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The flammable hydrogen-blended methane–air and natural gas–air mixtures raise specific safety and environmental issues in the industry and transportation; therefore, their explosion characteristics such as the explosion limits, explosion pressures, and rates of pressure rise have significant importance from a safety point of view. At the same time, the laminar burning velocities are the most useful parameters for practical applications and in basic studies for the validation of reaction mechanisms and modeling turbulent combustion. In the present study, an experimental and numerical study of the effect of hydrogen addition on the laminar burning velocity (LBV) of methane–air and natural gas–air mixtures was conducted, using mixtures with equivalence ratios within 0.90 and 1.30 and various hydrogen fractions rH within 0.0 and 0.5. The experiments were performed in a 14 L spherical vessel with central ignition at ambient initial conditions. The LBVs were calculated from p(t) data, determined in accordance with EN 15967, by using only the early stage of flame propagation. The results show that hydrogen addition determines an increase in LBV for all examined binary flammable mixtures. The LBV variation versus the fraction of added hydrogen, rH, follows a linear trend only at moderate hydrogen fractions. The further increase in rH results in a stronger variation in LBV, as shown by both experimental and computed LBVs. Hydrogen addition significantly changes the thermal diffusivity of flammable CH4–air or NG–air mixtures, the rate of heat release, and the concentration of active radical species in the flame front and contribute, thus, to LBV variation.
Performance of calcium phosphate cements in the augmentation of sheep vertebrae - An ex vivo study
(2021)
Oil-based calcium phosphate cement (Paste-CPC) shows not only prolonged shelf life and injection times, but also improved cohesion and reproducibility during application, while retaining the advantages of fast setting, mechanical strength, and biocompatibility. In addition, poly(L-lactideco-glycolide) (PLGA) fiber reinforcement may decrease the risk for local extrusion. Bone defects (diameter 5 mm; depth 15 mm) generated ex vivo in lumbar (L) spines of female Merino sheep (2–4 years) were augmented using: (i) water-based CPC with 10% PLGA fiber reinforcement (L3); (ii) Paste-CPC (L4); or (iii) clinically established polymethylmethacrylate (PMMA) bone cement (L5). Untouched (L1) and empty vertebrae (L2) served as controls. Cement performance was analyzed using micro-computed tomography, histology, and biomechanical testing. Extrusion was comparable for Paste-CPC(-PLGA) and PMMA, but significantly lower for CPC + PLGA. Compressive strength and Young’s modulus were similar for Paste-CPC and PMMA, but significantly higher compared to those for empty defects and/or CPC + PLGA. Expectedly, all experimental groups showed significantly or numerically lower compressive strength and Young’s modulus than those of untouched controls. Ready-to-use Paste-CPC demonstrates a performance similar to that of PMMA, but improved biomechanics compared to those of water-based CPC + PLGA, expanding the therapeutic arsenal for bone defects. O, significantly lower extrusion of CPC + PLGA fibers into adjacent lumbar spongiosa may help to reduce the risk of local extrusion in spinal surgery.
Polychromatic and wavelength-selective neutron transmission radiography were applied during bead-on-plate welding on 5 mm thick sheets on the face side of martensitic low transformation temperature (LTT) steel plates using gas tungsten arc welding (GTAW). The in situ visualization of austenitization upon welding and subsequent α’-martensite formation during cooling could be achieved with a temporal resolution of 2 s for monochromatic imaging using a single neutron wavelength and of 0.5 s for polychromatic imaging using the full spectrum of the beam (white beam).
The spatial resolution achieved in the experiments was approximately 200 µm. The transmitted monochromatic neutron beam intensity at a wavelength of λ = 0.395 nm was significantly reduced during cooling below the martensitic start temperature M s since the emerging martensitic phase has a ~10% higher attenuation coefficient than the austenitic phase. Neutron imaging was significantly influenced by coherent neutron scattering caused by the thermal motion of the crystal lattice (Debye–Waller factor), resulting in a reduction in the neutron transmission by approx. 15% for monochromatic and by approx. 4% for polychromatic imaging.
Raman spectroscopy is a well established tool for the analysis of vibration spectra, which then allow for the determination of individual substances in a chemical sample, or for their phase transitions. In the time-resolved-Raman-sprectroscopy the vibration spectra of a chemical sample are recorded sequentially over a time interval, such that conclusions for intermediate products (transients) can be drawn within a chemical process. The observed data-matrix M from a Raman spectroscopy can be regarded as a matrix product of two unknown matrices W and H, where the first is representing the contribution of the spectra and the latter represents the chemical spectra. One approach for obtaining W and H is the non-negative matrix factorization. We propose a novel approach, which does not need the commonly used separability assumption. The performance of this approach is shown on a real world chemical example.
Sample functions, i.e., stochastic process realizations, are used to define cumulative damage phenomena which end into an observable terminal state or failure. The complexity inherent to such phenomena justifies the use of phenomenological models associated with the evolution of a physical magnitude feasible to be monitored during the test. Sample functions representing the damage evolution may be identified, once normalized to the interval [0,1], with cumulative distribution functions (cdfs), generally, of the generalized extreme value (GEV) family. Though usually only a fraction of the whole damage evolution, according to the specific problem handled, is available from the test record, the phenomenological models proposed allow the whole damage process to be recovered. In this way, down- and upwards extrapolations of the whole damage process beyond the scope of the experimental program are provided as a fundamental tool for failure prediction in the practical design. The proposed methodology is detailed and its utility and generality confirmed by its successive application to representative well-known problems in fatigue and fracture characterization. The excellent fittings, the physical interpretation of the model parameters and the good expectations to achieve a complete probabilistic analysis of these phenomena justify the interest of the proposed phenomenological approach with possible applications to other cumulative damage processes.
The aim of this study is to develop polymeric thin films for corrosion protection of magnesium alloy AZ31. As polymer matrix, poly(4-vinyl pyridine) (P4VP) is selected due to its semiconducting properties and protonic conductivity. Polyacrylic acid is tested as crosslinking layers to improve interfacial adhesion. The macroscopic corrosion properties of the multilayer coatings are investigated by means of electrochemical methods, such as linear sweep voltammetry and electrochemical impedance spectroscopy (EIS), in corrosive media simulating technical and biomedical applications. It is demonstrated that thin multilayer coatings can suppress the corrosion rates of magnesium alloys. To our best knowledge, this is the first demonstration of the use of P4VP as a conducting polymer film with protonic conductivity for corrosion protection of magnesium alloys.
The space heating system accounts for 20%~50% of building energy consumption, and may lead to energy waste due to unreasonable controls. In this study, an energy-efficient floor heating system with intelligent control was proposed to improve energy efficiency of the system. In order to validate the concept of the proposed intelligent control, an experimental system was designed and constructed in Chengdu, China. Temperature, control cycle and energy consumption were then studied under different control strategies. The result shows that a larger flow rate of supply water will result in a longer control cycle and a lower control frequency, i.e., the average control cycle at 7 L min−1 is 1.7 h during the test day, while it is 1.5 h at 5 L min−1. Moreover, adopting water with a higher temperature and flow rate could achieve a higher efficiency of the system. The energy consumptions in case 1 (5 L min−1, 50 °C), case 2 (5 L min−1, 55 °C), case 5 (7 L min−1, 55 °C) and case 6 (7 L min−1, 60 °C) are 4746 kJ, 3534 kJ, 3093 kJ and 3028 kJ, respectively. Based on the experimental data, the supply water temperature is suggested to set lower than 60 °C considering human comfort.
Spherical lignin nanoparticles (LNPs) fabricated via nanoprecipitation of dissolved lignin are among the most attractive biomass-derived nanomaterials. Despite various studies exploring the methods to improve the uniformity of LNPs or seeking more application opportunities for LNPs, little attention has been given to the fundamental aspects of the solvent effects on the intrinsic properties of LNPs. In this study, we employed a variety of experimental techniques and molecular dynamics (MD) simulations to investigate the solvent effects on the intrinsic properties of LNPs. The LNPs were prepared from softwood Kraft lignin (SKL) using the binary solvents of aqueous acetone or aqueous tetrahydrofuran (THF) via nanoprecipitation. The internal morphology, porosity, and mechanical properties of the LNPs were analyzed with electron tomography (ET), small-angle X-ray scattering (SAXS), atomic force microscopy (AFM), and intermodulation AFM (ImAFM). We found that aqueous acetone resulted in smaller LNPs with higher uniformity compared to aqueous THF, mainly ascribing to stronger solvent−lignin interactions as suggested by MD simulation results and confirmed with aqueous 1,4-dioxane (DXN) and aqueous dimethyl sulfoxide (DMSO).
More importantly, we report that both LNPs were compact particles with relatively homogeneous density distribution and very low porosity in the internal structure. The stiffness of the particles was independent of the size, and the Young’s modulus was in the range of 0.3−4 GPa. Overall, the fundamental understandings of LNPs gained in this study are essential for the design of LNPs with optimal performance in applications.
This paper describes a new ultrasonic measuring device called “W-Box”. It was developed based on the requirements of the DFG Forschergruppe (research unit) CoDA for a portable device for monitoring of concrete specimens, models and actual structures using embedded ultrasonic transducers as well as temperature and humidity sensors. The W-Box can send ultrasonic pulses with a variable frequency of 50–100 kHz to one selectable transducer and records signals from up to 75 multiplexed channels with a sample rate of 1 MHz and a resolution of 14 bits. In addition, it measures temperature and humidity with high accuracy, adjustable amplification, restarts automatically after a power failure and can be fully controlled remotely. The measured data are automatically stored locally on-site data quality checks and transferred to remote servers. The comparison of the W-Box with a laboratory setup using commercial devices proves that it is equally reliable and precise, at much lower cost. The W-Box also shows that their measurement capacities, with the used embedded ultrasonic transducers, can reach above 6 m in concrete.
In this study, the ability of an electronic nose developed to analyze and monitor odor emissions from three poultry farms located in Meknes (Morocco) and Berlin (Germany) was evaluated. Indeed, the potentiality of the electronic nose (e-nose) to differentiate the concentration fractions of hydrogen sulfide, ammonia, and ethanol was investigated. Furthermore, the impact change of relative humidity values (from 15% to 67%) on the responses of the gas sensors was reported and revealed that the effect remained less than 0.6%. Furthermore, the relevant results confirmed that the developed e-nose system was able to perfectly classify and monitor the odorous air of poultry farms.
In this paper, we discuss the importance of scientifically investigating cultural artefacts in a non-invasive way. Taking as test case Leonardo da Vinci’s Manuscript with anatomic drawings and notes, which is stored in Weimar, we clarify fundamental steps in the chronology of this folio. By means of microscopy, infrared reflectography, UV photography, and X-ray fluorescence analysis, we were able to identify various types of sketching material and several varieties of iron gall ink. For his sketches, Leonardo used two different sketching tools, a lead pencil and a graphite pencil, as well as several types of ink for developing these sketches into drawings. With regard to ink, it is important to observe that there is no difference between the ink Leonardo used for drawing and the ink he used for writing text. Based on the materials analysed, we suggest a chronology for the creation of this unique folio.
Superalloy inspired Al10Co25Cr8Fe15Ni36Ti6 compositionally complex alloy is known for its gamma-gamma' microstructure and the third Heusler phase. Variations of this alloy, gained by replacing 0.5 or 1 at. pct Al by the equivalent amount of Mo, W, Zr, Hf or B, can show more phases in addition to this three-phase morphology. When the homogenization temperature is chosen too high, a eutectic phase formation can take place at the grain boundaries, depending on the trace elements: Mo and W do not form eutectics while Hf, Zr and B do. In order to avoid the eutectic formation and the potential implied grain boundary weakening, the homogenization temperature must be chosen carefully by differential scanning calorimetry measurements. A too low homogenization temperature, however, could impede the misorientation alignment of the dendrites in the grain. The influence of grain boundary phases and incomplete dendrite re-orientation are compared and discussed.
