoffgruppe der martensitischen nichtrostenden Stähle entwickelt, welche die geringe Lochkorrosionsbeständigkeit von Schneidwaren auf das Phänomen der Chromverarmung zurückzuführen. Derzeit wird in der wissenschaftlichen und in der industriellen Gemeinschaft der Schritt des Anlassens als Hauptursache der Chromverarmung angesehen. Bei Schneidwaren sind die Anlasstemperaturen aber zu gering, um die auftretende Chromverarmung zu erklären. Aus diesem Grund wurden drei verschiedene Wärmebehandlungsparameter (Austenitisierungsdauer, Abkühlgeschwindigkeit und Anlasstemperatur) systematische untersucht, um deren Beitrag zur Chromverarmung darzustellen. Dazu wird die Untersuchungsmethode der elektrochemisch potentiodynamischen Reaktivierung (EPR) eingesetzt, die sehr sensibel auf Veränderungen im Gefüge reagiert und den Grad an Chromverarmung ermittelt. Außerdem wurde die KorroPad-Prüfung durchgeführt und kritische Lochkorrosionspotentiale ermittelt, um den Zusammenhang zwischen Chromverarmung und Lochkorrosionsbeständigkeit herzustellen. Die Ergebnisse aller Untersuchungen verdeutlichen wie eng das Prozessfenster ist, in dem Schneidwaren mit hoher Korrosionsbeständigkeit hergestellt werden können.
Residual stresses of welds become more and more important influencing cold cracking as well as the fatigue life of welded components. Low transformation temperature (LTT) filler materials offer the opportunity to alter the residual stresses already during the welding process by means of ad- justed martensite phase transformation temperature (MS). In the current paper, welding residual stresses are studied putting the focus on MS while joining heavy steel sections with a thickness of 20 and 25 mm, respectively. The residual stress state was determined at the top surface using X-ray diffraction as well as in the bulk by neutron diffraction. The results com- pare the residual stresses present in a conventional weld and LTT welds when multi-pass welding of large-scale compo- nents was applied. Repeated phase transformation in the case of the LTT weld is more vital for the residual stresses present in the real-life-like joints. This accounts for the top surface in longitudinal direction but is most pronounced for the bulk of the welds. Detrimental tensile residual stresses are mainly re- duced in the bulk in comparison to a conventional filler wire even in multi-pass welds of thick steel sections.
Size and shape are crucial parameters which have impact on the potential of nanoparticles to penetrate cell membranes and epithelial barriers. Current research in nanotoxicology additionally focuses on particle coating. To distinguish between core- and coating-related effects in nanoparticle uptake and translocation, two nanoparticles equal in size, coating and charge but different in core material were investigated.
Silver and iron oxide nanoparticles coated with poly(acrylic acid) were chosen and extensively characterized by small-angle x-ray scattering, nanoparticle tracing analysis and transmission electron microscopy (TEM). Uptake and transport were studied in the intestinal Caco-2 model in a Transwell System with subsequent elemental analysis. TEM and ion beam microscopy were conducted for particle visualization.
Although equal in size, charge and coating, the behavior of the two particles in Caco-2 cells was different: while the internalized amount was comparable, only iron oxide nanoparticles additionally passed the epithelium. Our findings suggest that the coating material influenced only the uptake of the nanoparticles whereas the translocation was determined by the core material.
Knowledge about the different roles of the particle coating and core materials in crossing biological barriers will facilitate toxicological risk assessment of nanoparticles and contribute to the optimization of pharmacokinetic properties of nano-scaled pharmaceuticals.
Scattering on scattering
(2017)
Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is often applied to assess the dispersity and the end groups of synthetic polymers through the addition of cationizing agents. Here weaddress how these cation adducts are formed using polystyrene (PS) as a model polymer. We analyzed PSby MALDI-MS with a 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile (DCTB) as the matrix and a range of trifluoroacetate (TFA) salts as cationizing agents on a range of different targetplate materials (copper, 1.4301 stainless steel, aluminum, Inconel 625, Ti90/Al6/V4 and chromium-, gold-and silver-plated stainless steel). It was found that on a stainless steel substrate the metal cations Al+,Li+, Na+, Cu+and Ag+formed polystyrene adducts, whereas K+, Cs+, Ba2+, Cr3+, Pd2+, In3+, or their lower oxidation states, did not. For the copper and silver substrates, PS and DCTB adduct formation with cations liberated from these target plate materials was observed upon addition of a cationizing agent, which indicates the occurrence of redox reactions between the added TFA salts and the target plate material. Judging from their standard electrode potentials, these redox reactions would not normally occur, i.e.,they require an additional energy input, strongly suggesting that the observed redox reactions are laser-induced. Furthermore, copper granules were found to successfully sequester PS from a tetrahydrofuran(THF) solution, consistent with the view complex formation with the copper target plate can take place prior to the MALDI-MS measurement.
