Ingenieurwissenschaften und zugeordnete Tätigkeiten
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Predictive Methods for Determining the Thermal Decomposition Properties of Hazardous Substances
(2019)
Due to the fast development and availability of computers, predictive approaches are increasingly used in the evaluation process of hazardous substances complementary to experiments. Their use was recommended as alternative to experimental testing by the REACH regulation to complete the lack of knowledge on properties for existing substances that must be registered before 2018 (upon quantities). Among the proposed predictive approaches, Quantitative Structure Property Relationships (QSPR) are powerful methods to predict macroscopic properties from the only molecular structure of substances. In that context, the HAZPRED project (2015-2018, founded by the SAF€RA consortium) aims to develop theoretical models (e.g. QSPR) and small-scale tests to predict complex physico-chemical properties (e.g. thermal stability, explosivity) of hazardous substances to complete the lack of knowledge on these hazardous substances quickly or to understand their decomposition behaviour better. In particular, this contribution will present the work done in this project on the physical hazards of organic peroxides and self-reactive substances: gathering of existing experimental data, new experimental campaigns, review of existing models and proposition of new estimation methods.
To increase the competitiveness of jacket substructures compared to monopiles a changeover from an individual towards a serial jacket production based on automated manufactured tubular joints combined with standardized pipes has to be achieved. Therefore, this paper addresses fatigue tests of automatically welded tubular X-joints focusing on the location of the technical fatigue crack. The detected location of the technical crack is compared to numerical investigations predicting the most fatigue prone notch considering the structural stress approach as well as the notch stress approach. Besides, the welding process of the automated manufactured tubular X-joints is presented.
Dissolved water has major impact on the physical and chemical properties of phosphate glasses. In the present study we have investigated the structural response to water incorporation for glasses in the system Li2O–MgO–Al2O3–P2O5.
Glasses containing 0–8 wt% H2O were synthesised at 500 MPa confining pressure in internally heated gas pressure vessels at 1323 K (LMP, Al-poor glass) and 1423 K (LMAP, Al-enriched glass). Water contents of glasses were determined by pyrolysis and subsequent Karl-Fischer titration (KFT) and/or by infrared spectroscopy. Density varies nonlinearly with water content implying large structural changes when adding up to 2 wt% H2O to the dry glass. Glass Transition temperatures measured by differential thermal analysis (DTA) continuously decrease with water content. The trend can be explained by depolymerisation of the phosphate network. Near-infrared spectroscopy shows that even in Al poor glasses only a minority of dissolved water is present as H2O molecules, but the largest amount is present as OH Groups formed by hydrolysis of P–O–P bonds. The network is stabilised by aluminium which is predominantly six-coordinated in these glasses as shown by 27Al MAS NMR spectroscopy. With increase of Al in the glasses, breaking up of the Phosphate network through hydrolysis is depressed, i.e. much lower OH Contents are formed at same total water content.
Network depolymerisation upon addition of H2O is evident also from 31P MAS NMR spectroscopy. While Phosphate tetraheda are crosslinked by two to three bridging oxygen in dry glasses, diphosphate Groups are dominant in glasses containing 8 wt% H2O.
The Measurement- and Model-based Structural Analysis (MeMoS) integrates a finite element model into least squares adjustment and thus allows to evaluate a mechanical model and measurements in a combined analysis. To examine the capability to detect and localise damage using this integrated analysis MeMoS, a small-scale truss bridge made of aluminium profiles is built as a test specimen for this purpose.
Metal oxide/graphene photocatalysts have been attracting considerable attention in solving environmental pollution problems because of the limitations of the semiconductor-based photocatalysts. In this study, highly efficient and inexpensive zinc oxide (ZnO) nanoparticles with three different morphologies, such as nanospheres, nanodisks, and nanorods, anchored on reduced graphene oxide (RGO) were synthesized in solvent mixtures with different ethanol to water ratios. Among the three morphologies, the nanospherical ZnO/RGO (sZG) Composite exhibited the highest methylene blue (MB) and rhodamine B removal efficiencies at 99% and 98%, respectively, after only 60 min under low-power (40 W) ultraviolet irradiation at a low catalyst loading of 0.1 g L−1. This nanocomposite also showed excellent photocatalytic stability under UV irradiation, retaining 96% Efficiency even after 15 cycles of MB degradation. Moreover, the sZG composite exhibited a high MB degradation Efficiency of approximately 99% after 100 min at a low catalyst loading of 0.2 g L−1 under solar light illumination. The
excellent photocatalytic performance and high stability of this low-cost nanospherical ZnO/RGO Composite exemplarily highlights the potential of sustainable next-generation photocatalysis for treating wastewater containing organic pollutants.
The antibacterial features of natural pine/spruce rosin are well established, yet the functionality in various thermoplastics has not been surveyed. This work focuses on the processing of industrial grade purified rosin mixed with polyethylene (PE), polypropylene (PP), polylactic acid (PLA), polyamide (PA) and corn starch based biopolymer (CS). Homopolymer masterbatches were extrusion-compounded and melt-spun to form fibres for a wide range of products, such as filters, reinforcements, clothing and medical textiles. Due to the versatile chemical structure of rosin, it was observed compatible with all the selected polymers. In general, the rosin-blended systems were shear-thinning in a molten condition. The doped fibres spun of PE and PP indicated adequate melt-spinning capability and proper mechanical properties in terms of ultimate strength and Young's modulus. The antibacterial response was found dependent on the selected polymer. Especially PE with a 10 wt% rosin content showed significant antibacterial effects against Escherichia coli DH5α and Staphylococcus aureus ATCC 12598 when analysed in the Ringer's solution for 24 h.
Preactivation Crosslinking - An Efficient Method for the Oriented Immobilization of Antibodies
(2019)
Crosslinking of proteins for their irreversible immobilization on surfaces is a proven and popular method. However, many protocols lead to random orientation and the formation of undefined or even inactive by-products. Most concepts to obtain a more targeted conjugation or immobilization requires the recombinant modification of at least one binding partner, which is often impractical or prohibitively expensive. Here a novel method is presented, which is based on the chemical preactivation of Protein A or G with selected conventional crosslinkers. In a second step, the antibody is added, which is subsequently crosslinked in the Fc part. This leads to an oriented and covalent immobilization of the immunoglobulin with a very high yield. Protocols for Protein A and Protein G with murine and human IgG are presented. This method may be useful for the preparation of columns for affinity chromatography, immunoprecipitation, antibodies conjugated to magnetic particles, permanent and oriented immobilization of antibodies in biosensor systems, microarrays, microtitration plates or any other system, where the loss of antibodies needs to be avoided, and maximum binding capacity is desired. This method is directly applicable even to antibodies in crude cell culture supernatants, raw sera or protein-stabilized antibody preparations without any purification nor enrichment of the IgG. This new method delivered much higher signals as a traditional method and, hence, seems to be preferable in many applications.
Aldehyde moieties on 2D-supports or microand nanoparticles can function as anchor groups for the attachment of biomolecules or as reversible binding sites for proteins on cell surfaces. The use of aldehyde-based materials in bioanalytical and medical settings calls for reliable methods to detect and quantify this functionality. We report here on a versatile concept to quantify the accessible aldehyde moieties on particle surfaces through the specific binding and subsequent release of small reporter molecules such as fluorescent dyes and nonfluorescent chromophores utilizing acylhydrazone formation as a reversible covalent labeling strategy. This is representatively demonstrated for a set of polymer microparticles with different aldehyde labeling densities. Excess reporter molecules can be easily removed by washing, eliminating inaccuracies caused by unspecific adsorption to hydrophobic surfaces. Cleavage of hydrazones at acidic pH assisted by a carbonyl trap releases the fluorescent reporters rapidly and quasi-quantitatively and allows for their fluorometric detection at low concentration. Importantly, this strategy separates the signal-generating molecules from the bead surface. This circumvents common issues associated with light scattering and signal distortions that are caused by binding-induced changes in reporter fluorescence as well as quenching dye−
dye interactions on crowded particle surfaces. In addition, we demonstrate that the release of a nonfluorescent chromophore via disulfide cleavage and subsequent quantification by absorption spectroscopy gives comparable results, verifying that both assays
are capable of rapid and sensitive quantification of aldehydes on microbead surfaces. These strategies enable a quantitative
comparison of bead batches with different functionalization densities, and a qualitative prediction of their coupling efficiencies in bioconjugations, as demonstrated in reductive amination reactions with Streptavidin.
Dose enhancement by gold nanoparticles (AuNP) was shown to increase the biological effectiveness of radiation damage in biomolecules and tissue. Most of the current studies focus on external beam therapy on combination with AuNP. Here we present a Monte-Carlo study (Geant4) to characterise radioactive AuNP. Radioactive 198 Au emits beta and gamma rays and is considered for applications with solid tumours. To effectively apply 198 AuNP their energy deposit characteristics have to be determined in terms of intrinsic and extrinsic properties e.g. AuNP diameter, AuNP density, and their clustering behaviour. After each decay process, the energy deposit, inelastic scattering events, kinetic energy spectrum of secondary particles within the AuNP themselves and in a spherical target volume of water up to 1 μm radius were determined. Simulations were performed for AuNP radii ranging from 2.5 nm to 20 nm radius, different cluster sizes and densities. The results show an increase of the energy deposit in the vicinity of the AuNP up to 150 nm. This effect nearly vanishes for distances up to one micron. For the case of AuNP clusters and the same activity, the enhancement of the energy deposit increases with the relative gold mass percentage and therefore can be adjusted by changing AuNP radius or clustering behaviour.
Biofuels including ethanol and biodiesel (fatty acid methyl ester, FAME) represent an important renewable fuel alternative to petroleum-derived transport fuels. Increasing biofuels use would bring some benefits, such as a reduction in oil demands and greenhouse gas emissions, and an improvement in air quality. Materials compatibility is a major concern whenever the fuel composition is changed in a fuel system.
The objective of this research was to determine the resistance of frequently used sealing materials such as CR (chloroprene rubber), CSM (chlorosulfonated polyethylene), EPDM (ethylene-propylene-diene rubber), FKM (fluorocarbon rubber), FVMQ (methyl-fluorosilicone rubber), IIR (butyl rubber), NBR (acrylonitrile-butadiene rubber), PA (polyamides), PUR (polyester urethane rubber) and VMQ (methyl-vinyl-silicone rubber), in heating oil with admixtures of biogenic sources such as E10 (fuel with max. 10 % ethanol), E85 (fuel with 85 % ethanol), non-aged and aged biodiesel, diesel fuel with 5 % biodiesel, non-aged and aged B10 (heating oil with 10 % biodiesel) at 20 °C, 40 °C and 70 °C. Mass, tensile strength and breaking elongation of the test specimens were determined before and after the exposure for 84 days in the fuels. The visual examination of some elastomer test specimens clearly showed the great volume increase until break or partial dissolution. Shore hardness A and D (for PA) were determined before and after exposure of the test specimens in the biofuels for 42 days.
There is not determined a threshold for the reduction in tensile properties and Shore hardness in the international standards. Therefore, a threshold of 15 % was set for the evaluation of the compatibility. The sealing materials CR, CSM, EPDM, IIR and NBR were generally not resistant to biodiesel and B10. In summary, it can be therefore stated that the chemical resistance of the fluoropolymers FKM and FVMQ in fuels and biofuels is the best one.
An emerging class of inorganic optical reporters are nearinfrared (NIR) excitable lanthanide-based upconversion nanoparticles (UCNPs) with multicolor emission and long luminescence lifetimes in the range of several hundred microseconds. For the design of chemical sensors and optical probes that reveal analyte-specific changes in their spectroscopic properties, these nanomaterials must be combined with sensitive indicator dyes that change their absorption and/or fluorescence properties selectively upon interaction with their target analyte, utilizing either resonance energy transfer (RET) processes or reabsorption-related inner filter effects. The rational development of UCNP-based nanoprobes for chemical sensing and imaging in a biological environment requires reliable methods for the Surface functionalization of UCNPs, the analysis and quantification of Surface groups, a high colloidal stability of UCNPs in aqueous media as well as the chemically stable attachment of the indicator molecules, and suitable instrumentation for the spectroscopic characterization of the energy-transfer systems and the derived nanosensors. These topics are highlighted in the following feature article, and examples of functionalized core−shell nanoprobes for the sensing of different biologically relevant analytes in aqueous environments will be presented. Special emphasis is placed on the intracellular sensing of pH.