Our standard protocol for the characterisation of writing materials within advanced manuscript studies has been successfully used to investigate manuscripts written with a pure ink on a homogeneous writing surface. However, this protocol is inadequate for analysing documents penned in mixed inks. We present here the advantages and limitations of the improved version of the protocol, which now includes imaging further into the infrared region (1100−1700 nm).
The concept of a ‘plastisphere microbial community’ arose from research on aquatic plastic debris, while the effect of plastics on microbial communities in soils remains poorly understood. Therefore, we examined the inhabiting microbial communities of two plastic debris ecosystems with regard to their diversity and composition relative to plastic-free soils from the same area using 16S rRNA amplicon sequencing. Furthermore, we studied the plastic-colonizing potential of bacteria originating from both study sites as a measure of surface adhesion to UV-weathered polyethylene (PE) using high-magnification field emission scanning electron microscopy (FESEM). The high plastic content of the soils was associated with a reduced alpha diversity and a significantly different structure of the microbial communities. The presence of plastic debris in soils did not specifically enrich bacteria known to degrade plastic, as suggested by earlier studies, but rather shifted the microbial community towards highly abundant autotrophic bacteria potentially tolerant to hydrophobic environments and known to be important for biocrust formation. The bacterial inoculates from both sites formed dense biofilms on the surface and in micrometer-scale surface cracks of the UV-weathered PE chips after 100 days of in vitro incubation with visible threadlike EPS structures and cross-connections enabling surface adhesion. High-resolution FESEM imaging further indicates that the microbial colonization catalyzed some of the surface degradation of PE. In essence, this study suggests the concept of a ‘terrestrial plastisphere’ as a diverse consortium of microorganisms including autotrophs and other pioneering species paving the way for those members of the consortium that may eventually break down the plastic compounds.
Increasing contamination of environmental waters with pharmaceuticals represents an emerging threat for the drinking water quality and safety. In this regard, fast and reliable analytical methods are required to allow quick countermeasures in case of contamination. Here, we report the development of a magnetic bead-based immunoassay (MBBA) for the fast and cost-effective determination of the analgesic diclofenac (DCF) in water samples, based on diclofenac-coupled magnetic beads and a robust monoclonal anti-DCF antibody. A novel synthetic strategy for preparation of the beads resulted in an assay that enabled for the determination of diclofenac with a significantly lower limit of detection (400 ng/L) than the respective enzyme-linked immunosorbent assay (ELISA). With shorter incubation times and only one manual washing step required, the assay demands for remarkably shorter time to result (< 45 min) and less equipment than ELISA. Evaluation of assay precision and accuracy with a series of spiked water samples yielded results with low to moderate intra- and inter-assay variations and in good agreement with LC–MS/MS reference analysis. The assay principle can be transferred to other, e.g., microfluidic, formats, as well as applied to other analytes and may replace ELISA as the standard immunochemical method.
Through connecting genomic and metabolic information, metaproteomics is an essential approach for understanding how microbiomes function in space and time. The international metaproteomics community is delighted to announce the launch of the Metaproteomics Initiative (www.metaproteomics.org), the goal of which is to promote dissemination of metaproteomics fundamentals, advancements, and applications through collaborative networking in microbiome research. The Initiative aims to be the central information hub and open meeting place where newcomers and experts interact to communicate, standardize, and accelerate experimental and bioinformatic methodologies in this feld. We invite the entire microbiome community to join and discuss potential synergies at the interfaces with other disciplines, and to collectively promote innovative approaches to gain deeper insights into microbiome functions and dynamics.
Long-time behavior of surface properties of microstructures fabricated by multiphoton lithography
(2021)
The multiphoton lithography (MPL) technique represents the future of 3D microprinting, enabling the production of complex microscale objects with high precision. Although the MPL fabrication parameters are widely evaluated and discussed, not much attention has been given to the microscopic properties of 3D objects with respect to their surface properties and time-dependent stability. These properties are of crucial importance when it comes to the safe and durable use of these structures in biomedical applications. In this work, we investigate the surface properties of the MPL-produced SZ2080 polymeric microstructures with regard to the physical aging processes during the post-production stage. The influence of aging on the polymeric microstructures was investigated by means of Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS). As a result, a time-dependent change in Young’s Modulus, plastic deformation, and adhesion and their correlation to the development in chemical composition of the surface of MPL-microstructures are evaluated. The results presented here are valuable for the application of MPL-fabricated 3D objects in general, but especially in medical technology as they give detailed information of the physical and chemical time-dependent dynamic behavior of MPL-printed surfaces and thus their suitability and performance in biological systems.
In contrast to other cyclic tin bisphenoxides, polymerizations of glycolide and l-lactide with the spirocyclic tin(IV) bis-1,1′-bisnapthoxide yield linear chains having a 1,1′-bisnapthol end group and no cycles. In the case of l-lactide, LA/Cat ratio and temperature are varied and at 160 °C or below, all polylactides mainly consist of even-numbered chains. A total predominance of even-numbered chains is also found for homopolymerization of glycolide, or the copolymerization of glycolide and l-lactide, when conducted <120 °C.
Linear chains having a bisnaphthol end group are again the main reaction products of ring-expansion polymerizations (REP) of 𝝐-caprolactone, but above 150 °C cycles are also formed.
Static immersion tests of potential injection pipe steels 42CrMo4, X20Cr13, X46Cr13, X35CrMo4, and X5CrNiCuNb16-4 at T = 60 °C and ambient pressure, as well as p = 100 bar were performed for 700–8000 h in a CO2-saturated synthetic aquifer environment similar to CCS sites in the Northern German Basin (NGB). Corrosion rates at 100 bar are generally lower than at ambient pressure. The main corrosion products are FeCO3 and FeOOH with surface and local corrosion phenomena directly related to the alloy composition and microstructure. The appropriate heat treatment enhances corrosion resistance. The lifetime reduction of X46Cr13, X5CrNiCuNb16-4, and duplex stainless steel X2CrNiMoN22-5-3 in a CCS environment is demonstrated in the in situ corrosion fatigue CF experiments (axial push-pull and rotation bending load, 60 °C, brine: Stuttgart Aquifer and NGB, flowing CO2: 30 L/h, +/− applied potential). Insulating the test setup is necessary to gain reliable data. S-N plots, micrographic-, phase-, fractographic-, and surface analysis prove that the life expectancy of X2CrNiMoN22-5-3 in the axial cyclic load to failure is clearly related to the surface finish, applied stress amplitude, and stress mode. The horizontal grain attack within corrosion pit cavities, multiple fatigue cracks, and preferable deterioration of austenitic phase mainly cause fatigue failure. The CF life range increases significantly when a protective potential is applied.
First year students especially with migration background and language deficiencies rate material science in mechanical engineering as one of the fundamental courses with high work load and necessity of language skills due to the descriptive nature of the course. Therefore a blended learning course structure using based on inverted classroom teaching scenarios was established. Heart of the self-study period are visualizing peer-to-peer lecture films supported by micro-lectures along with various online teaching materials. Although students with migration background generally scored lower in tests due to the lack of language skills improved learning outcomes are demonstrated in high quality class discussions and in overall understanding. This paper introduces the learning structure and graded activities, evaluates the course and compares results of native German-speaking students to those of students with migration background.
Industrial processes release substantial quantities of waste heat, which can be harvested to generate electricity. At present, the conversion of low grade waste heat to electricity relies solely on thermoelectric materials, but such materials are expensive and have low thermodynamic efficiencies. Although thermomagnetic materials may offer a promising alternative, their performance remains to be evaluated, thereby hindering their real-world application. Here, the efficiency and cost effectiveness of thermomagnetic materials are evaluated for the usage in motors, oscillators, and generators for converting waste heat to electricity. The analysis reveals that up to temperature differences of several 10 K, the best thermomagnetic materials have the potential to compete with thermoelectric materials. Importantly, it is found that the price per watt of some thermomagnetic materials is much lower compared to that of present-day thermoelectrics, which can become competitive with conventional power plants. This materials library enables the selection of the best available thermomagnetic materials for harvesting waste heat and gives guidelines for their future development.
The Tsumeb Mine in Namibia represents one of the best-preserved mining sites in the world and is rapidly gaining cross-disciplinary interest among cultural and engineering scientists. Most of the open pit and the shaft mining equipment are still in place, including the ore processing units and the local power plant. The mining area thus deserves recognition as an industrial world heritage site, especially due to the rarity of such locations on the African continent. The Shaft #1 headgear, built in 1924, represents one of the oldest known riveted steel headgears of the Promnitz design worldwide. In contrast to similar steel structures located in the northern hemisphere, it has been exposed to a different rural semi-arid climate since it is located in the Otavi Mountain Land, characterized by semi-annual change of rainy and dry seasons. Parts of the Shaft #1 headgear have remained largely untouched for more than 70 years. Besides its outstanding heritage value, it thus also represents an interesting object for studying the composition of corrosion layers formed on mild steel surfaces when exposed to continental and industrial mining atmospheres. To find a suitable transparent corrosion prevention coating, various on-site coating samples were evaluated after 11 months of outdoor exposure, including Owatrol Oil®, which is based on natural oil and alkyd resin with strong wicking potential. The substance is frequently applied for the conservation of single components but is not yet widely used on large steel structures in the field of industrial heritage conservation. However, it represented the most stable anti-corrosion coating under the local atmospheric conditions in the on-site tests. Thus, the suitability of Owatrol Oil® as a transparent coating for corrosion protection of riveted mild steel structures in such climates was further investigated as a more recent approach for the conservation of large steel structures. Since the protective coatings are exposed to strong UV radiation in the local climate, the addition of a specific UV stabilizer mixture was also tested. For such laboratory tests, two mild steel samples were taken. The first one originated from a diagonal strut of the 1920s and the second one from a handrail mounted in the early 1960s. Using corresponding high-resolution scanning electron microscopy (HR-SEM) and energy-dispersive X-ray spectroscopy (EDX) it was found that the corrosion layers are predominantly composed of lepidocrocite and goethite. A weathering program simulating the specific environmental conditions at Tsumeb in a UV climate chamber was developed and the corrosion resistance of the mild steel surface was subsequently evaluated by potentiodynamic measurements. Such tests proved to be a fast and reliable procedure for ranking the corrosion resistance of the old mild steels. It was found that the long-term corrosion layers already provide significant protection against further corrosion in the simulated environment. However, the study also showed that this can be further improved by the application of the Owatrol Oil® as a protective coating that also seals crevices. The addition of the UV stabilizers, however, led to a significant deterioration in corrosion protection, even in comparison to that of the uncoated long-term corrosion layers on the surface. Regular overcoating seems more advisable for the long-term preservation of the Shaft #1 headgear than modifying the Owatrol Oil® Coating with the tested UV-stabilizing additives.
Metaproteomics has matured into a powerful tool to assess functional interactions in microbial communities. While many metaproteomic workflows are available, the impact of method choice on results remains unclear. Here, we carry out a community-driven, multi-laboratory comparison in metaproteomics: the critical assessment of metaproteome investigation study (CAMPI). Based on well-established workflows, we evaluate the effect of sample preparation, mass spectrometry, and bioinformatic analysis using two samples: a simplified, laboratory-assembled human intestinal model and a human fecal sample. We observe that variability at the peptide level is predominantly due to sample processing workflows, with a smaller contribution of bioinformatic pipelines. These peptide-level differences largely disappear at the protein group level. While differences are observed for predicted community composition, similar functional profiles are obtained across workflows. CAMPI demonstrates the robustness of present-day metaproteomics research, serves as a template for multi-laboratory studies in metaproteomics, and provides publicly available data sets for benchmarking future developments.