Normally, in analytical GD-MS, the doubly charged metallic ion signals from the sample are several orders of magnitude less than the corresponding singly charged signals. However, we have observed that using a neon plasma, the M++ signals of some elements, which have double ionization energies close to the first ionization energy of neon, are of the same order as the M+ signal. Doubly charged ions may be produced directly in the discharge cell by electron ionization (EI), and also by two electron Penning ionization (TEP), but these processes cannot explain the above effect. In this paper, we suggest that an additional process named as ‘Charge Transfer and Ionization’ (CTI) produces such ions either in their ionic ground state or in an excited state. To confirm that this process is typical of the discharges used in GD-MS and not an artefact of any particular form of cell and ion extraction system, we have carried out comprehensive experimental measurements using three different GD-MS instruments, viz., Nu Astrum, VG9000 and ELEMENT GD and our results provide clear evidence for CTI. This is the first time the process has been identified as an ionization process in analytical GD-MS. CTI must be differentiated from Asymmetric Charge Transfer (ACT), which is a “selective” process and requires a close energy match (e.g. ΔE < 0.5 eV for a strong effect). On the other hand, CTI is “non-selective” in the sense that a close energy match is not required (e.g. a strong effect is observed with ΔE ∼ 2 eV), although the process only occurs for a limited number of elements, depending on the plasma gas used and the total energy required to doubly ionize the metallic atom.
In this in vitro study, the protective qualities of different mouthguard types were examined during small hard object collisions. The aim was to investigate inconclusive aspects of hard inserts, nylon nets, and air spaces as reinforcements in the anterior region and the protection qualities of ethylene vinyl acetate (EVA).
Five different mouthguards with a labial thickness between 2 mm and 11 mm made of materials of varying stiffness were investigated. As a negative control, the same experiments were performed without a mouthguard. Different combinations of EVA and labial inserts ((polyethylene terephthalate glycol-modified [PETG]), nylon mesh, air space) were tested. Using a stainless steel pendulum device, blows of different energy (0.07-2.85 joules) were applied to the center of the crown of a pivoted tooth in a custom-built jaw model. A laser Doppler vibrometer measured the tooth deflection, while an acceleration sensor attached to the pendulum measured the braking accelerations.
Tooth deflection was reduced up to 99.7% compared to no mouthguard, and the braking acceleration was reduced up to 72.2% by increasing the mouthguards' labial thickness in combination with labial inserts of different stiffness and a built-in air space between the front teeth and the mouthguard. The mouthguards made of soft materials (EVA with nylon mesh) showed slightly better protection qualities than the more rigid mouthguards of similar thickness (PETG; P<.05). However, with increasing impact energy, their protective capacities decreased to a greater extent than the stiffer mouthguards.
The combination of increased labial thickness and labial inserts of varying stiffness and eventually an air space offers the best protection capacities for hard, small object collisions.
In den letzten 15 Jahren hat im deutschen Autobahnnetz die Anzahl von Schäden an Betonfahrbahnen, die vor 2005 er-richtet wurden zugenommen. Dies führt oft zu einer Vermin-derung der Lebensdauer von 30 auf 10 bis 15 Jahre. Trotz umfassender Untersuchungen wurde die Ursache bis jetzt nicht eindeutig geklärt, jedoch scheint die Alkali-Kieselsäure-Reaktion (AKR) hierbei eine Rolle zu spielen. Vor diesem Hintergrund wurden AKR-Performance-Tests entwickelt, die jedoch die mechanischen Einwirkungen aus Klima und Ver-kehr nicht berücksichtigen. Aus diesem Grund wurde eine AKR-Forschergruppe von der Deutschen Forschungsgemein-schaft ins Leben gerufen, welche sich experimentell und auf Simulationsebene mit diesem Thema befasst. Inhalt dieses Beitrages sind ausgewählte Ergebnisse des an der BAM bear-beiteten experimentellen Projektteils, welche in eine auf die Auswirkung einer mechanischen Degradation fokussierte Promotionsarbeit einfließen.