The TED-GC-MS analysis is a two-step method. A sample is first decomposed in a thermogravimetric analyzer (TGA) and the gaseous decomposition products are then trapped on a solid-phase adsorber. Subsequently, the solid-phase adsorber is analyzed with thermal desorption gas chromatography mass spectrometry (TDU-GC-MS). This method is ideally suited for the analysis of polymers and their degradation processes. Here, a new entirely automated System is introduced which enables high sample throughput and reproducible automated fractioned collection of decomposition products. Strengths and limitations of the system configuration are elaborated via three examples focused on practical challenges in materials analysis and identification: i) separate analysis of the components of a wood-plastic-composite material, ii) quantitative determination of weight concentration of the constituents of a polymer blend and iii) quantitative analysis of model samples of microplastics in suspended particulate matter.
Plasma-Transferred-Arc (PTA) welding is a process that enables high deposition rates, but also causes increased thermal load on the component. Laser metal deposition (LMD) welding, on the other hand, reaches a high level of precision and thus achieves comparatively low deposition rates, which can lead to high processing costs. Combining laser and arc energy aims to exploit the respective advantages of both technologies. In this study, a novel approach of this process combination is presented using a PTA system and a 2 kW disk laser. The energy sources are combined in a common process zone as a high-speed plasma laser cladding technology (HPLC), which achieves process speeds of 10 m/min at deposition rates of 6.6 kg/h and an energy per unit length of 39 J/mm.
Exposure response function for a quantitative prediction of weathering caused aging of polyethylene
(2019)
The exposure response function of the carbonyl formation over the bulk has been determined for a high-density polyethylene of a thickness of 200 μm, which was used as a weathering reference material according to ISO TR 19032. To this end, spectral sensitivity was studied by local measurement of the effect of spectrally dispersed irradiation. Both the exposure device and the methodology of determination are described.
The temperature dependency of photooxidation was determined by UV exposure at various temperatures between 23 and 80 °C. Deviations from linearity and thus reciprocity below 40 °C are discussed and assumed to be related to diffusion limitations. An Arrhenius approach –based on data of linear carbonyl formation – has been incorporated into the exposure response function. Using this exposure response function, aging in terms of the distribution of a quantitative property change over a plastic component can be predicted for a specific outdoor location with real chronologic weather data as input for the exposure. Thus, artificial and natural weathering can be linked and compared. The established exposure response function has been validated by outdoor exposure results from the literature. If an estimated diffusion limitation is taken into consideration, calculations and published data are in good agreement.
Resistance spot welding (RSW) is widely used in the automotive industry
as the main joining method. Generally, an automotive body contains
around 2000 to 5000 spot welds. Therefore, it is of decisive importance to characterize the mechanical properties of these areas for the further optimization and improvement of an automotive body structure. The present paper aims to introduce a novel method to investigate the mechanical properties and microstructure of the resistance spot weldment of DP1000 sheet steel. In this method, the microstructure of RSW of two sheets was reproduced on one sheet and on a bigger area by changing of the welding parameters, e. g. welding current, welding time, electrode force and type. Then, tensile tests in combination with digital Image correlation (DIC) measurement were performed on the notched tensile specimens to determine the mechanical properties of the weld metal.
The notch must be made on the welded tensile specimen to force the fracture and elongation on the weld metal, enabling the characterization of its properties. Additionally, the parameters of a nonlinear isotropic material model can be obtained and verified by the simulation of the tensile specimens. The parameters obtained show that the strength of DP1000 steel and the velocity of dislocations for reaching the Maximum value of strain hardening, are significantly increased after RSW. The effect of sample geometry and microstructural inhomogeneity of the welded joint on the constitutive property of the weld metal are presented and discussed.
The transformation of a base-catalyzed, mechano-assisted Knoevenagel condensation of mono-fluorinated benzaldehyde derivatives (p-, m-, o-benzaldehyde) with malonodinitrile was investigated in situ and in real time. Upon milling, the para-substituted product was found to crystallize initially into two different polymorphic forms, depending on the quantity of catalyst used. For low catalyst concentrations, a mechanically metastable phase (monoclinic) was initially formed, converting to the mechanically stable phase (triclinic) upon further grinding. Instead, higher catalyst concentrations crystallize directly as the triclinic product. Inclusion of catalyst in the final product, as evidenced by mass spectrometric analysis, suggests this complex polymorphic pathway may be due to seeding effects. Multivariate analysis for the in situ Raman spectra supports this complex formation pathway, and offers a new approach to monitoring multi-phase reactions during ball milling.
To arrive to sustainable hydrogen-based energy solutions, the understanding of water-splitting catalysts plays the most crucial role. Herein, state-of-the-art hypotheses are combined on electrocatalytic active metal sites toward the oxygen evolution reaction (OER) to develop a highly efficient catalyst based on Earth-abundant cobalt and zinc oxides.
The precursor catalyst Zn0.35Co0.65O is synthesized via a fast microwaveassisted approach at low temperatures. Subsequently, it transforms in situ from the wurtzite structure to the layered γ-Co(O)OH, while most of its zinc leaches out. This material shows outstanding catalytic Performance and stability toward the OER in 1 m KOH (overpotential at 10 mA cm−2 ηinitial = 306 mV, η98 h = 318 mV). By comparing the electrochemical results and ex situ analyses to today’s literature, clear structureactivity correlations are able to be identified. The findings suggest that coordinately unsaturated cobalt octahedra on the surface are indeed the active centers for the OER.
Nanocomposites based on MgAL layered double hydroxides (LDH) and an epoxy resin were prepared and investigated by a combination of complementary methods. As epoxy resin Bisphenol A diglycidyl ether (DGEBA) was used with Diethylenetriamine as curing agent. The LDH was modified with taurine, which acts as an additional crosslinking agent due to its amine groups. The epoxy resin was cured in a presence of the nanofiller, which was added to the system in various concentrations. X-ray scattering, by combination of SAXS and WAXS was used to characterize the morphology of the obtained nanocomposites. These investigations show that the filler is distributed in the matrix as small stacks of ca. 10 layers. The molecular dynamics of the system, as probe for structure, was investigated by broadband dielectric spectroscopy. In addition to the - and -relaxation (dynamic glass transition), characteristic for the unfilled materials, a further process was found which was assigned to localized fluctuations of segments physically adsorbed or chemically bonded to the nanoparticles. The dielectric -relaxation is shifted to higher temperatures for the nanocomposites in comparison to the pure material but depends weakly on the content of nanoparticles. Further, for the first time Flash DSC was employed to a thermosetting system to investigate the glass transition behavior of the nanocomposites. The heating rates were converted in to relaxation rates. For low concentrations of the nanofiller the thermal data overlap more or less with that of the pure epoxy. For higher concentrations the thermal data are shifted significantly to higher temperatures. This is discussed in terms the cooperativity approach to the glass transition.
High-density polyethylene becomes optically transparent during tensile drawing when previously saturated with diesel fuel. This unusual phenomenon is investigated as it might allow conclusions with respect to the material behavior. Microscopy, differential scanning calorimetry, density measurements are applied together with two scanning X-ray scattering techniques: wide angle X-ray scattering (WAXS) and X-ray refraction, able to extract the spatially resolved crystal orientation and internal surface, respectively. The sorbed diesel softens the material and significantly alters the yielding characteristics. Although the crystallinity among stretched regions is similar, a virgin reference sample exhibits strain whitening during stretching, while the diesel-saturated sample becomes transparent. The WAXS results reveal a pronounced fiber texture in the tensile direction in the stretched region and an isotropic orientation in the unstretched region. This texture implies the formation of fibrils in the stretched region, while spherulites remain intact in the unstretched parts of the specimens. X-ray refraction reveals a preferred orientation of internal surfaces along the tensile direction in the stretched region of virgin samples, while the sample stretched in the diesel-saturated state shows no internal surfaces at all. Besides from stretching saturated samples, optical transparency is also obtained from sorbing samples in diesel after stretching.
The paper provides an overview on material defects which may serve as fatigue crack initiation sites and can cause final fatigue failure of a component. These comprise nonmetallic inclusions in Steel and aluminum alloys, cavities such as pores, micro-shrinkages and un-welded regions in cast, sinter and additively manufactured alloys, graphite nodules, shrinkages and other items in modular cast iron, regions of defective microstructure, microcracks and secondary notches such as undercuts and surface roughness. Besides their origin, the effect and mechanisms on fatigue crack initiation and propagation are discussed.
The considerations are proceeded and accompanied by a Brief discussion of some Basic aspects such as the stages of crack propagation along their length scale, the overcoming of crack arrest and the question when a secondary notch can be treated as a crack.
What to measure? is a key question in nanoscience, and it is not straightforward to address as different physicochemical properties define a nanoparticle sample. Most prominent among these properties are size, shape, surface charge, and porosity. Today researchers have an unprecedented variety of measurement techniques at their disposal to assign precise numerical values to those parameters. However, methods based on different physical principles probe different aspects, not only of the particles themselves, but also of their preparation history and their environment at the time of measurement. Understanding these connections can be of great value for interpreting characterization results and ultimately controlling the nanoparticle structure–function relationship. Here, the current techniques that enable the precise measurement of these fundamental nanoparticle properties are presented and their practical advantages and disadvantages are discussed. Some recommendations of how the physicochemical parameters of nanoparticles should be investigated and how to fully characterize these properties in different environments according to the intended nanoparticle use are proposed. The intention is to improve comparability of nanoparticle properties and performance to ensure the successful transfer of scientific knowledge to industrial real‐world applications.
The explosion regions of 1-propanol, 2-propanol, acetone and 1-butanol in air were measured in the presence of CO2, He, N2 and Ar in accordance with EN1839 method T at high temperatures and at atmospheric pressure. The experimental results show that 1-propanol, 2-propanol and acetone have very similar lower explosion limits (LELs). 1-Butanol shows a slightly wider explosion area near the LEL line. In addition, the explosion regions of all combustible/inert gas/air mixtures were calculated with the method of constant adiabatic flame temperature profiles (CAFTP), using the flame temperature profile along the explosion region boundary curve of each combustible/N2/air mixture as a reference to determine the explosion regions of combustible/inert gas/air mixtures with inert gases other than N2 at different initial temperatures. To calculate the explosion regions for systems containing He, the calculation method was modified to include the very different physical transport properties of He. Moreover, the procedure for calculating the apexes in the ternary explosion diagrams was modified. The calculation results show good agreement with the experimental results.
Effect of Inter-Layer Dwell Time on Distortion and Residual Stresses of Laser Metal Deposited Wall
(2019)
The laser metal deposition is an advanced manufacturing technology enabling the production of large-sized parts and partially or completely elimination of machining and welding. The process is characterised by non-uniform local heating of the buildup leading to a stress distribution, which may exceed the yield strength of the material and leads to loss of dimensional accuracy. The interlayer dwell time has a strong influence on the temperature field. The effect of the interlayer dwell time on the distortion and the stress distribution during laser metal deposition of a single-pass wall on the edge of 2 mm thick plate was studied experimentally and numerically. The deposited material was IN625 and the substrate material was AISI 316. A decrease of the residual displacement, due to a uniform shrinkage after the deposition of the last layer and a lower level of the residual compressive longitudinal plastic strain, has been observed in the studies without dwell time. The peak increment of the free edge displacement corresponds to the first layer and hence the subsequent layers will be deposited on the already plastically deformed buildup. The tensile residual longitudinal stress near the top of the buildup and transverse stress near the edges of the buildup is higher than yield strength in the studies with dwell time.