Pseudomonas aeruginosa biofilms exhibit an intrinsic resistance to antibiotics and constitute a considerable clinical threat. In cystic fibrosis, a common feature of biofilms formed by P. aeruginosa in the airway is the occurrence of mutants deficient in flagellar motility. This study investigates the impact of flagellum deletion on the structure and antibiotic tolerance of P. aeruginosa biofilms, and highlights a role for the flagellum in adaptation and cell survival during biofilm development. Mutations in the flagellar hook protein FlgE influence greatly P. aeruginosa biofilm structuring and antibiotic tolerance. Phenotypic analysis of the flgE knockout mutant compared to the wild type (WT) reveal increased fitness under planktonic conditions, reduced initial adhesion but enhanced formation of microcolony aggregates in a microfluidic environment, and decreased expression of genes involved in exopolysaccharide formation. Biofilm cells of the flgE knock-out mutant display enhanced tolerance towards multiple antibiotics, whereas its planktonic cells show similar resistance to the WT. Confocal microscopy of biofilms demonstrates that gentamicin does not affect the viability of cells located in the inner part of the flgE knock-out mutant biofilms due to reduced penetration. These findings suggest that deficiency in flagellar proteins like FlgE in biofilms and in cystic fibrosis infections represent phenotypic and evolutionary adaptations that alter the structure of P. aeruginosa biofilms conferring increased antibiotic tolerance.
The production of materials with dimensions in the nanometre range has continued to increase in recent years. In order to ensure safety when handling these products, the hazard potential of such innovative materials must be known. While several studies have already investigated the effects of explosions (such as maximum explosion pressure and maximum pressure rise) of powders with primary particles in the nanometre range, little is known about the ignition temperatures and flame velocities. Therefore, the minimum ignition temperature (MIT) of metallic nano powders (aluminium, iron, copper and zinc) was determined experimentally in a so called Godbert-Greenwald (GG) oven. Furthermore, the flame velocities were determined in a vertical tube. In order to better classify the test results, the tested samples were characterised in detail and the lower explosion limits of the tested dust samples were determined. Values for the burning velocity of aluminium nano powders are higher compared to values of micrometre powders (from literature). While MIT of nanometre aluminium powders is within the range of micrometre samples, MIT of zinc and copper nano powders is lower than values reported in literature for respective micrometre samples.
The determination of the anisotropy of materials’ microstructure and morphology (pore space) in diesel particulate filter (DPF) materials is an important problem to solve, since such anisotropy determines the mechanical, thermal, and filtration properties of such materials. Through the use of a dedicated (and simple) segmentation algorithm, it is shown how to exploit the information yielded by 3D X-ray computed tomography data to quantify the morphological anisotropy. It is also correlated that such anisotropy of the pore space Such anisotropy of the pore space is also correlated with the microstructure and crystallographic anisotropy of the material in several showcases: a microstructurally isotropic material, such as SiC, and some morphologically and microstructurally anisotropic cordierite materials. In the later case, the finer the grain size, the more isotropic the microstructure.
Scientific material analysis of the elemental composition of inks from different strata of a manuscript has the potential to complement scholarly observations using palaeography and philology in reconstructing the history of the manuscript’s production, correction and repair.
There are three typologically different classes of black writing inks: soot inks consist of carbon particles.
Martensitic 9% Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. Limited data on room temperature diffusion coefficients reported in literature vary widely by several orders of magnitude (mostly attributed to variation in microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. From the results obtained, diffusion coefficients were calculated using to different methods, time-lag, and inflection point. Results show that, despite microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
Additive manufacturing (AM) is developing rapidly due to itsflexibility in producing complex geometries and tailored material compositions. However, AM processes are characterized by intrinsic limitations concerning their resolution and surface finish, which are related to the layer-by-layer stacking process. Herein, a self-organization process is promoted as an approach to improve surface quality and achieve optimization of 3D minimal surface lightweight structures. The self-organization is activated after the powder bed 3D printing process via local melting, thereby allowing surface tension-driven viscous flow.The surface roughness Ra (arithmetic average of the roughness profile) could bedecreased by a factor of 1000 and transparent lenses and complex gyroid structures could be produced for demonstration. The concept of self-organization is further elaborated by incorporating external magnetic fields to intentionally manipulate magnetic particles, which are mixed with the polymer before printing and self-organization. This concept can be applied to develop programmable materials with specific microtextures responding to the external physical conditions.
Effect of the Anchoring Layer and Transport Type on the Adsorption Kinetics of Lambda Carrageenan
(2021)
The kinetics of lambda carrageenan (λ-car) adsorption/desorption on/from anchoring layers under diffusion- and convection-controlled transport conditions were investigated. The eighth generation of poly(amidoamine) dendrimers and branched polyethyleneimine possessing different shapes and polydispersity indexes were used for anchoring layer formation. Dynamic light scattering, electrophoresis, streaming potential measurements, optical waveguide lightmode spectroscopy, and quartz crystal microbalance were applied to characterize the formation of mono- and bilayers. The unique combination of the employed techniques enabled detailed insights into the mechanism of the λ-car adsorption mainly controlled by electrostatic interactions. The results show that the macroion adsorption efficiency is strictly correlated with the value of the final zeta potentials of the anchoring layers, the transport type, and the initial bulk concentration of the macroions. The type of the macroion forming the anchoring layer had a minor impact on the kinetics of λ-car adsorption. Besides significance to basic science, the results presented in this paper can be used for the development of biocompatible and stable macroion multilayers of well-defined electrokinetic properties and structure.
One of the most important chemicals used in the production of polymer plastics and coatings is bisphenol A. However, despite the large number of studies on the toxicity and hormonal activity of BPA, there are still open questions and thus considerable media attention regarding BPA toxicity. Hence, it is necessary to develop a sensitive, simple, cost-efficient, specific, portable, and rapid method for monitoring bisphenol A and for high sample throughput and on-site screening analysis. Lateral flow immunoassays have potential as rapid tests for on-site screening. To meet sensitivity criteria, they must be carefully optimized. A latex microparticle-based LFIA for detection of BPA was developed. The sensitivity of the assay was improved by non-contact printing of spot grids as the control and test lines with careful parameter optimization. Results of the test could be visually evaluated within 10 min with a visual cut-off of 10 µg/L (vLOD). Alternatively, photographs were taken, and image analysis performed to set up a calibration, which allowed for a calculated limit of detection (cLOD) of 0.14 µg/L. The method was validated for thermal paper samples against ELISA and LC–MS/MS as reference methods, showing good agreement with both methods
Ring-opening polymerizations (ROPs) of L-lactide are performed in bulk at 130°C with tin(II) 2-ethylhexanoate as catalyst and various phenols of differentacidity as initiators. Crystalline polylactides having phenyl ester end groups are isolated, which are almost free of cyclics. The dispersities and molecular weights are higher than those obtained from alcohol-initiated ROPs under identical conditions. Polymerizations at 160°C yield higher molecular weights than expected from the monomer/initiator ratio and a considerable fraction of cycles. The fraction of cycles increases with higher reactivity of the ester end group indicating that the cycles are formed by end-to-end cyclization.
The co-crystallisation of [NiEn3](NO3)2 (En = ethylenediamine) with Na2MoO4 and Na2WO4 from a water solution results in the formation of [NiEn3](MoO4)0.5(WO4)0.5 co-crystals. According to the X-ray diffraction analysis of eight single crystals, the parameters of the hexagonal unit cell (space group P–31c, Z = 2) vary in the following intervals: a = 9.2332(3)–9.2566(6); c = 9.9512(12)–9.9753(7) Å with the Mo/W ratio changing from 0.513(3)/0.487(3) to 0.078(4)/0.895(9). The thermal decomposition of [NiEn3](MoO4)0.5(WO4)0.5 individual crystals obtained by co-crystallisation was performed in He and H2 atmospheres. The ex situ X-ray study of thermal decomposition products shows the formation of nanocrystalline refractory alloys and carbide composites containing ternary Ni–Mo–W phases. The formation of carbon–nitride phases at certain stages of heating up to 1000 °C were shown.
Rare-earth based luminescent materials are key functional components for the rational design of light-conversion smart devices. Stable Eu3+-doped strontium fluoride (SrF2) nanoparticles were prepared at room temperature in ethylene glycol. Their luminescence depends on the Eu content and changes after heat treatment. The crystallinity of heat-treated material increases in comparison with as-synthesized samples. Particles were investigated in solution using X-ray diffraction, small-angle X-ray scattering, and X-ray spectroscopy. After heat treatment, the size of the disordered nanoparticles increases together with a change of their local structure. Interstitial fluoride ions can be localized near Eu3+ ions. Therefore, non-radiative relaxation from other mechanisms is decreased. Knowledge about the cation distribution is key information for understanding the luminescence properties of any material.
Reported here is the production of molecularly imprinted polymer (MIP) films, integrating a fluorescent moiety that serves as both an element for template interaction and signalling, for the thermal and optical detection of the beta-lactam antibiotic nafcillin. Fluorescein methacrylate (FluMa) was synthesized and introduced during the molecular imprinting process as the sole monomer and in a 1 : 1 mixture with methacrylic acid (MAA), allowing to draw first conclusions on the MIP formation potential of such a rather large and rigid monomer. At first, MIP microparticles containing FluMa were prepared by free radical polymerisation. Optical batch rebinding experiments revealed that FluMa can act as a functional monomer for selective detection of nafcillin; however, the addition of MAA as co-monomer significantly improved performance. Subsequently, thin MIP films containing FluMa were deposited onto functionalised glass slides and the influence of porogen, drying time, and monomer composition was studied. These MIP-functionalised glass electrodes were mounted into a customised 3D-printed flow cell, where changes in the liquid were either evaluated with a thermal device or using fluorescence bright field microscopy. Thermal analysis demonstrated that multiple MIP layers enhanced sensor specificity, with detection in the environmentally relevant range. The fluorescence bright field microscope investigations validated these results, showing an increase in the fluorescence intensity upon exposure of the MIP-functionalised glass slides to nafcillin solutions. These are promising results for developing a portable sensor device that can be deployed for antibiotics outside of a dedicated laboratory environment, especially if sensor design and fluorophore architecture are optimised.
Detection of surface breaking cracks using flying line laser thermography: A Canny-based algorithm
(2021)
In this work, we introduce a new algorithm for effectual crack detection using flying line laser thermography, based on the well-known Canny approach. The algorithm transforms the input thermographic sequence into an edge map. Experimental measurements are performed on a metallic component that contains surface breaking cracks due to industrial use. The specimen is tested using flying line thermography at different scanning speeds and laser input powers. Results obtained with the proposed algorithm are additionally compared with a previously established algorithm for flying spot thermography. The proposed Canny-based algorithm can be used in automated systems for thermographic non-destructive testing.
Polycyclic aromatic hydrocarbons (PAHs) are a large group of priority organic pollutants, which contaminate environmental compartments, food, and consumer products as well. Due to their frequent occurrence associated with elevated Levels of PAHs, plastic and rubber parts of consumer products and toys are particular sources of exposure. Although European maximum levels exist for eight carcinogenic PAHs in consumer products and toys according to REACH Regulation (EC) No. 1907/2006, certified reference materials (CRM) are still not available. To overcome this lack, the first CRM for the determination of PAHs in rubber toys (BAM-B001) was developed according to the requirements of ISO Guide 35. The whole process of CRM development including preparation, homogeneity and stability studies, and value assignment is presented.
The assignment of the certified mass fractions was based upon in-house study at BAM using stable isotope Dilution analysis (SIDA) gas chromatography mass spectrometry (GC–MS). The obtained values were confirmed by the results of two interlaboratory comparison (ILC) studies with more than 50 expert laboratories from Germany and China. The mass fractions of 14 PAHs including all REACH and GS mark regulated compounds were certified ranging between 0.2 and 15.4 mg/
kg accompanied by expanded uncertainties (coverage factor k = 2). In addition, informative values were determined for 4 PAHs, mainly due to higher uncertainties and/or lack of ILC data for confirmation. BAM-B001 is intended for analytical quality control particularly based on the AfPS GS 2019:01 PAK method and contributes to improve the chemical safety of consumer products including toys.