Ziel der ausgewählten Untersuchung ist es, den Einfluss einer mechanisch induzierten Betondegradation auf den Stofftrans-port herauszuarbeiten. Hierzu wird ein großformatiger Balken einem zyklischen Vier-Punkt Biegezugversuch mit einer Anzahl von 5 Mio. Lastwechseln unterzogen. Während des Versuches findet ein Schadensmonitoring mit verschiedenen zerstörungsfreien Prüftechniken statt. Hierzu zählen Deh-nungsmessungen, Schallemissionsanalyse und Ultraschall-messungen. Nach dem zyklischen Belastungs-versuch werden kleinformatige Probekörper aus dem belasteten Balken entnommen. Als Referenz dienen unbelas-tete Probekörper aus der gleichen Herstellungscharge. Die Oberflächen der entnommenen Probekörper werden in einem kapillaren Saugversuch zum einen mit deionisiertem Wasser und zum anderen mit einer 3,6 %igen NaCl-Lösung beauf-schlagt. Während der Saugversuche dienen verschiedene zerstörungsfreie bzw. -arme Messmethoden dazu, die Feuch-teaufnahme bzw. -verteilung in den Probekörpern zu messen. Hierzu gehören neben der Gravimetrie die Messung mit NMR (Nuclear-Magnetic-Resonance) sowie TDR (Time-Domain-Reflectometry). Nach den Saugversuchen wird die Na- und Cl-Verteilung an den mit NaCl-Lösung beaufschlagten Pro-bekörpern zerstörend mittels LIBS (Laser-Induced-Breakdown-Spectroscopy) ermittelt. Erste Ergebnisse zeigen, dass die zyklische Ermüdungsdegradation den Stofftransport tendenziell verstärkt.
According to the objectives of the research group 1498, this paper deals with degradation effects in concrete structures that are caused by cyclic flexural loading. The goal is to determine their influence on the fluid transport processes within the material on the basis of experimental results and numerical simulations. The overall question was, to which extent the ingress of externally supplied alkalis and subsequently an alkali-silica reaction are affected by such modifications in the microstructure. Degradation in the concrete microstructure is characterized by ultrasonic wave measurements as well as by microscopic crack analysis. Furthermore, experiments on the penetration behavior of water into the investigated materials were performed. The penetration behavior into predamaged concrete microstructures was examined by the classical Karsten tube experiment, nuclear magnetic resonance method, and time domain reflectometry techniques. In order to create an appropriate model of the material's degradation on the water transport, the Darcy law was applied to describe the flow in partially saturated concrete. Material degradation is taken into account by an effective permeability that is dependent on the state of degradation. This effective permeability is obtained by the micromechanical homogenisation of the flow in an Representative Elementary Volume (REV) with distributed ellipsoidal microcracks embedded in a porous medium. The data gained in the microscopic crack analysis is used as input for the micromechanical model. Finite element simulations for unsaturated flow using the micromechanical model were compared with the experimental results showing good qualitative and quantitative agreement.
The primary aim of this paper is to analyze the impact of mechanical pre-damage and alkali–silica reaction (ASR) on the fracture mechanical properties of pavement concrete. For this purpose, a four point bending test was applied to large format beams to produce a defined level of cyclic pre-damage. The fatigue-induced concrete degradation process was simultaneously recorded using a testing procedure specifically developed for the purpose. In addition, fatigue-induced cracks on extracted drilling cores were spatially visualized and quantified using micro X-ray 3D-computed tomography (3D-CT). The storage of the small-format test specimens, with and without cyclic pre-damage, in an ASR-conducive environment showed that pre-damage leads to an increase in ASR damage processes. Subsequent structural mechanical investigations on small format specimens with and without pre-damage show that fatigue loading and ASR significantly influence fracture mechanical parameters of the concrete.
Over the last decade there have been increasing efforts to develop three-dimensional (3D) scaffolds for bone tissue Engineering from bioactive ceramics with 3D printing emerging as a promising technology. The overall objective of the present study was to generate a tissue engineered synthetic bone graft with homogenously distributed osteoblasts and mineralizing bone Matrix in vitro, thereby mimicking the advantageous properties of autogenous bone grafts and facilitating usage for reconstructing segmental discontinuity defects in vivo . To this end, 3D scaffolds were developed from a silica-containing calcium alkali orthophosphate, using, fi rst, a replica technique – the Schwartzwalder – Somers method – and, second, 3D printing, (i.e. rapid prototyping). The mechanical and physical scaffold properties and their potential to facilitate homogenous colonization by osteogenic cells and extracellular bone matrix formation throughout the porous scaffold architecture were examined.
Osteoblastic cells were dynamically cultured for 7 days on both scaffold types with two different concentrations of 1.5 and 3 × 10⁹ cells/l. The amount of cells and bone matrix formed and osteogenic marker expression were evaluated using hard tissue histology, immunohistochemical and histomorphometric analysis. 3D-printed scaffolds (RPS) exhibited more micropores, greater compressive strength and silica release. RPS seeded with 3 × 10⁹ cells/l displayed greatest cell and extracellular Matrix formation, mineralization and osteocalcin expression. In conclusion, RPS displayed superior mechanical and biological properties and facilitated generating a tissue engineered synthetic bone graft in vitro, which mimics the advantageous properties of autogenous bone grafts, by containing homogenously distributed terminally differentiated osteoblasts and mineralizing bone matrix and therefore is suitable for subsequent in vivo implantation for regenerating segmental discontinuity bone defects.