In this paper we report on the characterization by X-ray computed tomography of calcium phosphate (CaP) and polycaprolactone (PCL) coatings on Ti-6Al-4V alloy scaffolds used as a material for medical implants. The cylindrical scaffold has greater porosity of the inner part than the external part, thus, mimicking trabecular and cortical bone, respectively. The prismatic scaffolds have uniform porosity. Surface of the scaffolds was modified with calcium phosphate (CaP) and polycaprolactone (PCL) by dip-coating to improve biocompatibility and mechanical properties. Computed tomography performed with X-ray and synchrotron radiation revealed the defects of structure and morphology of CaP and PCL coatings showing small platelet-like and spider-web-like structures, respectively.
Most knowledge about the structure, function, and evolution of early compound eyes is based on investigations in trilobites. However, these studies dealt mainly with the cuticular lenses and little was known about internal anatomy. Only recently some data on crystalline cones and retinula cells were reported for a Cambrian trilobite species. Here, we describe internal eye structures of two other trilobite genera. The Ordovician Asaphus sp. reveals preserved crystalline cones situated underneath the cuticular lenses. The same is true for the Devonian species Archegonus (Waribole) warsteinensis, which in addition shows the fine structure of the rhabdom in the retinula cells. These results suggest that an apposition eye with a crystalline cone is ancestral for Trilobita. The overall similarity of trilobite eyes to those of myriapods, crustaceans, and hexapods corroborates views of a phylogenetic position of trilobites in the stem lineage of Mandibulata.
For the vast majority of ellipsometric measurements, the application of planar substrates is mandatory and requires a proper sample alignment prior to the measurement. Here, the authors present a generalized approach of how to extract the isotropic ellipsometric sample parameters from an imaging Mueller-matrix measurement even if the sample is significantly misaligned. They validate the method by layer-thickness calculations based on imaging Mueller-matrix measurements of flat crystalline silicon samples that were misaligned on purpose. Furthermore, they also exploit this method’s capabilities to perform spatially resolved layer-thickness measurements of a single-layer indium-tin-oxide coating on a fused-silica microlens without the need of realignment or repositioning of the sample during the measurement.
Among the various welding technologies, resistance spot welding (RSW) and laser beam welding (LBW) play a significant role as joining methods for the automobile industry. The application of RSW and LBW for the automotive body alters the microstructure in the welded areas. It is necessary to identify the mechanical properties of the welded material to be able to make a reliable statement about the material behavior and the strength of welded components. This study develops a method by which to determine the mechanical properties for the weldment of RSW and LBW for two dual phase (DP) steels, DP600 and DP1000, which are commonly used for the automotive bodies. The mechanical properties of the resistance spot weldment were obtained by performing tensile tests on the notched tensile specimen to cause an elongation of the notched and welded area in order to investigate its properties. In order to determine the mechanical properties of the laser beam weldment, indentation tests were performed on the welded material to calculate its force-penetration depth-curve. Inverse numerical simulation was used to simulate the indentation tests to determine and verify the parameters of a nonlinear isotropic material model for the weldment of LBW. Furthermore, using this method, the parameters for the material model of RSW were verified. The material parameters and microstructure of the weldment of RSW and LBW are compared and discussed. The results show that the novel method introduced in this work is a valid approach to determine the mechanical properties of welded high-strength steel structures. In addition, it can be seen that LBW and RSW lead to a reduction in ductility and an increase in the amount of yield and tensile strength of both DP600 and DP1000.
Spherical mesoporous bioactive glasses in the silicon dioxide (SiO2)-phosphorus pentoxide (P2O5)–calcium oxide (CaO) system with a high specific surface area of up to 300m2/g and a medium pore radius of 4 nm were synthesized by using a simple one-pot surfactant-assisted sol–gel synthesis method followed by calcination at 500–700°C. The authors were able to control the particle properties by varying synthesis parameters to achieve microscale powders with spherical morphology and a particle size of around 5–10 mm by employing one structure-directing agent. Due to a high Calcium oxide content of 33·6mol% and a phosphorus pentoxide content of 4·0mol%, the powder showed very good bioactivity up to 7 d of immersion in simulated Body fluid. The resulting microspheres are promising materials for a variety of life science applications, as further processing – for example, granulation – is unnecessary. Microspheres can be applied as materials for powder-based additive manufacturing or in stable suspensions for drug release, in bone cements or fillers.
The freeze casting technique assisted with cryo thiol-ene photopolymerization is successfully employed for the fabrication of macroporous polymer-derived silicon oxycarbide with highly aligned porosity. It is demonstrated that the free radical initiated thiol-ene click reaction effectively cross-linked the vinyl-containing liquid polysiloxanes into infusible thermosets even at low temperatures. Furthermore, mixed solution- and suspension-based freeze casting is employed by adding silica nanopowders. SiOC/SiO2 foams with almost perfect cylindrical shapes are obtained, demonstrating that the presence of nano-SiO2 does not restrict the complete photoinduced cross-linking. The post-pyrolysis HF acid treatments of produced SiOC monoliths yields hierarchical porosities, with SiOC/SiO2 nanocomposites after etching demonstrating the highest specific surface area of 494 m2/g and pore sizes across the macro-, meso- and micropores ranges. The newly developed approach gives a versatile solution for the fabrication of bulk polymer-derived ceramics with controlled porosity.
An understanding of the interactions of 2D nanomaterials with pathogens is of vital importance to developing and controlling their antimicrobial properties. In this work, the interaction of functionalized graphene with tunable hydrophobicity and bacteria is investigated. Poly-(ethylene glycol)-block-(poly-N-isopropylacrylamide) copolymer (PEG-b-PNIPAM) with the triazine joint point was attached to the graphene Surface by a nitrene [2 + 1] cycloaddition reaction. By thermally switching between hydrophobic and hydrophilic states, functionalized graphene sheets were able to bind to bacteria. Bacteria were eventually disrupted when the functionality was switched to the hydrophobic state. On the basis of measuring the different microscopy methods and a live/dead viability assay, it was found that Escherichia coli (E. coli) bacteria are more susceptible to hydrophobic interactions than B. cereus bacteria, under the same conditions. Our investigations confirm that hydrophobic interaction is one of the main driving forces at the presented graphene/bacteria interfaces and promotes the antibacterial activity of graphene derivatives significantly.
In this study, femtosecond laser-induced sub-micrometer structures are generated to modify polyethylene (PE) surface topographies. These surfaces were subjected to bacterial colonization studies with Escherichia coli and Staphylococcus aureus as test strains. The results reveal that the nanostructures do not influence S. aureus coverage, while the adhesion of E. coli is reduced.
Additive manufacturing of alkali-activated materials currently attracts a lot of attention, because of the possibility to produce customized high-performance elements for a range of applications, potentially being more resource-efficient than conventionally produced parts. Here, we describe a new additive manufacturing process for alkali-activated materials that is based on selective laser-heating of lithium aluminate/microsilica slurries. The new process-material combination allows to manufacture elements with complex geometries at high building rates and high accuracy. The process is versatile and transferrable to structures of sizes differing by orders of magnitude. The mechanical strength of the obtained materials was in the range of values reported for conventional metakaolin-based geopolymers, and superior to what has been hitherto reported for alkali-activated materials produced by additive manufacturing. This mechanical performance was obtained despite the fact that the degree of reaction of the lithium aluminate and the microsilica was low, suggesting that significant reactions took place only at the surface of the microsilica particles.
SnOct 2-Catalyzed Syntheses of Cyclic Poly (l-lactide) s with Catechol as Low-Toxic Co-catalyst
(2019)
Polymerizations of l-lactide in bulk at 160 or 180 °C were performed with 1/1 mixtures of catechol (CA) or 4-tert-butylcatechol (BuCA) and tin(II)-2-ethylhexanoate (SnOct2) as catalysts and a variation of the Lac/Cat ratio. Weight average molar masses (Mw) up to 170,000 g mol−1 were obtained with CA and up to 120,000 g mol−1 with BuCA. The cyclic structure of the resulting poly(l-lactide)s was proven by MALDI-TOF mass spectrometry and by comparison of their hydrodynamic volumes with those of commercial linear poly(l-lactide)s. The predominance of even-numbered cycles increased with lower temperatures and shorter polymerization times. This fnding indicates that the cyclic architecture is the results of a ring-expansion polymerization mechanism. Addition of silylated BuCA as co-catalyst was less favorable than addition of free BuCA.
L-Lactide was polymerized in bulk with tin(II)2-ethylhexanoate SnOct2) as catalyst and salicylic acid as cocatalyst. The Lac/Cat ratio, Cocat/Cat ratio, temperature and time were varied. Increasing Cocat/Cat ratios reduced both,polymerization rate and molecular weight. However,under optimized conditions high molar mass (Mw up to 178,000), colorless, cyclic polylactides were formed in a short time. A few polymerizations performed at 160 and 180°C with the combination of SnOct2 and silylated salicylic acid gave similar results. Neat tin II) salicylate was prepared from SnOct2 and used for REPs of L-lactide in bulk, but the results were not better than those obtained from combinations of SnOct2 and salicylic acid. Furthermore, dibutyltin salicylate was synthesized and used as catalyst for polymerizations of L-lactide in bulk at temperatures varying from 102 to 160°C. Cyclic polylactides with Mw’s up to 40,000 were the main reaction products. At 100–102°C a predominance of odd-numbered cycles was found proving a REP mechanism.
A novel cop olyme r based on supramolecular motif2,6-diaminopyridin e and water-soluble acrylamide, poly[N-(6-ace tamidopyridin-2-yl) acrylamide-co-acrylamide], was synthe-size d via rev ersible addi tion–fragmentation chain transfer (RAFT)polymerization with various monomer compositions. The thermo-respon sive behavior of the copolymers was studied by turbidime-try and dynamic light scattering (DLS). The obtained copolymersshowed an upper critical solution temperature (UCST)-typ e phasetransition behavior in water and electrolyte solution. The phasetransition temperature was found to increase with decreasingam ount of acrylamide in the copolymer and increasing concentra-tion of the solution. Furth ermore, the phase transition temperatureva ried in aqueous solutions of electrolytes according to the naturean d concentration of the electrolyte in accordance with theHoffmeister series. A dramatic solvent isotope effect on thetransition temperature was o bserved in this study, as the transitiontemperature was almost 10–12C higher in D2OthaninH2Oatthesame concentration and acrylamide co mposition. The size of theaggregates below the transition temperature was larger in D2Ocompared to that in H2O that can be explained by deuterium iso-tope effect. The thermoresponsive behavior of the copolymers wasalso investigated in different cell medium and found to be exhibitedUCST-type phase transition behavior in different cell medium.Such behavior of the copo lyme rs can be useful in many a pplica-tions including biomedical, microfluidics, optical materials, and indrug delivery.
The introduction of electromagnetic stirring to laser beam welding can bring several beneficial effects e.g. element homogenization and grain refinement. However, the underlying physics has not been fully explored due to the absence of quantitative data of heat and mass transfer in the molten pool. In this paper, the influence of electromagnetic stirring on the thermo-fluid flow and element transport in the wire feed laser beam welding is studied numerically and experimentally. A three-dimensional transient heat transfer and fluid flow model coupled with dynamic keyhole, magnetic induction and element Transport is developed for the first time. The results suggest that the Lorentz force produced by an oscillating magnetic field and its induced eddy current shows an important influence on the thermo-fluid flow and the keyhole stability. The melt flow velocity is increased by the electromagnetic stirring at the rear and lower regions of molten pool. The keyhole collapses more frequently at the upper part. The additional Elements from the filler wire are significantly homogenized because of the enhanced forward and downward flow. The model is well verified by fusion line shape, high-speed images of molten pool and measured element distribution. This work provides a deeper understanding of the transport phenomena in the laser beam welding with magnetic field.