In this paper, the accurate determination of the size and size distribution of bipyramidal anatase nanoparticles (NPs) after deposition as single particles on a silicon substrate by correlative Scanning Electron Microscopy (SEM) with Atomic Force Microscopy (AFM) analysis is described as a new measurement procedure for metrological purposes. The knowledge of the exact orientation of the NPs is a crucial step in extracting the real 3D dimensions of the particles. Two approaches are proposed to determine the geometrical orientation of individual nano‐bipyramides: (i) AFM profiling along the long bipyramid axis and (ii) stage tilting followed by SEM imaging. Furthermore, a recently developed method, Transmission Kikuchi Diffraction (TKD), which needs preparation of the crystalline NPs on electron‐transparent substrates such as TEM grids, has been tested with respect to its capability of identifying the geometrical orientation of the individual NPs. With the NPs prepared homogeneously on a TEM grid, the transmission mode in a SEM, i.e., STEM‐in‐SEM (or T‐SEM), can be also applied to extract accurate projection dimensions of the nanoparticles from the same sample area as that analysed by SEM, TKD and possibly AFM. Finally, Small Angle X‐ray Scattering (SAXS) can be used as an ensemble technique able to measure the NPs in liquid suspension and, with ab‐initio knowledge of the NP shape from the descriptive imaging techniques, to provide traceable NP size distribution and particle concentration.
Resistance spot welding is an established joining process for the production of safetyrelevant components in the automotive industry. Therefore, consecutive process monitoring is essential to meet the high quality requirements. Artificial neural networks can be used to evaluate the process parameters and signals, to ensure individual spot weld quality. The predictive accuracy of such algorithms depends on the provided training data set, and the prediction of untrained data is challenging. The aim of this paper was to investigate the extrapolation capability of a multi-layer perceptron model. That means, the predictive performance of the model was tested with data that clearly differed from the training data in terms of material and coating composition. Therefore, three multi-layer perceptron regression models were implemented to predict the nugget diameter from process data. The three models were able to predict the training datasets very well. The models, which were provided with features from the dynamic resistance curve predicted the new dataset better than the model with only process parameters. This study shows the beneficial influence of process signals on the predictive accuracy and robustness of artificial neural network algorithms.
Especially, when predicting a data set from outside of the training space.
Grain-boundary degradation via liquid-metal embrittlement (LME) is a prominent and long-standing failure process in next generation advanced high-strength steels. Here we reveal, well ahead of the crack tip, the presences of nano-scale grains of intermetallic phases in Zn-infiltrated but uncracked grain boundaries with scanning- and 4D transmission electron microscopy. Instead of the often-reported Znrich Fe-Zn intermetallics, the nano-scale phase in the uncracked infiltrated grain boundaries is identified as the G-phase, and its presence reveals the local enhancement of strain heterogeneities in the grain boundary network. Based on these observations, we argue that intermetallic phase formation is not occurring after cracking and subsequent liquid Zn infiltration but is instead one of the primary nanoscopic drivers for grain-boundary weakening and crack initiation. These findings shift the focus of LME from micro- and meso-scale crack investigations to the very early stages immediately following Zn diffusion, after which secondary phase nucleation and growth emerge as the root-cause for failure.
Laser-induced periodic surface structures (LIPSS) are a simple and robust route for the nanostructuring of solids that can create various surface functionalities featuring applications in optics, medicine, tribology, energy technologies, etc. While the current laser technologies already allow surface processing rates at the level of m2/min, industrial applications of LIPSS are sometimes hampered by the complex interplay between the nanoscale surface topography and the specific surface chemistry, as well as by limitations in controlling the processing of LIPSS and in the long-term stability of the created surface functions. This Perspective article aims to identify some open questions about LIPSS, discusses the pending technological limitations, and sketches the current state of theoretical modelling. Hereby, we intend to stimulate further research and developments in the field of LIPSS for overcoming these limitations and for supporting the transfer of the LIPSS technology into industry.
Mass Spectrometry (MS) and Nuclear Magnetic Resonance Spectroscopy (NMR) are valuable analytical and quality control methods for most industrial chemical processes as they provide information on the concentrations of individual compounds and by-products. These processes are traditionally carried out manually and by a specialist, which takes a substantial amount of time and prevents their utilization for real-time closed-loop process control. This paper presents recent advances from two projects that use Artificial Neural Networks (ANNs) to address the challenges of automation and performance-efficient realizations of MS and NMR. In the first part, a complete toolchain has been realized to develop simulated spectra and train ANNs to identify compounds in MS. In the second part, a limited number of experimental NMR spectra have been augmented by simulated spectra, to train an ANN with better prediction performance and speed than state-of-the-art analysis. These results suggest that, in the context of the digital transformation of the process industry, we are now on the threshold of a strongly simplified use of MS and MRS and the accompanying data evaluation by machine-supported procedures, and can utilize both methods much wider for reaction and process monitoring or quality control.
One of the challenges of the high-power hybrid laser welding of thick steels is the sensitivity of the process of the process to manufacturing tolerances. This usually leads to a time-consuming preparation of the welding edges, such as milling. The study deals with the influence of the edge quality of milled and plasma-cut steel made of S355J2 with a wall thickness of 20 mm on the laser hybrid welded seam quality. Furthermore, the gap bridgeability and the tolerances towards edge misalignment was investigated. An AC magnet was used as backing support to prevent sagging and positioned under the workpiece, to generate an upwards directed electromagnetic pressure. The profiles of the edges and the gap on the top and root side were measured using a digital camera. Single-pass laser hybrid welds of plasma-cut edges could be welded using a laser beam power of just 13.7 kW. A gap bridgeability up to 2 mm and misalignment of edges up to 2 mm could be achieved successful. Additionally, the independence of the cutting side and the welding side was shown, so that samples were welded to the opposite side to their cutting. For evaluation of internal defects or irregularities, X-ray images were carried out. Charpy impact strength tests were performed to determine the toughness of the welds.
The study deals with the determination of the influence of an externally applied oscillating magnetic field on the melt pool dynamics in high power laser beam and hybrid laser arc welding processes. An AC magnet was positioned under the workpiece which is generating an upward directed electromagnetic force to counteract the formation of the droplets. To visualise the melt flow characteristics, several experiments were carried out using a special technique with mild steel from S355J2 with a plate thickness of up to 20 mm and a quartz glass in butt configuration. The profile of the keyhole and the melt flow were recorded with a highspeed camera from the glass side. Additionally, the influence of the magnetic field orientation to the welding direction on the filler material dilution on laser hybrid welding was studied with variating oscillation frequency. The element distribution over the whole seam thickness was measured with X-ray fluorescence (XRF). The oscillation frequency demonstrated a great influence on the melt pool dynamics and the mixing of the elements of the filler wire. The highspeed recordings showed, under the influence of the magnetic field, that the melt is affected under strong vortex at the weld root, which also avoids the formation of droplets.
The Alpine Fault zone in New Zealand marks a major transpressional plate boundary that is late in its typical earthquake cycle. Understanding the subsurface structures is crucial to understand the tectonic processes taking place. A unique seismic survey including 2D lines, a 3D array, and borehole recordings, has been performed in the Whataroa Valley and provides new insights into the Alpine Fault zone down to ∼2 km depth at the location of the Deep Fault Drilling Project (DFDP)-2 drill site. Seismic images are obtained by focusing prestack depth migration approaches. Despite the challenging conditions for seismic imaging within a sediment filled glacial valley and steeply dipping valley flanks, several structures related to the valley itself as well as the tectonic fault system are imaged. A set of several reflectors dipping 40°–56° to the southeast are identified in a ∼600 m wide zone that is interpreted to be the minimum extent of the damage zone. Different approaches image one distinct reflector dipping at ∼40°, which is interpreted to be the main Alpine Fault reflector located only ∼100 m beneath the maximum drilled depth of the DFDP-2B borehole. At shallower depths (z < 0.5 km), additional reflectors are identified as fault segments with generally steeper dips up to 56°. Additionally, a glacially over-deepened trough with nearly horizontally layered sediments and a major fault (z < 0.5 km) are identified 0.5–1 km south of the DFDP-2B borehole. Thus, a complex structural environment is seismically imaged and shows the complexity of the Alpine Fault at Whataroa.
The present work deals with the recently confirmed widening of the weld pool interface, known as a bulging effect, and its relevance in high power laser beam welding. A combined experimental and numerical approach is utilized to study the influence of the bulge on the hot cracking formation and the transport of alloying elements in the molten pool. A technique using a quartz glass, a direct-diode laser illumination, a high-speed camera, and an infrared camera is applied to visualize the weld pool geometry in the longitudinal section. The study examines the relevance of the bulging effect on both, partial and complete penetration, as well as for different sheet thicknesses ranging from 8 mm to 25 mm. The numerical analysis shows that the formation of a bulge region is highly dependent on the penetration depth and occurs more frequently during partial penetration above 6 mm and complete penetration above 8 mm penetration depth, respectively. The location of the bulge correlates strongly with the cracking location. The obtained experimental and numerical results reveal that the bulging effect increases the hot cracking susceptibility and limits the transfer of alloying elements from the top of the weld pool to the weld root.
CFD simulations of near-ground gas dispersion depend significantly on the accuracy of the wind field. When simulating wind fields with conventional RANS turbulence models, the velocity and turbulence profiles specified as inlet boundary conditions change rapidly in the approach flow region. As a result, when hazardous materials are released, the extent of hazardous areas is calculated based on an approach flow that differs significantly from the boundary conditions defined. To solve this problem, a turbulence model with consistent boundary conditions was developed to ensure a horizontally homogeneous approach flow. Instead of the logarithmic vertical velocity profile, a power law is used to overcome the problem that with the logarithmic profile, negative velocities would be calculated for heights within the roughness length. With this, the problem that the distance of the wall-adjacent cell midpoint has to be higher than the roughness length is solved, so that a high grid resolution can be ensured even in the near-ground region which is required to simulate
gas dispersion. The evaluation of the developed CFD model using the German guideline VDI 3783/9 and wind tunnel experiments with realistic obstacle configurations showed a good agreement between the calculated and the measured values and the ability to achieve a horizontally homogenous approach flow.
Organic single crystals that combine mechanical flexibility and optical properties are important for developing flexible optical devices, but examples of such crystals remain scarce. Both mechanical flexibility and optical activity depend on the underlying crystal packing and the nature of the intermolecular interactions present in the solid state. Hence, both properties can be expected to be tunable by small chemical modifications to the organic molecule. By incorporating a chlorine atom, a reportedly mechanically flexible crystal of (E)-1-(4-bromo-phenyl)iminomethyl-2-hydroxylnaphthalene (BPIN) produces (E)-1-(4-bromo-2-chloro-phenyl)iminomethyl-2-hydroxyl-naphthalene (BCPIN). BCPIN crystals show elastic bending similar to BPIN upon mechanical stress, but exhibit a remarkable difference in their optical properties as a result of the chemical modification to the backbone of the organic molecule. This work thus demonstrates that the optical properties and mechanical flexibility of molecular materials can, in principle, be tuned independently.