Implementation of Ba0.6Sr0.4TiO3-ZnO-B2O3 based tunable microwave phase shifters in LTCC technology
(2017)
Tunable dielectric Ba0.6Sr0.4TiO3-ZnO-B2O3 thick-films were analyzed regarding their integration potential into the LTCC technology. Therefore, tunable loaded line phase shifters based on metal-insulator-metal varactors with single- and double- printed BST thick-films were fabricated and co-sintered inside a four layer LTCC module. Microstructural and chemical investigations showed a sufficient compatibility and adhesion between the silver, BST composite and LTCC layers and a resulting morphology depending on the processing route. The microwave characterization of the LTCC-embedded phase shifters revealed comparable results to phase shifters with the same design on alumina substrates.
Optimization of welding loads with narrow groove and application of modified spray arc process
(2017)
Current efforts for lightweight design result in a growing application of high-strength fine-grained structural steel in modern constructions, e.g. mobile cranes, with yield strength from 960 MPa. The design of welded structures and welding processes becomes more challenging with increasing material strength and elastic ratios. High residual stresses are able to diminish lifetime, load capacity and component safety and should be avoided. Recent analyses have shown strong influences of heat control and restraint of the weld due to arising reaction stresses, superimposing with local residual welding stresses. Modern inverter technologies allowed the development of numerous modified spray arc processes driven by power source manufacturers, which provide virtually similar features and several benefits, enabling welding of narrower seams with reduced weld volumes and total heat inputs. This research focuses on welding loads due to modified weld seams. The global reaction forces and moments and their superposition with local residual stresses in welded components due to external shrinkage restraints were investigated using a special testing facility and XRD. The restraint intensity, weld seam geometry and welding process were varied for statistical evaluations of resulting welding loads. When welding under restraint, a reduction of the weld seam volume causes significantly lower reaction stress levels.
The increased use of fibre reinforced plastic (FRP) composites for improved efficiency and reliability in energy related applications, e.g. wind and marine turbine blades, nacelles, oil and gas flexible risers, also increases the demand for innovative non-destructive testing technologies. In this contribution, results concerning the characterisation of CFRP and GFRP during and after quasi-static tensile loading are presented. It includes the measurement of optical properties in the infrared spectral range, tensile loading tests with the observation of the temperature distribution at one or both sides of the specimens using an infrared camera for the preparation and monitoring of intended natural defects, and active thermography inspections after tensile loading. It is shown that the defect preparation was successful. Thermographic monitoring during and active thermography testing after tensile loading enable the detection of the lateral extend of the generated defects. Differences between CFRP and GFRP materials are discussed.
The choice of a pure cohesive or a pure frictional viscoplastic model to represent the rheological behaviour of a flowslide is of paramount importance in order to obtain accurate results for real cases. The principal Goal of the present work is to clarify the influence of the type of viscous model—pure cohesive versus pure frictional—with the numerical reproduction of two different real flowslides that occurred in 1966: the Aberfan flowslide and the Gypsum tailings impoundment flowslide. In the present work, a depth-integrated model based on the v-pw Biot–Zienkiewicz formulation, enhanced with a diffusion-like equation to account for the pore pressure Evolution within the soil mass, is applied to both 1966 cases. For the Aberfan flowslide, a frictional viscous model based on Perzyna viscoplasticity is considered, while a pure cohesive viscous model (Bingham model) is considered for the case of the Gypsum flowslide. The numerical approach followed is the SPH method, which has been enriched by adding a 1D finite difference grid to each SPH node in order to improve the description of the pore water evolution in the propagating mixture. The results obtained by the performed simulations are in agreement with the documentation obtained through the UK National Archive (Aberfan flowslide) and the International Commission of large Dams (Gypsum flowslide).
The presentation will discuss the difference between EU and US standards for the determination of explosion (flammability) limits and limiting oxygen concentration. Small differences observed in measured values can be traced back to the different test apparatuses and criteria. The discrepancies can be much greater in the case of limiting oxygen concentration because of the high amount of inert gases and the corresponding low laminar burning velocities. The paper describes some examples and the influence of the chosen criteria on the results. The European and US standards use the criteria of flame propagation in open test vessels and of pressure rise in closed ones. The examples discussed show that flame propagation is still possible at very small pressure rise values, as observed much below the pressure rise criterion of usual standards. However, flame propagation in a process plant can cause an accident or explosion and must be avoided. Therefore, the flame propagation criterion is recommended to be used in chemical safety engineering. The European safety database CHEMSAFE contains expertevaluated safety data for cases where the determination method and criteria are known. Flammability characteristics based on the pressure rise criterion may suffice in certain cases, e.g. for explosion protection in closed vessels without any connecting pipes.