Increasing Exposed Metal Site Accessibility in a Co-MOF-74 Material With Induced Structure-Defects
(2019)
Metal-organic frameworks (MOFs) are promising nanoporous materials with many practical applications. This owes largely to their remarkable porosity and the presence of specific chemical functionalities, such as exposed metal sites (EMS). The MOF-74 structure is known for exhibiting one of the highest EMS densities among porous materials. Moreover, the inclusion of structural defects has been proposed to enhance activity further. This was previously achieved by mixing the original linker together with a second one, having lower topology. The presence of structural defects was evidenced by the resulting crystalline properties and thermal stability. In this work, different mixtures of tetratopic 2,5-dihydroxyterephthalic acid with up to 60% of the tritopic hydroxyterephtalic acid were used to synthesize crystalline Co-MOF-74-like materials. Materials synthesized from higher proportions than 30% of hydroxyterephtalic acid in the synthesis media collapse upon partial removal of the solvent molecules. This indicates the presence of structural defects and the importance of the solvent molecules in stabilizing the crystalline structures. Electron microscope images show that crystal size reduces with inclusion of hydroxyterephtalic acid as the second linker. The presence of coordinated solvent molecules at the EMS was evaluated by Fourier-transform infrared spectra (FTIR) spectroscopy, so that a higher degree of solvent-exchange was observed during washing for defective structures. Furthermore, TG analysis suggests defective structures exhibit lower desolvation temperatures than the defect-free structures. Finally, N2 adsorption-desorption analyses at −196°C showed an enhanced accessibility of the gas to the inner porosity of the defective structures and therefore, the EMS of the material. All these finding make this pathway interesting to enhance the potential interest of these materials for an industrial application because of both a facilitated activation and a better access to the active sites.
Based on the three-phase model of semi-crystalline polymers, we determined all phase fractions of the NiAl-LDH/PLLA nanocomposites in dependence on the concentration of the nanofiller. Moreover, the rigid amorphous fraction (RAF) was separated into the RAFcrystal and the RAFfiller unbiasedly. A detailed comparison to the related nanocomposite system MgAl-LDH/PLLA was made considering that Mg and Ni have different atomic weights. As a first result is was found that NiAl-LDH/PLLA displays a higher crystallization rate compared to MgAl-LDH/PLLA, which is related to the different morphologies of the two nanocomposite systems. For both systems RAFcrystal increases with increasing concentration of the nanofiller. This means in the case of the nanocomposite not each crystal produces the same amount of RAF, as often assumed. Also, RAFfiller increases with the concentration for both systems but in a different way. This is discussed considering again the different morphologies of both nanocomposites.
In order to characterise the material and damage behaviour of additively manufactured polyamide 12 (PA12) under quasi-static load and to implement it in a numerical model, experiments under quasi-static load as well as microstructural investigations were carried out. Selective laser sintering (SLS) was used as the manufacturing process. For the classification of the material behaviour, quasi-static cyclic tests with holding times as well as tensile tests were performed. X-ray refraction and computed tomography (CT) were used to investigate the damage behaviour. The Chaboche model, which has already been applied for metallic materials under thermomechanical loading, served as the basis for the selection of the numerical material model. The same procedure was used for the selection of the damage model, where the Gurson–Tvergaard–Needleman (GTN) model was chosen, which was already used for porous metallic materials. The Chaboche model shows very good agreement with experimental results. Furthermore, the coupling with the GTN model allows a very good modelling of the damage behaviour. Finally, it could be shown that the selected models are suitable to simulate the material and damage behaviour of 3D printed PA12.
An effective method for evaluating the fatigue strength of thick unidirectional composite laminates of wing spar caps has been presented here. A typical width-tapered bending specimen has been developed for a four-point loading set up. Static and fatigue loading was performed at a load ratio R = -1. The complex stress state has been investigated numerically by finite element analysis. Finally, the concept is proven experimentally on specimens made of pultruded fibre rods.
The fatigue behavior of the continuously tapered width by water Jet cutting has been compared to discrete tapering via rod-drop. The new method enables a screening of material fatigue behavior caused by normal and shear loading.
The potential of lowered surface features as well as the application of wear resistant coatings have been known for many years to improve the tribological behavior of forming tools. More recent studies also discuss the capability of protruded microfeatures for adjusting the tribological behavior between contacting surfaces. The demand for a high wear resistance of such structures as well as their economical and reliable production, however, often limits the industrial application. The laser implantation process can overcome these limitations. In contrast to conventional cw-laser dispersing processes, where the formation of uniform metal matrix composite layers is intended, this surface engineering technique aims to improve the tribological behavior of contacting surfaces by a localized dispersing of pre-placed hard ceramic particles. This enables the formation of deterministic textures composed of separated wear resistant dome- or ring-shaped microstructures (implants).
Since TaC shows very promising material properties for improving the wear resistance of tools exposed to severe operating conditions, this paper analyzes its suitability for pulsed laser implantation on X38CrMoV5-3 tool steel for the first time. In the experiments, the influence of the particles and the laser parameters (pulse power, pulse duration and focal diameter) on the material properties of the localized dispersed zones was studied by optical microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. The composite´s (micro-) hardness was measured and calculated by using a rule of mixture. Additionally, the influence of the laser parameters and the TaC particles on the geometrical properties of the implants was studied by optical microscopy and white light interferometry.
The results showed that defect-free implants with hardness values of ~900 HV1 can be obtained at the focal spot, since a localized dispersing of the TaC particles is possible using a pulsed millisecond laser. However, in dependence of the laser intensity, also a partial dissolution of the initial particles occurs. This leads to the precipitation of new dendritic TaC nanoparticles and to varying contents of retained austenite in the matrix. Both effects have a strong influence on the implant hardness and must be considert by the rule of mixture. Regarding the geometrical response it was pointed out that protruded microfeatures with heights up to 10 µm can be created. In comparison to laser remelted zones, the implanted zones showed significantly altered weld pool profiles due to the influence of the particles on the melt convection. A transition of the implant shape from predominantly dome-shaped to predominantly ring-shaped was observed for intensities >1.7∙106 W/cm2 due to the onset of the keyhole effect.
The efficient and sensitive detection of pathogenic microorganisms in aqueous environments, such as water used in medical applications, drinking water, and cooling water of industrial plants, requires simple and fast methods suitable for multiplexed detection such as flow cytometry (FCM) with optically encoded carrier beads. For this purpose, we combine fluorescent Cd-free Ag−In−S ternary quantum dots (t-QDs) with fluorescence Lifetimes (LTs) of several hundred nanoseconds and superparamagnetic Fe3O4 nanoparticles (SPIONs) with mesoporous CaCO3 microbeads to a magneto-fluorescent bead platform that can be surface-functionalized with bioligands, such as antibodies. This inorganic bead platform enables immuno-magnetic separation, target enrichment, and target quantification with optical readout. The beads can be detected with steady-state and time-resolved fluorescence microscopy and flow cytometry (FCM). Moreover, they are suited for readout by time gated emission. In the following, the preparation of these magneto-fluorescent CaCO3 beads, their spectroscopic and analytic characterization, and their conjugation with bacteria-specific antibodies are presented as well as proof-of-concept measurements with Legionella pneumophila including cell cultivation and plating experiments for bacteria quantification. Additionally, the possibility to discriminate between the long-lived emission of the LT-encoded capture and carrier CaCO3 beads and the short-lived Emission of the dye-stained bacteria with time-resolved fluorescence techniques and single wavelength excitation is demonstrated.
In summary, we report a highly modular solid TTA-UC system comprising of a crystalline, thermally stable PCN222(Pd) MOF with CA-coated MOF channels and with a DPA annihilator embedded in a solution-like environment in the MOF channels. This solid material displays blue upconverted delayed emission with a luminescence lifetime of 373 us, a threshold value of 329 mW*cm-2 and a triplet–triplet energy transfer efficiency of 82%. This optical application adds another facet to the versatile chemistry of PCN-222 MOFs. The design concept is also applicable to other TTA-UC pairs and enables tuning of the UCL color, for example, by replacing DPA with other dyes as exemplarily shown for 2,5,8,11-tetra-tert-butyl-perylene, that yields UCL at 450 nm. Current work aims to reduce the oxygen sensitivity and to increase the retention of the trapped annihilators in organic environments, for example, by tuning the chain length of the carboxylic acid and by coating the MOF surface. In addition, the TTA-UC efficiency will be further enhanced by reducing the reabsorption of the UC emission caused by Pd(TCPP) and by optimizing the sensitizer/annihilator interface.
Der 60 °C-Betonversuch ist eine in Deutschland und international verbreitete Methode um die Empfindlichkeit von Gesteinskörnungen und Betonen hinsichtlich einer Alkali-Kieselsäure Reaktion (AKR) zu prüfen. Dieser Beitrag stellt eine neuentwickelte automatisierte Variante der Prüfmethode in einem Minireaktor vor. Dabei werden die Dehnungen von Betonprismen nicht, wie beim konventionellen Test manuell, sondern automatisch in entsprechend ausgerüsteten Prüfbehältern gemessen. Neben einer Reduzierung des Messaufwands bringt die automatisierte Prüfung im Minireaktor weitere Vorteile. Die Dehnungssignale werden, anders als bei der konventionellen Messung, quasi-kontinuierlich aufgezeichnet und bilden das Expansionsverhalten der Prismen detailliert ab. Außerdem bleiben Unterbrechungen der AKR-provozierenden Lagerung aus, die bei der konventionellen Prüfung notwendig sind. Im Beitrag werden die automatisierte und konventionelle Prüfung anhand der Dehnungen von Prismen zweier Gesteinskörnungen verglichen. In Übereinstimmung mit vorhergehenden Untersuchungen sind im Minireaktor gemessene Dehnungen systematisch kleiner als manuell gemessene. Als mögliche Ursache werden Unterschiede im Auslaugverhalten experimentell untersucht. Zur Überprüfung der Einstufung der zwei Gesteinskörnungen erfolgen außerdem Referenzprüfungen in der Nebelkammerlagerung bei 40 °C.
Singlet oxygen can severely damage biological tissue, which is exploited in photodynamic therapy (PDT). In PDT, the effective range is limited by the distribution of the photosensitizer (PS) and the illuminated area. However, no distinction is made between healthy and pathological tissue, which can cause undesired damage. This encouraged us to exploit the more acidic pH of cancerous tissue and design pH-controllable singlet oxygen-generating boron-dipyrromethene (BODIPY) dyes. A pH sensitivity of the dyes is achieved by the introduction of an electronically decoupled, photoinduced electron transfer (PET)-capable subunit in meso-position of the BODIPY core. To favor triplet-state formation as required for singlet Oxygen generation, iodine substituents were introduced at the chromophore core. The resulting pH-controlled singlet oxygen-generating dyes with pKa values in the physiological range were subsequently assessed regarding their potential as pH-controlled PS for PDT.
Using HeLa cells, we could successfully demonstrate markedly different pH-dependent cytotoxicities upon illumination.
The hydration process of Portland cement in a cementitious system is crucial for development of the high-quality cementbased construction material. Complementary experiments of Xray diffraction analysis (XRD), scanning electron microscopy (SEM) and time-resolved laser fluorescence spectroscopy (TRLFS) using europium (Eu(III)) as an optical probe are used to analyse the hydration process of two cement systems in the absence and presence of different organic admixtures.
We Show that different analysed admixtures and the used sulphate carriers in each cement system have a significant influence on the hydration process, namely on the time-dependence in the formation of different hydrate phases of cement. Moreover, the effect of a particular admixture is related to the type of sulphate carrier used.
The quantitative information on the amounts of the crystalline cement paste components is accessible via XRD analysis. Distinctly different morphologies of ettringite and calcium-silicate-hydrates (C-S-H) determined by SEM allow visual conclusions about formation of these phases at particular ageing times. The TRLFS data provides information about the admixture influence on the course of the silicate reaction. The dip in the dependence of the luminescence decay times on the hydration time indicates the change in the structure of C-S-H in the early hydration period. Complementary information from XRD, SEM and TRLFS provides detailed information on distinct periods of the cement hydration process.
Hydrogen gas diffusivity of fourteen glasses of the Na2O-Al2O3-SiO2 system are studied along the joins quartzalbite-jadeite-nepheline (Qz-Ab-Jd-Np, fully polymerized) and albite-sodium disilicate (Ab-Ds, depolymerized).
Density measurements show that ionic porosity decreases from 54.4% (Qz) to 51.5% (Np) and from 52.4% (Ab) to 50.2% (Ds). Hydrogen diffusivity D follows similar trends but at another scale. D at 523 K decreases from 4×10−12 to 3×10−14m2 s−1 (Qz-Np) and from 4×10−13 to 3×10−15m2 s−1 (Ab-Ds). Charge compensating Na+ acting as a filling agent in fully polymerized network structures leads to up to one order of Magnitude higher diffusivities as depolymerized glass structures of the same SiO2 content where Na+ takes the role of a
modifier ion. Temperature dependence of the diffusivity indicates that both the activation energy involved with the moving H2 molecule as well as the accessible volume in the structure contribute to this compositional trend.