For the first time, fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to detect per- and polyfluoroalkyl substances (PFAS) in various soil and sewage sludge samples. The method can be used to determine the speciation of inorganic and organic fluorides, without pre-treatment of solid samples. Therefore, XANES spectra of several inorganic fluorides as well as selected fluorinated organic compounds were recorded. While inorganic fluorides partially exhibit a variety of sharp spectral features in the XANES spectrum, almost all inspected organofluorine compounds show two distinct broad features at 688.5 and 692.0 eV. Moreover, the peak intensity ratio 688.5 eV/692.0 eV in the PFAS XANES spectrum can be inversely correlated to the chain length of the perfluoro sulfonic acid group. The detection of targeted PFAS by bulk-XANES spectroscopy in combination with linear combination fitting in soils and sewage sludges was not applicable due to the low organic fluorine to total fluorine ratio of the samples (0.01–1.84%). Nonetheless, direct analysis of pure PFAS revealed that analysis of organofluorine species might be achieved in higher concentrated samples. Furthermore, quantitative measurements by combustion ion chromatography (CIC) evaluated as sum parameters extractable organically bound fluorine (EOF) and total fluorine (TF) emphasize that besides soils, sewage sludges are a significant source of organic fluorine in agriculture (154–7209 μg/kg).
Chemical modification of wood applying benzotriazolyl-activated carboxylic acids has proven to be a versatile method for the durable functionalization of its lignocellulosic biopolymers. Through this process, the material properties of Wood can be influenced and specifically optimized. To check the scope and limitations of this modification method, various benzamide derivatives with electron-withdrawing (EWG) or electron-donating (EDG) functional groups in different positions of the aromatic ring were synthesized and applied for covalent modification of Scots pine (Pinus sylvestris L.) sapwood in this study. The bonded amounts of substances (up to 2.20 mmol) were compared with the reactivity constants of the Hammett equation, revealing a significant correlation between the modification efficiency and the theoretical reactivity constants of the corresponding aromatic substitution pattern. The successful covalent attachment of the respective substituted benzamides was proven by attenuated total reflection infrared (ATR-IR) spectroscopy, while the stability of the newly formed ester bond was proven in a standardized leaching test.
Glass-ceramic composites as insulation material for thermoelectric oxide multilayer generators
(2021)
Thermoelectric generators can be used as energy harvesters for sensor applications.
Adapting the ceramic multilayer technology, their production can be
highly automated. In such multilayer thermoelectric generators, the electrical insulation material, which separates the thermoelectric legs, is crucial for the performance of the device. The insulationmaterial should be adapted to the thermoelectric regarding its averaged coefficient of thermal expansion α and its sintering temperature while maintaining a high resistivity.
In this study, starting from theoretical calculations, a glass-ceramic Composite material adapted for multilayer generators fromcalciummanganate and Calcium cobaltite is developed. The material is optimized towards an α of 11 × 10−6 K−1 (20–500◦C), a sintering temperature of 900◦C, and a high resistivity up to 800◦C.
Calculated and measured α are in good agreement. The chosen glass-ceramic composite with 45 vol.% quartz has a resistivity of 1 × 107 Ωcm and an open porosity of <3%. Sintered multilayer samples from tape-cast thermoelectric oxides and screen-printed insulation show only small reaction layers. It can be concluded that glass-ceramic composites are a well-suited material class for insulation layers as their physical properties can be tuned by varying glass composition or dispersion phases.
The evolution of biological complexity is associated with the emergence of bespoke immune systems that maintain and protect organism integrity. Unlike the well-studied immune systems of cells and individuals, little is known about the origins of immunity during the transition to eusociality, a major evolutionary transition comparable to the evolution of multicellular organisms from single-celled ancestors. We aimed to tackle this by characterizing the immune gene repertoire of 18 cockroach and termite species, spanning the spectrum of solitary, subsocial and eusocial lifestyles. We find that key transitions in termite sociality are correlated with immune gene family contractions. In cross-species comparisons of immune gene expression, we find evidence for a caste-specific social defence system in termites, which appears to operate at the expense of individual immune protection. Our study indicates that a major transition in organismal complexity may have entailed a fundamental reshaping of the immune system optimized for group over individual defence.
An overview is given on the synthesis of TiO2 nanoparticles with well-defined nonspherical shapes (platelet like, bipyramidal, and elongated), with the focus on controlled, reproducible synthesis, as a key requirement for the production of reference materials with homogeneous and stable properties. Particularly with regard to the nanoparticle shapes, there is a high need of certified materials,
solely one material of this type being commercially available since a few months (elongated TiO2). Further, measurement approaches with electron microscopy as the golden method to tackle the nanoparticle shape are developed to determine accurately the size and shape distribution for such nonspherical particles. A prerequisite for accurate and easy (i.e., automated) image analysis is the sample preparation, which ideally must ensure a deposition of the nanoparticles from liquid suspension onto a substrate such that the particles do not overlap, are solvent-free, and have a high deposition density. Challenges in the Synthesis of perfectly monodispersed and solvent-free TiO2 nanoparticles of platelet and acicular shapes are highlighted as well as successful measurement approaches on how to extract from 2D projection electron micrographs the most accurate spatial information, that is, true 3D size, for example, of the bipyramidal nanoparticles with different geometrical orientations on a substrate.
While sociality is present in a taxonomically diverse number of species, most animals remain solitary (Bourke, 2011). Over the last centuries, this apparent imbalance in social and non-social animals has led to a great deal of research aimed at shedding light on the biotic and abiotic factors explaining the emergence and maintenance of sociality in nature (West et al., 2015).
Among them, microbes were quickly identified as a major problem for the evolution of social life, because frequent contact between group members typically facilitates the transmission of pathogens, high nest fidelity favours the establishment of microbial pathogens close to their social hosts and, finally, because social groups often exhibit limited genetic diversity and thus limited genetic resistance against certain pathogen strains (Schmid-Hempel, 1998; Cremer et al., 2007). However, this long-standing view has changed considerably over the last few years. Recent research indeed revealed that group living may be more effective than solitary living to Limit the risk of infection by pathogenic microbes because group living also allows the development of an additional layer of defence against pathogens in the form of social immunity (Cremer et al., 2007; Cotter and Kilner, 2010). Under strong pressure from pathogens, microbes could therefore promote, rather than hinder, the evolutionary transition from solitary to group Living (Meunier, 2015; Biedermann and Rohlfs, 2017). Moreover, we are increasingly aware that many microbes provide essential benefits to their hosts by performing critical digestive, physiological, and reproductive functions (Engel and Moran, 2013; McFall-Ngai et al., 2013). The need to Access beneficial microbes may thus have played a role in the expression of frequent and tight interactions between conspecifics and ultimately promoted social evolution (Wilson, 1971; Onchuru et al., 2018). Finally, a growing number of studies suggest that microbes could enforce the Aggregation and expression of cooperative behaviours of the hosts to increase their chance of reaching new hosts and may therefore be involved in the evolution of host sociality (Lewin-Epstein et al., 2017) (but see Johnson and Foster, 2018).
Twice recrystallized L-lactide was polymerized with a dozen of different tin or bismuth catalysts in bulk at 160°C for 24 h and was annealed at 150°C afterwards. In two cases Tm values above 197.0°C were obtained. The parameters causing a scattering of the DSC data were studied and discussed. The samples prepared with SnCl2, 2,2-dibutyl-2-stanna-1,3-ditholane (DSTL) or cyclic tin(II) bisphenyldioxide (SnBiph) were subject to annealing programs with variation of time and temperatures, revealing that the Tm´s did not increase. However, an increase of Hm was achieved with maximum values in the range of 93-96 J g-1 corresponding to crystallinities off around 90%. Further studies were performed with once recrystallized L-lactide. Again, those samples directly crystallized from the polymerization process showed the highest Tm values. These data were compared with the equilibrium Tm0 and Hm0 data calculated by several research groups for perfect crystallites. A Tm0 of 213+/-2°C and a Hm0 of 106 J g-1 show the best agreement with the experimental data. The consequences of annealing for the thickness growth of crystallites are discussed on the basis of SAXS measurements. Finally, a comparison of cyclic and linear poly L-lactide)s is discussed.
X-ray emission hazards from ultrashort pulsed laser material processing in an industrial setting
(2021)
Interactions between ultrashort laser pulses with intensities larger than 10^13 W/cm^2 and solids during material processing can lead to the emission of X-rays with photon energies above 5 keV, causing radiation hazards to operators. A framework for inspecting X-ray emission hazards during laser material processing has yet to be developed. One requirement for conducting radiation protection inspections is using a reference scenario, i.e., laser settings and process parameters that will lead to an almost constant and high level of X-ray emissions. To study the feasibility of setting up a reference scenario in practice, ambient dose rates and photon energies were measured using traceable measurement equipment in an industrial setting at SCHOTT AG. Ultrashort pulsed (USP) lasers with a maximum average power of 220 W provided the opportunity to measure X-ray emissions at laser peak intensities of up to 3.3 × 10^15 W/cm^2 at pulse durations of ~1 ps. The results indicate that increasing the laser peak intensity is insufficient to generate high dose rates. The investigations were affected by various constraints which prevented measuring high ambient dose rates. In this work, a list of issues which may be encountered when performing measurements at USP-laser machines in industrial settings is identified.
Lignosulfonates are industrial biorefinery products that are characterized by significant variability and heterogeneity in their structural composition. Typically, they exhibit high dispersities in molar mass (molar mass distribution-MMD) and in functionalities (functionality-type distribution - FTD), which crucially affect their material usage. In terms of FTD, state-of-the-art Lignin analytics still rely mainly on the determination of functional group contents, which are statistical averages with limited explanatory power. In contrast, our online hydrophobic interaction chromatography−size-exclusion chromatography 2D-LC approach combines the determination of both MMD and FTD in a single measurement to provide a comprehensive picture of the characteristic composition of industrial lignosulfonates information hitherto inaccessible by state-of-the-art lignin analytics. In this way, the complex inter - relationships between these two important structural parameters can be studied in an unprecedented manner. In this study, we reveal the considerable differences in terms of hydrophobic composition and its dispersity present in a range of different industrial lignosulfonates - data desperately needed in tailoring and refining of lignosulfonate composition for material usage.
This work is aimed at exploring the recovery of heavy metals from the fine fraction of solid waste incineration bottom ash.
For this study, wet-discharged bottom ash fine-fraction samples from full-scale treatment plants in Germany and Sweden were analyzed. The potential for the recovery of heavy metal compounds was investigated through wet density-separation with a shaking table. The feed materials were processed without any pre-treatment and the optimum processing conditions were determined by means of design of experiments. Tilt angle and stroke frequency were identified as the most relevant parameters, and the optimum settings were − 7.5° and 266 rpm, respectively. The obtained balanced copper enrichments (and yields) were 4.4 (41%), 6.2 (28%) and 2.4 (23%). A maximum copper enrichment of 14.5 with 2% yield was achieved, providing a concentrate containing 35.9 wt.% relevant heavy metal elements. This included 26.3 wt.% iron, 4.3 wt.% zinc and 3.8 wt.% copper. In conclusion, density separation with shaking tables can recover heavy metals from bottom ash fine fractions. Medium levels of heavy metal enrichment (e.g., for Cu 2.7–4.4) and yield (Cu: 26–41%) can be reached simultaneously.
However, the separation performance also depends on the individual bottom ash sample.
Biocides used as disinfectants are important to prevent the transmission of pathogens, especially during the current antibiotic resistance crisis. This crisis is exacerbated by phenotypically tolerant persister subpopulations that can survive transient antibiotic Treatment and facilitate resistance evolution. Here, we show that E. coli displays persistence against a widely used disinfectant, benzalkonium chloride (BAC). Periodic, persister-mediated failure of disinfection rapidly selects for BAC tolerance, which is associated with reduced cell Surface charge and mutations in the lpxM locus, encoding an enzyme for lipid A biosynthesis.
Moreover, the fitness cost incurred by BAC tolerance turns into a fitness benefit in the presence of antibiotics, suggesting a selective advantage of BAC-tolerant mutants in antibiotic environments. Our findings highlight the links between persistence to disinfectants and resistance evolution to antimicrobials.