Due to the stochastic nature of crack nucleation by Vickers indentation, a statistical analysis of propagation rates of 185 radial cracks was performed. Crack growth was observed directly using a video camera with high Image acquisition rate. It is found that propagation rates are controlled by the environmental reactions at the crack-tip shortly after their initiation (< 1 s). Calibration of the stress intensity KI showed that the residual stress factor χ and the exponent n of the equation KI==χPc−n (with P==load and c==crack length) are broadly distributed among the 185 analyzed cracks, ranging from 10−16 to 104 and from 0.1 to 5, respectively. For the most frequent crack, the equation KI==0.052Pc−1.47 holds. The results show that correlations of indentation-induced crack length to stress intensity necessitate the use of statistical significant data that are calibrated by the environmental reactions at the crack-tip.
Приведено аналитическое решение задачи теплопроводности после прекращения действия подвижного источника теплоты для различных комбинаций источника и свариваемого тела. Показано, что после выключения источника возможно дополнительное плавление основного металла за счет перегретого жидкого металла сварочной ванны. Например, при лазерной сварке со сквозным проплавлением стальной пластины толщиной 2 мм длина кратера шва может быт на 19% больше установившейся длины сварочной ванны. Установлено, что центр кратера, в котором заканчивается затвердевание жидкого металла, смещен в сторону хвостовой части кратера относительно оси теплового источника в момент прекращения его действия. Скорость и направление кристаллизации металла сварочной ванны и кратера различны.
Biofouling constitutes a major challenge in the application of biosensors and biomedical implants, as well as for (food) packaging and marine equipment. In this work, an antifouling surface coating based on the combination of mussel-inspired dendritic polyglycerol (MI-dPG) and an amine-functionalized block copolymer of linear polyglycerol (lPG−b−OA11, OA = oligo-amine) was developed. The coating was compared to a MI-dPG surface which was postfunctionalized with commercially available amine-terminated Polyethylene glycol (HO−PEG−NH2) of similar molecular weight. In the current work, These coatings were compared in their chemical stability, protein fouling characteristics, and cell fouling characteristics. The lPG−b−OA11-functionalized coating showed high chemical stability in both phosphate buffered saline (PBS) and sodium dodecyl sulfate (SDS) solutions and reduced the adhesion of fibrinogen from human plasma with 99% and the adhesion of human serum albumin with 96%, in comparison to the bare titanium dioxide substrate. Furthermore, the Proliferation of human umbilical vein endothelial cells (HUVECs) was reduced with 85% when the lPG−b−OA11 system was compared to bare titanium dioxide. Additionally, a reduction of 94% was observed when the lPG−b−OA11 system was compared to tissue culture polystyrene.
Zeolitic imidazolate frameworks (ZIFs) have been widely investigated for their use in separation, gas adsorption, catalysis, and biotechnology. Their practical applications, however, can be hampered by their structural instability in humid acidic conditions. Here, guided by density functional theory calculations, we demonstrate that the acidic stability of two polymorphic ZIFs (i.e., ZIF-8 and ZIF-L) can be enhanced by the incorporation of functional groups on polypeptides or DNA. A range of complementary synchrotron investigations into the local chemical structure and bonding environment suggest that the enhanced acidic stability arises from the newly established coordinative interactions between the Zn centers and the inserted carboxylate (for polypeptides) or phosphate (for DNA) groups, both of which have lower pKas than the imidazolate ligand. With functional biomolecular homologs (i.e., enzymes), we demonstrate a symbiotic stability reinforcement effect, i.e., the encapsulated biomolecules stabilize the ZIF matrix while the ZIF exoskeleton protects the enzyme from denaturation.
Calcium cobaltite (Ca3Co4O9) is considered as one of the most promising thermoelectric p-type oxides for energy harvesting applications at temperatures above 500 °C. It is challenging to sinter this material as its stability is limited to 920 °C. To facilitate a practicable and scalable production of Ca3Co4O9 for multilayer generators, a systematic study of the influence of powder calcination, Bi-doping, reaction sintering, and pressure-assisted sintering (PAS) on microstructure and thermoelectric properties is presented. Batches of doped, undoped, calcined, and not calcined powders were prepared, tape-cast, and sintered with and without uniaxial pressure at 900 °C. The resulting phase compositions, microstructures and thermoelectric properties were analysed. It is shown that the beneficial effect of Bi-doping observed on pressureless sintered samples cannot be transferred to PAS. Liquid phase formation induces distortions and abnormal grain growth. Although the Seebeck coefficient is increased to 139 µV/K by Bi-doping, the power factor is low due to poor electrical conductivity. The best results were achieved by PAS of calcined powder. The dense and textured microstructure exhibits a high power factor of 326 µW/mK² at 800 °C but adversely high thermal conductivity in the relevant direction. The figure of merit is higher than 0.08 at 700 °C.
To understand the impact of dissolved water on structure and properties, four boron-rich glasses of molar compositions 15-x Na2O x CaO 15 SiO2 70 B2O3 (with x=0, 7.5, 10) and 10 Na2O 15 SiO2 75 B2O3 were prepared and subsequently hydrated (up to 8 wt% H2O). Density measurements show a non-linear trend upon hydration implying large structural changes in particular at water contents<2 wt%. Near-infrared spectroscopy shows hydroxyl groups are the dominant species in all glasses upon the entire range of water content. Molecular H2O is detectable only at total water contents>2 wt%. 11B MAS NMR spectra show that the abundance of BO4 species is mainly controlled by ratio of (Na2O+CaO)/B2O3 while incorporation of water plays a minor role.
Compared to borate glasses, the efficiency of formation of BO4 tetrahedra is favored by crosslinking of the network by SiO4-units. The glass transition temperatures, determined by differential thermal analysis, decreases continuously with water content due to breakage of B-O-B bonds by hydrolysis. However, compared to Silicates and aluminosilicates, the effect of dissolved water is less pronounced which can be explained by weaker B-O-B bonds in comparison to Si-O-Si bonds.
The effect of structural water on density, elastic constants and microhardness of water-bearing soda-lime-silica glasses of up to 21.5 mol% total water is studied. It is found that the Poisson ratio and the water content are positively correlated, while density and the elastic moduli decrease with increasing water content. Vickers hardness decreases by approximately 27% from the dry to the most hydrous glass. For water fractions <3 mol%, the dependencies are non-linear reflecting the non-linear change in the concentrations of OH and H2O molecules dissolved, whereas for water fractions >3 mol% linear dependencies are found. To distinguish the effect of structural water and environmental water, indentations were performed in toluene, nitrogen gas and air. Timedependent softening was evident for testing dry glasses in humid atmospheres as well as for tests of hydrous glasses in dry atmospheres. This indicates that the response times of dissolved water species are effectively equal in both scenarios.
The fabrication and characteristics of amorphous silica reinforced Al matrix composites are studied in this paper. The major starting materials were commercial Al powder and extracted nanoparticle SiO2 (NPS) powder from Indonesian silica sands. Two different active solutions,namely N-butanol and tetramethylammonium hydroxide (TMAH), were introduced during synthesis. Characterisations in terms of physical, mechanical, microstructural and corrosion rate examinations were also employed. Introducing the SiO2 nanoparticles into the Al matrix has decreased the density and increased the porosity of the composites. The addition of N-butanol into Al/SiO2(Al/SiO2(B)) led to broader and lower X-ray diffraction profiles than the addition of TMAH (Al/SiO2(T)). From the microstructural analysis, we found that the SiO2 particles enter and agglomerate into the opening gap of the Al sheets. Furthermore, yield strength, ultimate compression strength and modulus of elasticity tended to reduce the addition of SiO2. The corrosion rate of Al/SiO2(T) was lower than that of Al/SiO2(B) composites.
Fitz's Atlas of coating surveys is designed as loose‐leave binder with a resistant cover that not only provides the possibility of updating the Atlas easily but also makes it practicable for on‐site use. This binder is well structured by sheet dividers with tabs for each of the 16 chapters.
All in all, this atlas supports the surveyor by giving practicable hints and advice, lists and pictures to prepare and conduct investigations and write surveys.
Thermally-induced moisture transport in high-performance concrete studied by X-ray-CT and 1H-NMR
(2019)
The thermohydraulic damage mechanism is one of the primary causes for explosive spalling of highperformance concrete. This paper presents the spatially- and temporally-resolved analysis of the thermally-induced moisture transport and reconfiguration processes by means of X-ray-CT and 1HNMR.
Thermal testing results for a high-performance concrete, which is sensitive to explosive spalling and which was prepared with and without added polypropylene fibres, are presented in this paper. These results indicate that the addition of fibres leads to a faster and deeper migration of the drying front and, thus, to a lower likelihood of vapour-pressure induced explosive spalling.
As resistance to traditional drugs emerges for treatment of Virus infections, the need for new methods for virus inhibition increases. Graphene derivatives with large surface areas have shown strong activity against different viruses. However, the inability of current synthetic protocols to accurately manipulate the structure of graphene sheets in order to control their antiviral activity remains a major challenge. In this work, a series of graphene derivatives with defined polyglycerol sulfate and fatty amine functionalities have been synthesized and their interactions with herpes simplex Virus type 1 (HSV-1) are investigated. While electrostatic interactions between polyglycerol sulfate and virus particles trigger the binding of graphene to virus, alkyl chains induce a high antiviral activity by secondary hydrophobic interactions. Among graphene sheets with a broad range of alkyl chains, (C3–C18), the C12-functionalized sheets showed the highest antiviral activity, indicating the optimum synergistic effect between electrostatic and hydrophobic interactions, but this derivative was toxic against the Vero cell line.
In contrast, sheets functionalized with C6- and C9-alkyl chains showed low toxicity against Vero cells and a synergistic Inhibition of HSV-1. This study shows that antiviral agents against HSV-1 can be obtained by controlled and stepwise functionalization of graphene sheets and may be developed into antiviral agents for future biomedical applications.
Neutron cameras allow visualizing hydrogen distributions with radiographic or tomographic imaging methods in iron (and steel) and many other metals. The necessary contrast between hydrogen and these metals stems from the high difference in the total neutron cross section of both elements. This allows, e.g., the in situ measurement of hydrogen mass flow inside cm thick metal samples with a temporal resolution of at best 10 s using neutron radiography as well as the quantitative measurement of hydrogen accumulations, e.g., at the crack’s inner surfaces in hydrogen embrittled iron samples with neutron tomography. This new quality of the information on a micrometer scale allows new insights for the analysis of hydrogen-assisted damage mechanisms. Further, this method is non-destructive and provides local information in situ and in three dimensions with a spatial resolution of 20 μm - 30 μm. In this contribution, we give a short historical overview of neutron imaging and show examples that demonstrate the spatial and temporal resolution of the neutron radiography and tomography methods in order to visualize and quantify hydrogen accumulations, absorption processes, and diffusion. The examples are taken from the works of researchers dealing with titanium, palladium, zirconium, and iron or steel. More detailed descriptions of the experimental and analytic procedures are given for hydrogen detection using radiography and tomography on iron and steel samples.
The mechanochemical formation of the ionic cocrystals of glucose (Glc) and sodium salts Glc2NaCl·H2O (1) and Glc2NaX (X = Br (2), I (3)) is presented. Products are formed by co-milling Glc with three sodium salts (NaCl, NaBr, NaI). The ionic cocrystals were obtained under both neat grinding and liquid-assisted grinding conditions, the later found to accelerate the reaction kinetics. The crystal structures of the ionic cocrystals (2) and (3) were solved from powder X-ray diffraction data. The structure solution contrasts with the structure of Glc2NaCl·H2O (1) where the electron density at three halide crystallographic sites is modeled as of being the intermediate between water molecule and a chloride ion. The reaction pathways of the three ionic cocrystals were investigated in real time using our tandem approach comprising a combination of in situ synchrotron powder X-ray diffraction and Raman spectroscopy. The results indicate the rapid formation of each cocrystal directly from their respective starting materials without any intermediate moiety formation. The products were further characterized by DTA-TG and elemental analysis.
CsCoO2, featuring a two-dimensional layered architecture of edge- and vertex-linked CoO4tetrahedra, is subjected to a temperature-driven reversible second-order phase transformation at 100 K, which corresponds to a structuralrelaxation with concurrent tilting and breathing modes of edge-sharing CoO4tetrahedra. In the present investigation, it was found that pressure induces a phase transition, which encompasses a dramatic change in the connectivity ofthe tetrahedra. At 923 K and 2 GPa, beta-CsCoO2 undergoes a first-order phasetransition to a new quenchable high-pressure polymorph,alpha-CsCoO2. It is built up of a three-dimensional cristobalite-type network of vertex-sharing CoO4 tetrahedra. According to a Rietveld refinement of high-resolution powderdiffraction data, the new high-pressure polymorph gamma-CsCoO2 crystallizes in the tetragonal space groupI41/amd:2 (Z= 4) with the lattice constants a= 5.8711 (1) and c= 8.3214 (2) A, corresponding to a shrinkage in volume by 5.7% compared with the ambient-temperature and atmospheric pressure-CsCoO2polymorph.The pressure-induced transition (beta>gamma) is reversible;-CsCoO2 stays metastable under ambient conditions, but transforms back to the-CsCoO2structure upon heating to 573 K. The transformation pathway revealed isremarkable in that it is topotactic, as is demonstrated through a clean displacive transformation track between the two phases that employs the symmetry oftheir common subgroupPb21a(alternative setting of space group No. 29 that matches the conventional-phase cell).
A selected series of dipole functionalized triphenylene-based discotic liquid crystals (DLCs) was synthesized and investigated in a systematic way to reveal the phase behavior and molecular dynamics. The later point is of particular importance to understand the charge transport in such systems which is the key property for their applications such as organic field-effect transistors, solar cells or as nanowires in molecular electronics, and also to tune the properties of DLCs. The mesomorphic properties were studied by polarizing optical microscopy, X-ray diffraction, and differential scanning calorimetry, which were compared to the corresponding unfunctionalized DLC. The molecular dynamics were investigated by a combination of state-of-the-art broadband dielectric spectroscopy (BDS) and advanced calorimetry such as fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). Besides localized fluctuations, surprisingly multiple glassy dynamics were detected for all materials for the first time. Glassy dynamics were proven for both processes unambiguously due to the extraordinary broad frequency range covered. The a1-process is attributed to fluctuations of the alky chains in the intercolumnar space because a polyethylene-like glassy dynamics is observed. This corresponds to a glass transition in a confined three-dimensional space. The a2-process found at temperatures lower than a1-process, is assigned to small scale rotational and/or translational in plane fluctuations of the triphenylene core inside distorted columns. This can be considered as a glass transition in a one-dimensional fluid. Therefore, obtained results are of general importance to understand the glass transition, which is an unsolved problem of condensed matter science.
The composites combining aluminum and silica nanoparticles with the addition of tetramethylammonium hydroxide (Al-SiO2(T)) and butanol (Al-SiO2(B)) as mixing media have been successfully fabricated. Corrosion behavior of Al-SiO2 composites before and after exposure in 1M NaCl solution was examined using potentiodynamic polarization (Tafel curve analysis). The study was also equipped with scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and X-ray diffraction (XRD) investigations. Before exposure, Al-SiO2(T) exhibited the best corrosion resistance. Performance improvement was indicated by Al-SiO2(B) up to 10 times better than Al-SiO2(T) after exposure. The increased SiO2 content did not significantly enhance the corrosion resistance of the composites. The Al-SiO2 composites with 5% SiO2 content showed very high corrosion resistance (as the optimum composition). Furthermore, pitting corrosion was observed in the Al-SiO2 composites, indicated by the formation of corrosion products at grain boundaries. The product was affected by the presence of SiO2 in the Al matrix and the NaCl environment at 90 °C (approach to synthetic geothermal media: Na+, Cl, H+, OH-). Our study revealed the presence of γ-Al2O3, γ-Al(OH)3, and Al(OH)2Cl as the dominant corrosion products.
Im Rahmen dieses Übersichtsbeitrages werden die aktuell relevanten Themen des Forums der benannten Stellen für pyrotechnische Gegenstände nach der Richtlinie 2013/29/EU kurz dargestellt. Hierbei wird unter anderem auf das zeitlich dringende Thema BREXIT und die möglichen Auswirkungen auf die benannten Stellen, Wirtschaftsakteure und Marktaufsichtsbehörden eingegangen. Des Weiteren werden Bewertungen von aktuellen Produktentwicklungen diskutiert, bei denen die Anwendung der allseits anerkannten Produktnormen als schwierig erscheint.
Geothermal energy is an interesting alternative to polluting fossil energy sources. Therefore, in Belgium, two wells have been drilled for a deep geothermal power plant. However, the environment to which the installations are exposed is challenging. The geothermal brine has 165 g/l total dissolved solids (of which 90% are sodium and chlorine) and the production temperature can be up to 130 °C. To assess their suitability to be used in a geothermal power plant, the corrosivity of the artificial brine to three common construction materials was investigated with exposure and electrochemical tests. The metals under consideration are a low-alloyed carbon steel (S235JR), an austenitic stainless steel (UNS S31603) and a duplex stainless steel (UNS S31803). The carbon steel, that was found to corrode uniformly, could be considered as a constructional material if a sufficient wall thickness is chosen. The austenitic stainless steel and the duplex stainless steel demonstrate very low uniform
corrosion rates. They are however susceptible to pitting and crevice corrosion. To guarantee safe operation of the geothermal power plant, the susceptibility of the alloys to stress corrosion cracking should be tested and in situ experiments should be performed.
Porous materials play an important role in several fields of technology, especially for energy applications like photovoltaics, electrolysis or batteries. The activity of porous films is affected by properties like porosity, film thickness, chemical composition of the material as well as the crystallinity of the framework. The complex morphology of such porous films constitutes a challenge even for modern analytical techniques and requires new approaches employing the combination/complementation of data of different analytical methods. In this contribution we characterize thin mesoporous iridium-titanium mixed oxide film properties by Electron Probe Microanalysis (EPMA) with energy dispersive X-ray spectroscopy (EDS) at an SEM.
In September 2018, the First European Workshop on Metal Phosphonates Chemistry brought together some prominent researchers in the field of metal phosphonates and phosphinates with the aim of discussing past and current research efforts and identifying future directions. The scope of this perspective article is to provide a critical overview of the topics discussed during the workshop, which are divided into two main areas: synthesis and characterisation, and applications. In terms of synthetic methods, there has been a push towards cleaner and more efficient approaches. This has led to the introduction of high-throughput synthesis and mechanochemical synthesis. The recent success of metal–organic frameworks has also promoted renewed interest in the synthesis of porous metal phosphonates and phosphinates. Regarding characterisation, the main advances are the development of electron diffraction as a tool for crystal structure determination and the deployment of in situ characterisation techniques, which have allowed for a better understanding of reaction pathways. In terms of applications, metal phosphonates have been found to be suitable materials for several purposes: they have been employed as heterogeneous catalysts for the synthesis of fine chemicals, as solid sorbents for gas separation, notably CO2 capture, as materials for electrochemical devices, such as fuel cells and rechargeable batteries, and as matrices for drug delivery.
Lead isotopes are a well-established tool to trace the geographic origin of samples and artefacts in archaeology and geochemistry. In archaeology, lead isotopes are often applied to gain information on the provenance of the used ores especially in lead and silver artefacts. The assignment of a specific and unambiguous provenance in most cases is not possible or at least hindered due to several limitations such as ore deposits overlapping in their lead isotopic composition, a large spread within one ore deposit or a missing overlap with known mining sites. Such difficult cases can only be solved by using information from sources being independent of the isotope data. This information can be of chemical nature such as concentrations of key elements or they can be of archaeological nature such as cultural or trade route information.Within this study, we combined lead isotope data of ores and artefacts with silver mass fractions in the ore deposits, Au/Ag-ratios in ores and artefacts and finally archaeological Information on the cultural context in the Mediterranean and Anatolian Region. This approach enabled us to significantly reduce the potential number of mining regions. Finally, the potential sources could be narrowed down to the three remaining locations the Central Taurus, Arap Dağ and the Eastern Troad. Beneath these three locations, the Central Taurus shows the highest probability for the geographic origin of the galena which has been used to create the Trojan silver artefacts.
Nitrogen-rich noble metal nitrides possess unique mechanical and catalytic properties, therefore their synthesis and characterization is of interest for fundamental solid state chemistry and materials science. In this study we have synthesized a singlesource precursor [Rh(NH3)6]3(N3)5Cl4 (Rh:N ratio 1:11). Its controlled decomposition in a laser-heated diamond anvil cell at 39 GPa resulted in a formation of rhodium pernitride, RhN2. According to the results of single-crystal X-ray diffraction RhN2 has arsenopyrite structure type crystal structure previously unknown for this compound (P21/c (no. 14).
Today glass is broadly used in modern architecture. For indoor applications it is possible to produce decorated glass by using enamel colours and glass painting techniques without any problems. However, this is more limited for applications out of doors. Humidity and environmental pollution attack the surface of the coating and can damage it. There are only a few colours on the market which are resistant towards acids and bases until now. Additionally, most of those colours are opaque. To extend the colour palette, chemically resistant low melting coloured glasses are being developed which are transparent and intensively toned even in thin coating thicknesses. To achieve such an ambitious aim, many parameters have to combine and act in a complex manner. New compositions of lead borosilicate, zinc borosilicate and lead-zinc borosilicate glasses were produced and milled as powder. The thermal properties as well as the environmental stability were analysed. The influence of PbO and ZnO on the thermal properties and the environmental stability were investigated. Evaluation of the fusing results shows that the production and mixture of transparent vitreous enamels for the exterior side of glasses is possible. The tests made it clear that the original materials for making the vitreous enamels must be excellently ground and prepared to achieve a satisfactory result. The method to produce durable vitreous enamels for exterior application also seems to allow the production of glass colours.
Laser-induced periodic surface structures (LIPSS, ripples) with ~500–700 nm period were produced on titanium alloy (Ti6Al4V) surfaces upon scan processing in air by a Ti:sapphire femtosecond laser. The tribological performance of the surfaces were qualified in linear reciprocating sliding tribological tests against balls made of different materials using different oilbased lubricants. Extending our previous work, we studied the admixture of the additive 2-ethylhexyl-zinc-dithiophosphate to a base oil containing only anti-oxidants and temperature stabilizers. The presence of this additive along with the variation of the chemical composition of the counterbodies allows us to explore the synergy of the additive with the laseroxidized nanostructures.
Reliable performance of structural sealant glazing (SSG) systems is necessary to utilise advantages of SSG in glass facades. Conventional durability assessment of structural sealant joints is based on separated weathering tests and empirical fatigue testing. This work presents a new test methodology for performance assessment of SSGjoints at simultaneous weathering and two-dimensional mechanical loading. The climatic and mechanical load function were derived from common loading scenarios according to a worst case approach. A System test specimen, resembling a common SSG-joint, was exposed to 24 h of combined loading in a custom-designed test facility. From the recorded mechanical system response, characteristic parameters were evaluated to assess the performance of the system at varying climatic and mechanical conditions. These experimental results reveal effects of ambient conditions, previous loading and deformation Amplitude peaks on the system response. The proposed test methodology opens up for new performance-related approaches in durability testing.