Amorphous, porous materials represent by far the largest proportion of natural and men-made materials. Their pore networks consists of a wide range of pore sizes, including mesoand macropores. Within such a pore network, material moisture plays a crucial role in almost all transport processes. In the hygroscopic range, the pores are partially saturated and liquid water is only located at the pore fringe due to physisorption. Therefore, material parameters such as porosity or median pore diameter are inadequate to predict material moisture and moisture transport. To quantify the spatial distribution of material moisture, Hillerborg’s adsorption Theory is used to predict the water layer thickness for different pore geometries. This is done for all pore sizes, including those in the lower nanometre range. Based on this approach, it is shown that the material moisture is almost completely located in mesopores, although the pore network is highly dominated by macropores. Thus, mesopores are mainly responsible for the moisture storage capacity, while macropores determine the moisture transport capacity, of an amorphous material. Finally, an electrical analogical circuit is used as a model to predict the diffusion coefficient based on the pore-size distribution, including physisorption.
The microscopic diffusion and the low frequency density of states (VDOS) of PIM-EATB(CH3) are investigated by inelastic and quasi-elastic neutron scattering where also the demethylated counterpart of PIM-EA-TB(H2) is considered. These intrinsic microporous polymers are characterized by large BET surface area values of several hundred m2/g and pore sizes between 0.5 and 2 nm. Detailed comparison is made to the archetype of polymers of intrinsic microporosity, PIM-1, and polynorbornenes also bearing a microporosity. Due to the wavelength of neutrons, the diffusion and vibrations can be addressed on microscopic length and time scales. From the inelastic neutron scattering experiments the low frequency density of states (VDOS) is estimated which shows excess contributions to the Debye-type VDOS known as Boson peak. It was found that the maximum frequency of the Boson peak decreases with increasing microporosity characterized by the BET surface area. However, besides the BET surface area, additional factors such as the backbone stiffness govern the maximum frequency of the Boson peak. Further the mean squared displacement related to microscopic motions was estimated from elastic fixed window scans. At temperatures above 175 K, the mean squared displacement PIM-EA-TB(CH3) is higher than that for the demethylated counterpart PIM-EA-TB(H2). The additional contribution found for PIM-EATB(CH3) is ascribed to the rotation of the methyl group in this polymer because the only difference between the two structures is that PIM-EA-TB(CH3) has methyl groups where PIM-EA-TB(H2) has none. A detailed comparison of the molecular dynamics is also made to that of PIM-1 and the microporous polynorbornene PTCNSi1. The manuscript focuses on the importance of vibrations and the localized molecular mobility characterized by the microscopic diffusion on the gas Transport in polymeric separation membranes. In the frame of the random gate model localized fluctuations can open or close bottlenecks between pores to enable the diffusion of gas molecules.
One of the most commonly diagnosed cancers in men is prostate cancer (PCa). Understanding tumor progression can help diagnose and treat the disease at an early stage. Components of the extracellular matrix (ECM) play a key role in the development and progression of PCa. Elastin is an essential component of the ECM and constantly changes during tumor development. This article visualizes and quantifies elastin in magnetic resonance imaging (MRI) using a small molecule probe. Results were correlated with histological examinations. Using an elastin-specific molecular probe, we were able to make predictions about the cellular structure in relation to elastin and thus draw conclusions about the size of the tumor, with smaller tumors having a higher elastin content than larger tumors.
Human prostate cancer (PCa) is a type of malignancy and one of the most frequently diagnosed cancers in men. Elastin is an important component of the extracellular matrix and is involved in the structure and organization of prostate tissue. The present study examined prostate cancer in a xenograft mouse model using an elastin-specific molecular probe for magnetic resonance molecular imaging. Two different tumor sizes (500 mm3 and 1000 mm3) were compared and analyzed by MRI in vivo and histologically and analytically ex vivo. The T1-weighted sequence was used in a clinical 3-T scanner to calculate the relative contrast enhancement before and after probe administration. Our results show that the use of an elastin-specific probe enables better discrimination between tumors and surrounding healthy tissue. Furthermore, specific binding of the probe to elastin fibers was confirmed by histological examination and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS). Smaller tumors showed significantly higher signal intensity (p > 0.001), which correlates with the higher proportion of elastin fibers in the histological evaluation than in larger tumors. A strong correlation was seen between relative enhancement (RE) and Elastica–van Gieson staining (R2 = 0.88). RE was related to inductively coupled plasma–mass spectrometry data for Gd and showed a correlation (R2 = 0.78). Thus, molecular MRI could become a novel quantitative tool for the early evaluation and detection of PCa.
Wire arc additive manufacturing enables the production of near-net shape large-volume metallic components leveraging an established industrial base of welding and cladding technology and adapting it for layer-wise material deposition. However, the complex relationship between the process parameters and resulting mechanical properties of the components still remains challenging. In case of high-strength Al-Mg-Si aluminum alloys, no commercial filler wires are yet available due the high susceptibility of solidification cracking as well as the necessary efforts to obtain acceptable mechanical properties. To address this need, we evaluated a novel filler wire based on AlMg0.7Si doped with a Ti5B1 master alloy to foster fine equiaxed grains within the deposited metal. The correlation between the process parameters and component quality was examined by analyzing the size and distribution of pores as well as the grain morphology. Furthermore, we evaluated the influence of different post-weld heat treatment strategies to achieve mechanical properties corresponding to the reference wrought material. We demonstrated that fine equiaxed grains in the weld metal reduced the susceptibility of solidification cracking significantly. The novel AlMg0.7Si-TiB (S Al 6063-TiB) filler wire facilitated wire arc additive manufacturing of high-strength aluminum components with mechanical properties that were almost as superior as the corresponding wrought base material.
Laser-based additive manufacturing methods allow the production of complex metal structures within a single manufacturing step. However, the localized heat input and the layer-wise manufacturing manner give rise to large thermal gradients. Therefore, large internal stress (IS) during the process (and consequently residual stress (RS) at the end of production) is generated within the parts. This IS or RS can either lead to distortion or cracking during fabrication or in-service part failure, respectively. With this in view, the knowledge on the magnitude and spatial distribution of RS is important to develop strategies for its mitigation. Specifically, diffraction-based methods allow the spatial resolved determination of RS in a non-destructive fashion. In this review, common diffraction-based methods to determine RS in laser-based additive manufactured parts are presented. In fact, the unique microstructures and textures associated to laser-based additive manufacturing processes pose metrological challenges. Based on the literature review, it is recommended to (a) use mechanically relaxed samples measured in several orientations as appropriate strain-free lattice spacing, instead of powder, (b) consider that an appropriate grain-interaction model to calculate diffraction-elastic constants is both material- and texture-dependent and may differ from the conventionally manufactured variant. Further metrological challenges are critically reviewed and future demands in this research field are discussed.
Polychromatic and wavelength-selective neutron transmission radiography were applied during bead-on-plate welding on 5 mm thick sheets on the face side of martensitic low transformation temperature (LTT) steel plates using gas tungsten arc welding (GTAW). The in situ visualization of austenitization upon welding and subsequent α’-martensite formation during cooling could be achieved with a temporal resolution of 2 s for monochromatic imaging using a single neutron wavelength and of 0.5 s for polychromatic imaging using the full spectrum of the beam (white beam). The spatial resolution achieved in the experiments was approximately 200 µm. The transmitted monochromatic neutron beam intensity at a wavelength of λ = 0.395 nm was significantly reduced during cooling below the martensitic start temperature Ms since the emerging martensitic phase has a ~10% higher attenuation coefficient than the austenitic phase. Neutron imaging was significantly influenced by coherent neutron scattering caused by the thermal motion of the crystal lattice (Debye–Waller factor), resulting in a reduction in the neutron transmission by approx. 15% for monochromatic and by approx. 4% for polychromatic imaging.
In the framework of non-destructive-testing advanced seismic imaging techniques have been applied to ultrasonic echo data in order to examine the integrity of an engineered test-barrier designed to be used for sealing an underground nuclear waste disposal site. Synthetic data as well as real multi-receiver ultrasonic data acquired at the test site were processed and imaged using Kirchhoff prestack depth migration reverse time migration (RTM). In general, both methods provide a good Image quality as demonstrated by various case studies, however deeper parts within the test barrier containing inclined reflectors were reconstructed more accurately by RTM. In particular, the image quality of a specific target reflector at a depth of 8 m in the test-barrier has been significantly improved compared to previous investigations using synthetic aperture Focusing technique, which justifies the considerable computing time of this method.
We present a preliminary investigation on distributed humidity monitoring during the drying process of concrete based on an embedded polymer optical fiber (POF). The water dissipated into the POF changes several properties of the fiber such as refractive index, scattering coefficient and attenuation factor, which eventually alters the Rayleigh backscattered light. The optical time Domain reflectometer (OTDR) technique is performed to acquire the backscattered signal at the wavelengths 650 nm and 500 nm, respectively. Experimental results show that the received signal increases at 650 nm while the fiber attenuation factor clearly increases at 500 nm, as the concrete dries out. In the hygroscopic range, the information retrieved from the signal change at 650 nm agrees well with the measurement result of the electrical humidity sensors also embedded in the concrete sample.
Microscope slide collections represent extremely valuable depositories of research material in a natural history, forensic, veterinary, and medical context. Unfortunately, most mounting media of these slides deteriorate over time, with the reason for this not yet understood at all. In this study, Raman spectroscopy, ultraviolet–visible (UV–Vis) spectroscopy, and different types of light microscopy were used to investigate the ageing behaviour of naturally aged slides from museum collections and the experimentally aged media of Canada balsam and Permount™, representing a natural and a synthetic resin, respectively, with both being based on mixtures of various terpenes. Whereas Canada balsam clearly revealed chemical ageing processes, visible as increasing colouration, Permount™ showed physical deterioration recognisable by the increasing number of cracks, which even often impacted a mounted specimen. Noticeable changes to the chemical and physical properties of these mounting media take decades in the case of Canada balsam but just a few years in the case of Permount™. Our results question whether or not Canada balsam should really be regarded as a mounting medium that lasts for centuries, if its increasing degree of polymerisation can lead to a mount which is no longer restorable.
We previously described the observation of a characteristic narrowband red luminescence emission of burnt lime (CaO), whose reason was unknown so far. This study presents Raman spectra of Mg5 CO3)4(OH)2∙4H2O, Mg5(CO3)4(OH)2, MgCO3, CaMgCO3 and CaCO3 (in limestone powder) as well as luminescence spectra of their calcination products. Comparison of the latter revealed MgO:Cr3+ as the source of the red lime luminescence in all studied samples, containing magnesium oxide as major component, minor component or trace. Spectral characteristics and theoretical background of the luminescence emission of d-block elements integrated in crystal lattices are discussed with the aim of sharpening the awareness for this effect in the Raman community and promoting its application in materials analysis. The latter is demonstrated by the Raman microspectroscopic imaging of the distributions of both Raman-active and Raman-inactive phases in clinker remnants in a 19th-century meso Portland cement mortar sample, which contain relatively high amounts of free lime detected in the form of both luminescing CaO and Raman-scattering Ca(OH)2, owing to exposure of the surface of the thin section to humid air. A combination of light and Raman spectroscopy revealed a calcium–magnesium–iron sulphide phase, indicating sulphurous raw materials and/or solid fuels employed in the calcination process, which in contrast to previously described morphologies of sulphides in cement clinker form extensive greenish black layers on free lime crystals.
Only a few scientific evidences for the use of Egyptian blue in Early Medieval wall paintings in Central and Southern Europe have been reported so far. The monochrome blue fragment discussed here belongs to the second church building of St. Peter above Gratsch (South Tyrol, Northern Italy, fifth/ sixth century A.D.). Beyond cuprorivaite and carbon black (underpainting), 26 accessory minerals down to trace levels were detected by means of Raman microspectroscopy, providing unprecedented insights into the raw materials blend and conversion reactions during preparation, application, and ageing of the pigment. In conjunction with archaeological evidences for the manufacture of Egyptian blue in Cumae and Liternum and the concordant statements of the antique Roman writers Vitruvius and Pliny the Elder, natural impurities of the quartz sand speak for a pigment produced at the northern Phlegrean Fields (Campania, Southern Italy). Chalcocite (and chalcopyrite) suggest the use of a sulphidic copper ore, and water-insoluble salts a mixed-alkaline flux in the form of plant ash. Not fully reacted quartz crystals partly intergrown with cuprorivaite and only minimal traces of silicate glass portend solid-state reactions predominating the chemical reactions during synthesis, while the melting of the raw materials into glass most likely played a negligible role.
In this work, we present our results achieved in several research activities for development of distributed fiber optic radiation sensors using glass and polymer optical fibers. The findings show that both the measurement of the radiation-induced attenuation (RIA) along the entire sensing fiber and the accompanying change in the refractive index of the fiber core can be used for distributed radiation monitoring.
Spatial Period of Laser-Induced Surface Nanoripples on PET Determines Escherichia coli Repellence
(2021)
Bacterial adhesion and biofilm formation on surfaces are associated with persistent microbial contamination, biofouling, and the emergence of resistance, thus, calling for new strategies to impede bacterial surface colonization. Using ns-UV laser treatment (wavelength 248 nm and a pulse duration of 20 ns), laser-induced periodic surface structures (LIPSS) featuring different submicrometric periods ranging from ~210 to ~610 nm were processed on commercial poly(ethylene terephthalate) (PET) foils. Bacterial adhesion tests revealed that these nanorippled surfaces exhibit a repellence for E. coli that decisively depends on the spatial periods of the LIPSS with the strongest reduction (~91%) in cell adhesion observed for LIPSS periods of 214 nm. Although chemical and structural analyses indicated a moderate laser-induced surface oxidation, a significant influence on the bacterial adhesion was ruled out. Scanning electron microscopy and additional biofilm studies
using a pili-deficient E. coli TG1 strain revealed the role of extracellular appendages in the bacterial repellence observed here.
Stir bar sorptive extraction (SBSE) was compared with standardized pump sampling regarding the prospects to assess airborne levels of polycyclic aromatic hydrocarbons (PAHs) in indoor environments. A historic railway water tower, which will be preserved as a technical monument for museum purposes, was sampled with both approaches because the built-in insulationmaterial was suspected to release PAHs to the indoor air. The 16 PAHs on the US EPA list were quantified using gas chromatography with mass spectrometric detection in filters from pump sampling after solvent extraction and on SBSE devices after thermal desorption. SBSEwas seen to sample detectable PAHmasseswith excellent repeatability and a congener pattern largely similar to that observed with pump sampling. Congener patterns were however significantly different from that in the PAH source because release from the insulation material is largely triggered by the respective congener vapor pressures. Absolute masses in the ng range sampled by SBSE corresponded to airborne concentrations in the ng L−1 range determined by pump sampling. Principle differences between SBSE and pump sampling as well as prospects of SBSE as cost-effective and versatile complement of pump sampling are discussed.
Influence of pre-ignition pressure rise on safety characteristics of dusts and hybrid mixtures
(2021)
For the determination of the safety characteristics of dusts it is necessary to disperse the dust in the oxidating atmosphere (usually air). In the standard procedures for dusts this is realized by a partially evacuated explosion vessel (20L-sphere) in which the dust gets injected from a dust chamber pressurized with air. Shortly after that injection (60 ms) the dust cloud gets ignited under turbulent conditions, that are otherwise seen as almost ambient with 20 ◦C and about 1 bar (abs). While there has been a lot of research about the influence of the ignition delay time and the level of turbulence in the recent years little attention was paid to the pre–ignition pressure rise and the allowed variations in the standards. In the following work we showed that the allowed ranges for the pressures in the different dust standards influence the safety characteristics of dust alone severely.
Even though hybrid mixtures are an emerging risk problem in an interconnected industry there is no standard for the determination of their safety characteristics. In this work it is shown that especially for the preparation of hybrid mixtures of flammable dust and gas the pressures after injection of the dust and the mixing procedure have a large influence on the composition of the tested mixtures and therefore on the safety characteristics.
Considering both effects, wrong concentration of gas and wrong initial pressure, the discrepancy of safety characteristics from different facilities will be too big to applicable. The methods to overcome these weaknesses are also presented.
Photon upconversion upon 1550 nm excitation is of high relevance for applications in the third biological excitation window, for photovoltaics beyond current limitations, and enables appealing options in the field of glass Fiber telecommunications. Trivalent doped erbium ions (Er3+) are the material of choice for 1550 nm excited upconversion, however, they suffer from a low absorption cross-section and a low brightness. Therefore, the ability of Silicon metasurfaces to provide greatly enhanced electrical near-fields is employed to enable efficient photon upconversion even at low external Illumination conditions. Hexagonally shaped β-NaYF4:Er3+ nanoparticles are placed on large-area silicon metasurfaces designed to convert near-infrared (1550 nm) to visible light. More than 2400-fold enhanced photon upconversion luminescence is achieved by using this metasurface instead of a planar substrate.
With the aid of optical simulations based on the finite-element method, this result is attributed to the coupling of the excitation source with metasurface resonances at appropriate incident angles. Analysis of the excitation power density dependence of upconversion luminescence and red-to-green-emission ratios enables the estimation of nanoscale near-field enhancement on the metasurface. The findings permit the significant reduction of required external excitation intensities for photon upconversion of 1550 nm light, opening perspectives in biophotonics, telecommunication, and photovoltaics.
The increasingly sophisticated nature of modern, more environmentally friendly cementitious binders requires a better understanding and control particularly of the complex, dynamic processes involved in the early phase of cement hydration. In-situ monitoring of properties of a constantly changing system over a defined period of time calls for simple, sensitive, fast, and preferably also non-invasive methods like optical spectroscopy
Nitrapyrin (NP) is applied to cultivated soils to inhibit the enzymatic activity of ammonia monooxygenase (AMO), but its poor aqueous solubility and high volatility severely limit its application. β-Cyclodextrin (β-CD) is commonly used to form inclusion complexes with hydrophobic molecules, improving water solubility and stability upon complexation. Here we report on the mechanochemical synthesis of the inclusion complex β-CD·NP, characterized via a combination of solid-state techniques, including exsitu and in situ X-ray diffraction, Raman and NMR spectroscopies, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The pure inhibitor NP was also structurally characterized. The β-CD·NP complex presents improved solubility and thermal stability, and still inhibits the enzymatic activity of AMO with high efficacy. All results indicate that the inclusion of NP into β-CD represents a viable route for the preparation of a novel class of inhibitors, with improved properties related to stability, water solubility, and good inhibition activity.
The visualization of index-of-refraction (IoR) distribution is one of the common methods to investigate fluid flow or pressure fields. While schlieren and shadowgraphy imaging techniques are widely accepted, their inherent limitations often lead to difficulties in elucidating the IoR distribution and extracting the true IoR information from the resulting images. While sophisticated solutions exist, the IoR-gradient-to-image was achieved by purposely introducing a commonly avoided “defect” into the optical path of a conventional coincident schlieren/shadowgraphy setup; the defect is a combination of slight defocusing and the use of non-conjugate optical components. As such, the method presented in this work is referred to as defocusing shadowgraphy, or DF-shadowgraphy. While retaining the ease of a conventional schlieren/shadowgraphy geometry, this DF approach allows direct visualization of complicated resonant acoustic fields even without any data processing. For instance, the transient acoustic fields of a common linear acoustic resonator and a two-dimensional one were directly visualized without inversion. Moreover, the optical process involved in DF-shadowgraphy was investigated from a theoretical perspective. A numerical solution of the sophisticated impulse response function was obtained, which converts the phase distortion into intensity distributions. Based on this solution, the IoRs of various gas streams (e.g., CO2 and isopropanol vapor) were determined from single images.
Cast magnesium alloys welds produced by refill friction stir spot welding (refill FSSW) show low lap shear strength (LSS) and constantly fail in stirred zone (SZ) shear mode. The cause is most probably related to the heavily textured microstructure. Here, to re-engineer the resulting microstructure, we pro- pose a novel process variant, the differential rotation refill FSSW (DR-refill FSSW). DR-refill FSSW stim- ulates discontinuous dynamic recrystallization and produces a bimodal microstructure with weakened texture. Therefore, the deformation incompatibility between SZ and thermal-mechanically affected zone is avoided. The welds have 50% higher LSS than that of standard refill FSSW welds, and fail in a different failure mode, i.e., SZ pull-out mode. DR-refill FSSW provides a new and effective strategy for improving the performance of spot welds based on microstructural engineering.
The application of magnesium (Mg) inevitably involves dissimilar welding with steel. A novel solid state spot welding method, refill friction stir spot welding (refill FSSW), was utilized to weld AZ31 Mg alloy to galvanized DP600 steel. Although Mg/Fe is an immiscible alloy system, defect-free welds with high strength were successfully obtained in a wide parameter window. The results of microstructure, interfacial reactions, and mechanical properties are reported to reveal the underlying joining mechanism. Due to the melting of Zn coating and subsequent Mg-Zn reactions, Mg-Zn eutectic and intermetallic compounds were detected within welds. Heterogeneous interfacial reactions occur along Mg/steel interface, and the relationship between interfacial structure and fracture behavior was investigated. The joining mechanism is associated with Zn coating and Fe-Al layer: 1) the presence of Zn coating is beneficial for achieving high-quality welding between Mg and steel, it protects the interface from oxidation and contributes to brazing of the weld; 2) the Al present in Mg alloy reacts with Fe, resulting in the growth of Fe-Al layer, which contributes to the diffusion bonding in the interface. The overall results clearly show that Refill FSSW is a competitive welding method for joining Mg and galvanized steel.
Fungi are ecologically outstanding decomposers of lignocellulose. Fungal lignocellulose degradation is prominent in saprotrophic Ascomycota and Basidiomycota of the subkingdom Dikarya. Despite ascomycetes dominating the Dikarya inventory of aquatic environments, genome and transcriptome data relating to enzymes involved in lignocellulose decay remain limited to terrestrial representatives of these phyla. We sequenced the genome of an exclusively aquatic ascomycete (the aquatic hyphomycete Clavariopsis aquatica), documented the presence of genes for the modification of lignocellulose and its constituents, and compared differential gene expression between C. aquatica cultivated on lignocellulosic and sugar-rich substrates. We identified potential peroxidases, laccases, and cytochrome P450 monooxygenases, several of which were differentially expressed when experimentally grown on different substrates. Additionally, we found indications for the regulation of pathways for cellulose and hemicellulose degradation. Our results suggest that C. aquatica is able to modify lignin to some extent, detoxify aromatic lignin constituents, or both. Such characteristics would be expected to facilitate the use of carbohydrate components of lignocellulose as carbon and energy sources.
Cardiolipin (CL) is a major cardiac mitochondrial phospholipid maintaining regular mitochondrial morphology and function in cardiomyocytes. Cardiac CL production includes ist biosynthesis and a CL-remodeling process. Here we studied the impact of CL-biosynthesis and the enzyme Cardiolipin Synthase (CLS) on cardiac function.