Dual-phase membranes for high-temperature carbon dioxide Separation have emerged as promising technology to mitigate anthropogenic greenhouse gases emissions, especially as a pre- and post-combustion separation technique in coal burning power plants. To implement These membranes industrially, the carbon dioxide permeability must be improved. In this study, Ce_(0.8) Sm_(0.2) O_(2-d) (SDC) and Ce_(0.8)Sm_(0.19)Fe_(0.01)O_(2-d) (FSDC) ceramic powders were used to form the skeleton in dual-Phase membranes. The use of MgO as an environmentally friendly pore generator allows control over the membrane porosity and microstructure in order to compare the effect of the membrane’s ceramic phase. The ceramic powders and the resulting membranes were characterized using ICP-OES, HSM, gravimetric analysis, SEM/EDX, and XRD, and the carbon dioxide flux density was quantified using a high-temperature membrane permeation setup. The carbon dioxide permeability slightly increases with the addition of iron in the FSDC membranes compared to the SDC membranes mainly due to the reported scavenging effect of iron with the siliceous impurities, with an additional potential contribution of an increased crystallite size due to viscous flow sintering. The increased permeability of the FSDC system and the proper microstructure control by MgO can be further extended to optimize carbon dioxide permeability in this membrane system.
Synthesis of cyclic poly(l-lactide) catalyzed by Bismuth salicylates-A combination of two drugs
(2019)
l‐lactide was polymerized in bulk at 160 or 180°C with mixtures of bismuth subsalicylate (BiSub) and salicylic (SA) as catalysts. The SA/Bi ratio and the monomer/Bi ratio were varied. The highest molecular weights (weight average, Mw) were achieved at a SA/Bi ratio of 1/1 (Mw up to 92 000 g mol−1). l‐Lactide was also polymerized with combinations of BiSub and silylated SA, and Mw values up to 120 000 g mol−1 were achieved at 180°C. MALDI‐TOF mass spectrometry and Mark‐Houwink‐Sakurada measurements proved that under optimized reaction conditions the resulting polylactides consist of cycles.
Diaminodicyanoquinones: Fluorescent dyes with high dipole moments and electron-acceptor properties
(2019)
Fluorescent dyes are applied in various fields of research,includingsolarcellsandlight-emittingdevices,andas reporters for assays and bioimaging studies.Fluorescent dyes with an added high dipole moment pave the way to nonlinear optics and polarity sensitivity.Redox activity makes it possible to switch the moleculeQsphotophysical properties.Diaminodicyanoquinone derivatives possess high dipole moments,yet only lowfluorescence quantum yields,and have therefore been neglected as fluorescent dyes.Here we investigate the fluorescencepropertiesofdiaminodicyanoquinonesusingacombined theoretical and experimental approach and derive molecules with afluorescence quantum yield exceeding 90%. The diaminodicyanoquinone core moiety provides chemical versatility and can be integrated into novel molecular architectures with unique photophysical features.
Low-velocity impact damages were monitored in-situ using an infrared camera before, during and after Impact load. Thermal images were recorded as a function of time at the front side (impact) as well as at the rear side of the plates using a high frame rate. In CFRP and GFRP specimens with different thicknesses and made of various types of fibers and matrix materials, different kind of damages were observed. The sizes of the heated areas being related to the damages and the amount of energy dissipated into heat was determined quantitatively as a function of impact energy and are a measure of the resistance of the different materials against impact load.
Preparation of new bimetallic compounds, including double complex salts (DCSs), containing both a platinumgroup metal and a transition metal of the fourth period is of great interest since these compounds can act as precursors of bimetallic materials. One example of using such compounds is the preparation of ultrafine particles of solid solutions of metals or intermetallic compounds on various supports to fabricate highly efficient catalysts with a low content of noble
metals.
Compounds containing coordinated oxalate anions are important objects of synthetic chemistry and interesting precursors. For example, a lot of attention is given to salts with [M(C2O4)2]2– anions, where M = Co, Ni, Cu, Pt, Pd. On the one hand, the uniqueness of oxalate coordinated anions is due to the fact that they are easily obtained and are stable both in aqueous solutions and in the solid phase; on the other hand, they are thermally decomposed at relatively low temperatures, which makes them promising precursors for the fabrication of metallic and oxide materials.
The ease with which an energetic material (explosives, propellants, and pyrotechnics) can be initiated is a critical parameter to assess their safety and application. Impact sensitivity parameters are traditionally derived experimentally, at great cost and risk to safety. In this work we explore a fully ab initio Approach based on concepts of vibrational energy transfer to predict impact sensitivities for a series of chemically, structurally and energetically diverse molecular materials. The quality of DFT calculations is assessed for a subset of the materials by comparison with experimental inelastic neutron scattering spectra (INS). A variety of models are considered, including both qualitative and quantitative analysis of the vibrational spectra. Excellent agreement against experimental impact sensitivity is achieved by consideration of a multi-phonon ladder-type up-pumping mechanism that includes both overtone and combination pathways, and is improved further by the added consideration of temperature. This fully ab initio approach not only permits ranking of energetic materials in terms of their impact sensitivity but also provides a tool to guide the targeted design of advanced energetic compounds with tailored properties.
Due to the complexity of friction materials, the characterization of the tribological properties is prioritised over the bulk material properties even though the tribology is expected to be influenced by the material behaviour. The extent of this relationship is still unknown and further knowledge is required to account for the load history and evolution of the bulk properties. With this view, the compression behaviour and microstructure of a semi-metallic friction material with reduced formulation were investigated before and after a braking program. The thermal loading was monitored with inserted thermocouples. Uniaxial compression tests coupled with Digital Image Correlation (DIC) show significant changes in the worn material, which develops a compression behaviour similar to that of a tri-layered material. The microstructural analysis indicates microcracking of the metallic matrix and carbon diffusion in the Fe-phase. The thermal loading was found to be the key parameter controlling both the friction behaviour and evolution of the material properties. The expected effects of material evolution on the contact uniformity, durability and tribology are discussed.
Hybrid laser-arc welding offers many advantages, such as deep penetration, good gap bridge-ability, and low distortion due to reduced heat input. The filler wire which is supplied to the process is used to influence the microstructure and mechanical properties of the weld seam.
A typical problem in deep penetration high-power laser beam welding with filler wire and hybrid laser-arc welding is an insufficient mixing of filler material in the weld pool, leading to a non-uniform element distribution in the seam. In this study, oscillating magnetic fields were used to form a non-conservative component of the Lorentz force in the weld pool to improve the element Distribution over the entire thickness of the material. Full penetration hybrid laser-arc welds were performed on 20-mm-thick S355J2 steel plates with a nickel-based wire for different arrangements of the oscillating magnetic field. The Energy-dispersive X-ray spectroscopy (EDS) data for the distribution of two tracing elements (Ni and Cr) were used to analyze the homogeneity of dilution of the filler wire.
With a 30° turn of the magnetic field to the welding direction, a radical improvement in the filler material distribution was demonstrated. This would lead to an improvement of the mechanical properties with the use of a suitable filler wire.
The advantage of selective laser melting (SLM) is its high accuracy and geometrical flexibility.
Because the maximum size of the components is limited by the process chamber, possibilities must be found to combine several parts manufactured by SLM. An application where this is necessary, is, for example, the components of gas turbines, such as burners or oil return pipes, and inserts, which can be joined by circumferential welds. However, only a few investigations to date have been carried out for the welding of components produced by SLM. The object of this paper is, therefore, to investigate the feasibility of laser beam welding for joining SLM tube connections made of nickel-based alloys.
For this purpose, SLM-manufactured Inconel 625 and Inconel 718 tubes were welded with a Yb:YAG disk laser and subsequently examined for residual stresses and defects. The results showed that the welds had no significant influence on the residual stresses. A good weld quality could be achieved in the seam circumference. However, pores and pore nests were found in the final overlap area, which meant that no continuous good welding quality could be accomplished. Pore formation was presumably caused by capillary instabilities when the laser power was ramped out.
The presented study deals with the performing and mechanical testing of single pass hybrid laser-arc welds (HLAW) on 25 mm thick plates made of steel grade S355J2. One of the challenges have to be solved at full penetration HLAW of thick plates is the drop formation occurring due to the disbalances of the forces acting in the keyhole and on the melt pool surface. Such irregularities mostly limit the use of high-power laser beam welding or HLAW of thick-walled constructions. To overcome this problem, an innovative concept of melt pool support based on generating Lorentz forces in the weld pool is used in this work. This method allows to perform high quality welds without sagging even for welding of 25 mm thick plates in flat position at a welding speed of 0.9 m min-1. For the obtain of full penetrated welds a laser beam power of 19 kW was needed. A high V-impact energy of up to 160 J could be achieved at the test temperature of 0 °C. Even at the most critical part in the weld root an impact energy of 60 J in average could be reached. The tensile strength of the weld reaches that of the base material. An introduce of the HLAW process with electromagnetic support of the melt pool in the industrial practice is an efficient alternative to the time- and cost-intensive arc-based multi-layer welding techniques which are established nowadays for joining of thick-walled constructions.
Due to their high strength-to-weight ratio and excellent fatigue resistance, glass fiber reinforced polymers (GFRP) are used as a construction material in a variety of applications including composite high-pressure gas storage vessels. Thus, an early damage detection of the composite material is of great importance. Material degradation can be determined via measuring the distributed strain profile of the GFRP structures. In this article, swept wavelength interferometry based distributed strain sensing (DSS) was applied for structural health monitoring of internal pressure loaded GFRP tube specimens. Measured strain profiles were compared to theoretical calculation considering Classical Lamination Theory. Reliable strain measurements with millimeter resolution were executed even at elongations of up to 3% in the radial direction caused by high internal pressure load. Material fatigue was localized by damaged-induced strain changes during operation, and detected already at 40% of burst pressure.
Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si and S have found their way into their building blocks so far. Here, we expand the toolbox available to polymer and materials chemists by one additional nonmetal, phosphorus. Starting with a building block that contains a λ⁵‐phosphinine (C₅P) moiety, we evaluate a number of polymerisation protocols, finally obtaining a π‐conjugated, covalent phosphinine‐based framework (CPF‐1) via Suzuki‐Miyaura coupling. CPF‐1 is a weakly porous polymer glass (72.4 m2 g‐1 N2 BET at 77 K) with green fluorescence (λmax 546 nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co‐catalyst at a rate of 33.3 μmol h‐¹ g‐¹. Our results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine‐based frameworks show promising electronic and optical properties that might spark future interest in their applications in light‐emitting devices and heterogeneous catalysis.
Low temperature functionalization of two-dimensional boron nitride for electrochemical sensing
(2019)
Two-dimensional hexagonal boron nitride(h-BN)as an emerging nanomaterial exhibits uniquephysicochemical properties, making it suitable candidate for a wide spectrum of applications.However, due to its poor functionality, the processability of this nanomaterial is low. In this work, wereport on a straightforward and scalable approach for the functionalization of h-BN by nitrene[2+1]cycloaddition at room temperature. The triazine-functionalized h-BN(Trz-BNs)showed ahigh reactivity toward nucleophiles, through which post-modifications are performable. The post-modification of Trz-BNs by L-cysteine was studied using cyclic voltammetry and differential pulsevoltammetry. Taking advantage of the scalable and straightforward functionalization as well as abilityof triazine functional groups for the controlled post-modifications, Trz-BNs is a promisingnanoplatform for a wide range of future applications.
The influence of processing parameters on X‑ray emission during ultra‑short pulse laser machining
(2019)
During ultra-short laser material processing at high laser pulse repetition rates unwanted X-ray radiation can be generated in a quantity that may constitute a potential risk for health. An adequate X-ray radiation protection requires a thoroughly understanding of the influence of the laser processing parameters on the generation of X-ray radiation. In the present work, the generated X-ray dose during laser machining was investigated in air for varying beam scanning conditions at a pulse duration of 925 fs, a center wavelength of 1030 nm and a laser peak intensity of 2.6 × 10^14 W/cm^2. The X-ray radiation dose and the corresponding spectral X-ray emission were investigated in dependence on the laser’s pulse repetition rate and on the beam scanning speed. The results show a strong dependence of the X-ray emission on these laser processing parameters.
Thin films (200-7nm) of the asymmetric polymer blend poly(vinyl methyl ether) (PVME)/polystyrene (PS) (25/75wt%) were investigated by broadband dielectric spectroscopy (BDS). Thicker samples ([Formula: see text]37 nm) were measured by crossed electrode capacitors (CEC), where the film is capped between Al-electrodes. For thinner films ([Formula: see text]37 nm) nanostructured capacitors (NSC) were employed, allowing one free surface in the film. The dielectric spectra of the thick films showed three relaxation processes ( [Formula: see text] -, [Formula: see text] - and [Formula: see text] -relaxation), like the bulk, related to PVME fluctuations in local spatial regions with different PS concentrations. The thickness dependence of the [Formula: see text] -process for films measured by CECs proved a spatially heterogeneous structure across the film with a PS-adsorption at the Al-electrodes. On the contrary, for the films measured by NSCs a PVME segregation at the free surface was found, resulting in faster dynamics, compared to the CECs. Moreover, for the thinnest films ([Formula: see text]26 nm) an additional relaxation process was detected. It was assigned to restricted fluctuations of PVME segments within the loosely bounded part of the adsorbed layer, proving that for NSCs a PVME enrichment takes place also at the polymer/substrate interface.
A numerical framework for simulation of the steady-state thermal behaviour in keyhole mode welding has been developed. It is based on the equivalent heat source concept and consists of two parts: computational thermo-fluid dynamics and heat conduction. The solution of the thermo-fluid dynamics problem by the finite element method for a bounded domain results in a weld pool interface geometry being the input data for a subsequent heat conduction problem solved for a workpiece by a proposed boundary element method. The main physical phenomena, such as keyhole shape, thermo-capillary and natural convection and temperature-dependent material properties are taken into consideration. The developed technique is applied to complete-penetration keyhole laser beam welding of a 15 mm thick low-alloyed steel plate at a welding speed of 33 mm/s and a laser power of 18 kW. The fluid flow of the molten metal has a strong influence on the weld pool geometry. The thermo-capillary convection is responsible for an increase of the weld pool size near the plate surfaces and a bulge formation near the plate middle plane. The numerical and experimental molten pools, cross-sectional weld dimensions and thermal cycles of the heat affected zone are in close agreement.
Metal carbides have shown great promise in a wide range of applications due to their unique catalytic, electrocatalytic and magnetic properties. However, the scalable production of dispersible metal carbide nanoparticles remains a challenge. Here, we report a simple and scalable route to dispersible iron carbide (Fe3C) nanoparticles. This uses MgO nanoparticles as a removable ‘cast’ to synthesize Fe3C nanoparticles from Prussian blue (KFeIII[FeII(CN)6]). Electron tomography demonstrates how nanoparticles of the MgO cast encase the Fe3C nanoparticles to prevent sintering and agglomeration during the high-temperature synthesis. The MgO cast is readily removed with ethylenediaminetetraacetic acid (EDTA) to generate Fe3C nanoparticles that can be used to produce a colloidal ferrofluid or dispersed on a support material.
Yb,Nd,Er-doped upconversion nanoparticles (UCNPs) have attracted considerable interest as luminescent reporters for bioimaging, sensing, energy conversion/shaping, and anticounterfeiting due to their capability to convert multiple near-infrared (NIR) photons into shorter wavelength ultraviolet, visible or NIR luminescence by successive absorption of two or more NIR photons. This enables optical measurements in complex media with very little background and high penetration depths for bioimaging. The use of Nd3+ as substitute for the commonly employed sensitizer Yb3+ or in combination with Yb3+ shifts the excitation wavelength from about 980 nm, where the absorption of water can weaken upconversion luminescence, to about 800 nm, and laser-induced local overheating effects in cells, tissue, and live animal studies can be minimized. To systematically investigate the potential of Nd3+ doping, we assessed the performance of a set of similarly sized Yb3+,Nd3+,Er3+-doped core- and core–shell UCNPs of different particle architecture in water at broadly varied excitation power densities (P) with steady state and time-resolved fluorometry for excitation at 980 nm and 808 nm. As a measure for UCNPs performance, the P-dependent upconversion quantum yield (Φ) and its saturation behavior were used as well as particle brightness (B). Based upon spectroscopic measurements at both excitation wavelengths in water and in a lipid phantom and B-based calculations of signal size at different penetration depths, conditions under which excitation at 808 nm is advantageous are derived and parameters for the further optimization of triple-doped UCNPs are given.
Advantages such as element homogenization and grain refinement can be realized by introducing electromagnetic stirring into laser beam welding. However, the involved weld pool behavior and its direct role on determining the final microstructure have not been revealed quantitatively. In this paper, a 3D transient heat transfer and fluid flow model coupled with element transport and magnetic induction is developed for wire feed laser beam welding with electromagnetic stirring. The magnetohydrodynamics, temperature profile, velocity field, keyhole evolution and element distribution are calculated and analyzed. The model is well tested against the experimental results. It is suggested that a significant electromagnetic stirring can be produced in the weld pool by the induced Lorentz force under suitable electromagnetic parameters, and it shows important influences on the thermal fluid flow and the solidification parameter. The forward and downward flow along the longitudinal plane of the weld pool is enhanced, which can bring the additional filler wire material to the root of the weld pool. The integrated thermal and mechanical impacts of electromagnetic stirring on grain refinement which is confirmed experimentally by electron backscatter diffraction analysis are decoupled using the calculated solidification parameters and a criterion of dendrite fragmentation.
Determining a suitable and reliable end-of-lifetime criterion for O-ring seals is an important issue for long-term seal applications. Therefore, seal failure of ethylene propylene diene rubber (EPDM) and hydrogenated nitrile butadiene rubber (HNBR) O-rings aged in the compressed state at 125 °C and at 150 °C for up to 1.5 years was analyzed and investigated under static conditions, using both non-lubricated and lubricated seals. Changes of the material properties were analyzed with dynamic-mechanical analysis and permeability experiments. Indenter modulus measurements were used to investigate DLO effects. It became clear that O-rings can remain leak-tight under static conditions even when material properties have already degraded considerably, especially when adhesion effects are encountered. As a feasible and reliable end-of-lifetime criterion for O-ring seals under static conditions should include a safety margin for slight dimensional changes, a modified leakage test involving a small and rapid partial decompression of the seal was introduced that enabled determining a more realistic but still conservative end-of-lifetime criterion for an EPDM seal.
The mechanism of ternary cocrystal formation, and the potential role of intermediate binary phases, has been debated for some time. We report here the first in situ real-time monitoring of two prototypic ternary cocrystals. Our results suggest that the question is more complicated than previously considered. The mechanism of mechanochemical ternary cocrystal formation depends on the milling conditions, here the milling frequency and addition of liquid. Binary phases can form under certain conditions, but do not act as intermediates in the formation of the ternary cocrystals. Rather, binary phases are competitive with the ternary phase, and their formation appears to compete with that of the ternary components. The presence of binary phases leads to an increase in the overall reaction time. The results reported here offer the first insights into the true complexities of mechanochemical multi-component synthesis of higher order multi-component crystals and demonstrate a new understanding of the influence of milling condition for the study of mechanisms and kinetics.
Polymers of Intrinsic Microporosity (PIMs) of high performance have developed as materials with a wide application range in gas separation and other energy-related fields. Further optimization and long-term behavior of devices with PIMs require an understanding of the structure-property relationships including physical aging. In this context the glass transi-tion plays a central role, but with conventional thermal analysis a glass transition is usually not detectable for PIMs be-fore their thermal decomposition. Fast scanning calorimetry provides evidence of the glass transition for a series of PIMs, as the time scales responsible for thermal degradation and for the glass transition are decoupled by employing ultrafast heating rates of tens of thousands K s-1. The investigated PIMs were chosen considering the chain rigidity. The estimated glass transition temperatures follow the order of the rigidity of the backbone of the PIMs.
Elastomers are used in almost all areas of industrial applications, such as tires, engine mounts, bridge bearings, seals or coatings. During their use in operation, they are exposed to different environmental influences. These include, in particular, climatic factors such as air oxygen, high temperatures, light (UV radiation) and the influence of media (e.g. oils, fuels). A very important result of these factors is the chemical ageing of elastomers. In this case, the elastomer degenerates and changes its chemical structure in the aged regions, which leads to an irreversible change in the material properties in connection with the reduction in its usability. In this paper, chemical ageing of nitrile butadiene rubber (NBR) is investigated. Especially in case of thermo-oxidative ageing at elevated operating temperatures, the ageing processes run inhomogeneously. These effects are known as diffusion-limited oxidation (DLO) and are associated with the diffusion–reaction behaviour of atmospheric oxygen with the elastomer network. For these reasons, NBR samples are artificially aged in air and subjected to different experimental methods, which are presented and discussed. Additional results from inhomogeneous mechanical tests and permeation tests indicate the causes of the DLO-effect, show the influence of chemical ageing and are subsequently used for parameter identification in relation to the diffusion–reaction equation. A continuum-mechanical modelling approach is also presented here, which describes the finite hyperelasticity, diffusion–reaction processes as well as chemical degradation and reformation of the elastomer network. This multifield problem leads to a system of partial and ordinary differential equations and constitutive equations and is solved within the finite element method.
We present a comprehensive investigation of the magnetic and optical properties of an ytterbium complex, which combines two desirable and practical features into a single molecular system. Based upon YbIII Ions that promote near-infrared optical activity and a chemical backbone that is ideal for an in-depth understanding of the magnetic behaviour, we have designed a multifunctional opto-magnetic species that operates as a luminescent thermometer and as a single-molecule magnet (SMM). Our magnetic investigations, in conjunction with ab initio calculations, reveal one of the highest energy barriers reported for an YbIII-based complex. Moreover, we correlate this anisotropic barrier with the Emission spectrum of the compound, wherein we provide a complete assignment of the energetic profile of the complex. Such studies lay the foundation for the design of exciting multi-faceted materials that are able to retain information at the single-molecule level and possess built-in thermal self-monitoring capabilities.
Biopolymers are very efficient for significant applications ranging from tissue engineering, biological devices to water purification. There is a tremendous potential value of cellulose because of ist being the most abundant biopolymer on earth, swellability, and functional groups to be modified. A novel, highly efficient route for the fabrication of mechanically stable and natural hydrogels is described in which cellulose and glycine are dissolved in an alkaline solution of NaOH and neutralized in an acidic solution. The dissolving temperature and the glycine amount are essential parameters for the self-assembly of cellulose chains and for Tuning the morphology and the aggregate structures of the resulting hydrogels. Glycine plays the role of a physical crosslinker based on the Information obtained from FTIR and Raman spectra. Among the prepared set of hydrogels, CL5Gly30 hydrogels have the highest capacity to absorb water. The prepared CL5Gly30 gels can absorb up to seven times their dry weight due to its porous 3-D network structure. CL5Gly10 hydrogel exhibits 80% deformation under 21 N force executed. The method developed in this article can contribute to the application of heavy metal adsorption in aqueous solutions for water purification and waste management.
Ageing at 600 °C (from 0.1 h up to 20 h) leads to the formation of precipitations at the ferrite-ferrite (α/α) and ferrite-austenite (α/γ) grain boundaries of the lean duplex stainless steel (LDSS) X2CrNiN22-2. This leads to sensitisation due to chromium depletion and decreased pitting corrosion resistance proven by the results of various electrochemical methods (DL-EPR and determination of CPT, Epit). These results were compared with the KorroPad method, which uses an agar-based gel-electrolyte for the detection of stainless steel surfaces prone to pitting corrosion. However, the standard configuration of the KorroPad showed no differentiation for the various ageing conditions. Therefore, modified versions of the KorroPad with two, five and ten times higher NaCl and potassium ferrocyanide III (K3[Fe(CN)6]) concentrations were successfully used to visualise the behaviour detected by DL-EPR, Epit and CPT. Therefore, the KorroPad method can also detect a microstructure related reduction of pitting corrosion resistance, which can drastically reduce the experimental effort to generate sensitisation diagrams for stainless steels.
A discussion is provided on demands that must be met in order to apply fracture mechanics to the determination of overall fatigue lifetime and strength, i.e., S-N curves and fatigue limits. These comprise the determination of the cyclic crack driving force for all stages of fatigue crack propagation, in particular for the short crack stage where the crack driving force has to be determined for elastic-plastic deformation and the gradual build-up of the crack closure phenomenon. Special emphasis is put on a fatigue damage relevant specification of the initial crack size. Different approaches in the literature are discussed. Another important aspect is the adequate treatment of multiple crack propagation. Finally, the discussion is illustrated by an example of a butt weld made of a medium strength steel.