CLS and cardiac CL-species were significantly downregulated in cardiomyocytes following catecholamine-induced cardiac damage in mice, accompanied by increased oxygen consumption rates, signs of oxidative stress and mitochondrial uncoupling. RNAi-mediated cardiomyocyte-specific knockdown of CLS in Drosophila melanogaster resulted in marked cardiac dilatation, severe impairment of systolic performance and slower diastolic filling velocity assessed by fluorescence-based heart imaging. Finally, we showed that CL72:8 is significantly decreased in cardiac samples from patients with heart failure with reduced ejection fraction (HFrEF). In summary, we identified CLS as a regulator of cardiac function. Considering the cardiac depletion of CL-species in HFrEF, pharmacological targeting of CLS may be a promising therapeutic approach.zeige mehrzeige weniger
Atherosclerosis is a progressive inflammatory vascular disease characterized by endothelial dysfunction and plaque burden. Extracellular matrix (ECM)-associated plasma proteins play an important role in disease development. Our magnetic resonance imaging (MRI) study investigates the feasibility of using two different molecular MRI probes for the simultaneous assessment of ECM-associated intraplaque albumin deposits caused by endothelial damage and progressive inflammation in atherosclerosis. Male apolipoprotein E-deficient (ApoE-/-)-mice were fed a high-fat diet (HFD) for 2 or 4 months. Another ApoE-/--group was treated with pravastatin and received a HFD for 4 months. T1- and T2*-weighted MRI was performed before and after albumin-specific MRI probe (gadofosveset) administration and a macrophage-specific contrast agent (ferumoxytol). Thereafter, laser ablation inductively coupled plasma mass spectrometry and histology were performed. With advancing atherosclerosis, albumin-based MRI signal enhancement and ferumoxytol-induced signal loss areas in T2*-weighted MRI increased. Significant correlations between contrast-to-noise-ratio (CNR) post-gadofosveset and albumin stain (R2 = 0.78, p < 0.05), and signal loss areas in T2*-weighted MRI with Perls’ Prussian blue stain (R2 = 0.83, p < 0.05) were observed. No interference of ferumoxytol with gadofosveset enhancement was detectable. Pravastatin led to decreased inflammation and intraplaque albumin. Multi-target MRI combining ferumoxytol and gadofosveset is a promising method to improve diagnosis and treatment monitoring in atherosclerosis.
ISO 18516:2019 Surface chemical analysis—Determination of lateral resolution and sharpness in beam-based methods with a range from nanometres to micrometres revises ISO 18516:2006 Surface chemical analysis—Auger electron spectroscopy and X-ray photoelectron spectroscopy—Determination of lateral resolution. It implements three different methods delivering parameters useful to express the lateral resolution: (1) the straight edge method, (2) the narrow line method and (3) the grating method. The theoretical background of these methods is introduced in ISO/TR 19319:2013 Surface chemical analysis—Fundamental approaches to determination of lateral resolution and sharpness in beam-based methods. The revised International Standard ISO 18516 delivers standardized procedures for the determination of the (1) effective lateral resolution by imaging of square-wave gratings, the (2) lateral resolution expressed as the parameter D12–88 characterizing the steepness of the sigmoidal edge spread function (ESF) determined by imaging a straight edge and (3) the lateral resolution expressed as the full width of half maximum of the line spread function (LSF), wLSF, determined by imaging a narrow line. The last method also delivers information on the shape of the LSF, which characterizes an individual imaging instrument. Finally, the implementation of all three standardized methods in the field of imaging laboratory X-ray photoelectron spectroscopy (XPS) is shortly presented. This part of the letter is based on the use of a new test sample developed at ETH Zurich, Switzerland. This test sample displays a micrometre scaled pattern motivated by the resolving power of recent imaging XPS instruments.
Phosphorus rich sewage sludge ash is a promising source to produce phosphorus recycling fertilizer. However, the low plant availability of phosphorus in these ashes makes a treatment necessary. A thermochemical treatment (800–1000 °C) with alkali additives transforms poorly plant available phosphorus phases to highly plant available calcium alkali Phosphates (Ca,Mg)(Na,K)PO4. In this study, we investigate the use of K2SO4 as additive to produce a phosphorus potassium fertilizer in laboratory-scale experiments (crucible). Pure K2SO4 is not suitable as high reaction temperatures are required due to the high melting point of K2SO4.
To overcome this barrier, we carried out series of experiments with mixtures of K2SO4 and Na2SO4 resulting in a lower economically feasible reaction temperature (900–1000 °C). In this way, the produced phosphorus potassium fertilizers (8.4 wt.% K, 7.6 wt.% P) was highly plant available for phosphorus indicated by complete extractable phosphorus in neutral ammonium citrate solution. The added potassium is, in contrast to sodium, preferably incorporated into silicates instead of phosphorus phases. Thus, the highly extractable phase (Ca,Mg)(Na,K)PO4 in the thermochemical products contain less potassium than expected. This preferred incorporation is confirmed by a pilot-scale trial (rotary kiln) and thermodynamic calculation.
Thermally stable carbon nitride nanostructures have potential applications in surface coatings and automotive fields. In this work, hydrogenated nitrogen-rich carbon nitride nanoparticles have been synthesised via low-pressure low-power plasma vapour deposition technique from methane/Nitrogen gas mixture in a dry process. Thermal stability of the initially prepared hydrogenated carbon Nitride structures has been analysed by near-edge X-ray absorption fine-structure spectroscopy (NEXAFS, insitu), Raman spectroscopy, scanning and transmission electron microscopy and nuclear reaction Analysis (NRA). Thermal studies reveal the excellent stability of the material and nitrogen-rich characteristics (N/C ratio 0.5e0.2 ± 0.01). The obtained results suggest transformation of sp3-rich as-deposited carbon Nitride into sp2-carbon phase with more graphitic features upon thermal annealing. Such in-situ thermal studies of plasma deposited carbon nitrides confirm the conversion of sp3-rich phase to sp2-rich carbon phase at the critical temperature (about 450 K), without a huge loss in nitrogen content. The analysis revealed that the material is a stable plasma deposit after this critical temperature up to >1100 K. Additionally, super hydrophilic carbon nitride nanostructure transforms into a hydrophobic surface after thermal annealing.
These thermally stable hydrophobic carbon nitride nanoparticles could be used as a promising material for the hydrophobic coatings for various applications, especially for harsh conditions.
For the large-scale generation of hydrogen via water electrolysis the design of long term stable and active catalysts for the oxygen evolution reaction (OER) remains a key challenge. Most catalysts suffer from severe structural corrosion that becomes even more pronounced at fluctuating potentials. Herein, MnCo based cubic particles were prepared via a hydrothermal approach, in which the edge length of the micron-sized particles can be controlled by changing the pH value of the precursor solution. The cubes are composed of varying amounts of MnCo2O4, CoCO3 and a mixed (Mn/Co)CO3 phase. Structure–activity relationships were deduced revealing a volcano-type behavior for the intrinsic OER activity and fraction of spinel oxide phase.
A low overpotential of 0.37 V at 10 mA cm−2 and a stability of more than 25 h was achieved in 1.0 M KOH using a rotating disc electrode (RDE) setup. The best performing catalyst material was successfully tested under dynamic process conditions for 9.5 h and shows a superior catalytic activity as anode for the Overall water splitting in an electrolyser setup in 1.0 M KOH at 333 K compared to a reference NiCo-spinel catalyst.
This study reports on the stress relaxation potential of stress-relieving heat treatments for laser powder bed fused 316L. The residual stress is monitored non-destructively using neutron diffraction before and after the heat treatment. Moreover, the evolution of the microstructure is analysed using scanning electron microscopy. The results show, that a strong relaxation of the residual stress is obtained when applying a heat treatment temperature at 900°C. However, the loss of the cellular substructure needs to be considered when applying this heat treatment strategy.
Time resolved in situ (TRIS) monitoring has revolutionised the study of mechanochemical transformations but has been limited by available data quality. Here we report how a combination of miniaturised grinding jars together with innovations in X-ray powder diffraction data collection and state-of-the-art analysis strategies transform the power of TRIS synchrotron mechanochemical experiments. Accurate phase compositions, comparable to those obtained by ex situ measurements, can be obtained with small sample loadings. Moreover, microstructural parameters (crystal size and microstrain) can be also determined with high confidence. This strategy applies to all chemistries, is readily implemented, and yields high-quality diffraction data even using a low energy synchrotron source. This offers a direct avenue towards the mechanochemical investigation of reactions comprising scarce, expensive, or toxic compounds. Our strategy is applied to model systems, including inorganic, metal-organic, and organic mechanosyntheses, resolves previously misinterpreted mechanisms in mechanochemical syntheses, and promises broad, new directions for mechanochemical research.
Extensive research is being conducted on magnesium (Mg) alloys for bone implant manufacturing, due to their biocompatibility, biodegradability and mechanical properties. Gadolinium (Gd) is among the most promising alloying elements for property control in Mg alloy implants; however, its toxicity is contro- versial. Investigating Gd behavior during implant corrosion is thus of utmost importance. In this study, we analyzed the degradation byproducts at the implant site of biodegradable Mg-5Gd and Mg-10Gd implants after 12 weeks healing time, using a combination of different imaging techniques: histology, energy-dispersive x-ray spectroscopy (EDX), x-ray microcomputed tomography (μCT) and neutron μCT. The main finding has been that, at the healing time in exam, the corrosion appears to have involved only the Mg component, which has been substituted by calcium and phosphorus, while the Gd remains localized at the implant site. This was observed in 2D by means of EDX maps and extended to 3D with a novel application of neutron tomography. X-ray fluorescence analysis of the main excretory organs also did not reveal any measurable accumulation of Gd, further reinforcing the conclusion that very limited or no removal at all of Gd-alloy happened during degradation.
Deep understanding of the effects associated with fabrication parameters and their influence on the resulting structures shape is essential for the further development of direct laser writing (DLW). In particular, it is critical for development of reference materials, where structure parameters are precisely fabricated and should be reproduced with use of DLW technology. In this study we investigated the effect of various fabrication and preparation parameters on the structural precision of interest for reference materials. A well-studied photo-curable system, SZ2080 negative photo-resist with 1 wt.% Michler's ketone (Bis) photo-initiator, was investigated in this work. The correlation between applied laser power, laser velocity, fabrication direction on the deviations in the structure shape were observed by means of white light interferometry microscopy. Moreover, influence of slicing and hatching distances as well as prebake time were studied as function of sample shape. Deviations in the structure form between the theoretically expected and the one detected after DLW fabrication were observed in the range up to 15%. The observed shape discrepancies show the essential importance of fine-tuning the fabrication parameter for reference structure production.
Three chromatographic procedures were investigated regarding their potential for the quantification of aniline and 19 of its methylated and chlorinated derivatives in groundwater. These methods were based on liquid-liquid-extraction in combination with gas chromatography and single quadrupole mass spectrometry (GC/MS) according to German standard DIN 38407-16:1999 and its extension using tandem mass spectrometry (GC/MS-MS), both following liquid-liquid extraction, and as third alternative the direct injection of the water sample into a liquid chromatograph coupled to tandem mass spectrometry (LC/MS-MS). Results were compared using fortified water and real-world contaminated groundwater used in an interlaboratory comparison. It could be shown that GC/MS and GC/MS-MS yielded results deviating less than 10% from each other while all three procedure displayed quantification results deviating less than 15% from the intercomparison reference values in case of each analyte in the concentration range between 1 and 45 µg L-1. Though GC/MS-MS displays a ten-fold higher sensitivity than single quadrupole GC/MS, the precision of both methods in the concentration range was similar. LC/MS-MS has the advantage of no further sample preparation due to the direct injection and leads for methylanilines and meta-, para- substituted chloroanilines to results sufficiently equivalent to the standardised GC/MS method. However, LC/MS-MS is not suitable for ortho-chloroaniline derivates due to significantly lower ion yields than meta- and para-substituted chloroanilines.
The impact sensitivity (IS) of FOX-7 polymorphs is predicted by phonon up-pumping to decrease as layers of FOX-7 molecules flatten. Experimental validation proved anomalous owing to a phase transition during testing, raising questions regarding Impact sensitivity measurement and highlighting the need for models to predict IS of polymorphic energetic materials.
Iron-based catalysts have been reported manifold and studied as platinum group metal (PGM) free alternatives for the catalysis of the oxygen reduction reaction (ORR). However, their sustainable preparation by greener synthesis approaches is usually not discussed. In this work, we propose a new method for the sustainable preparation of such catalysts by using a mechanochemical approach, with no solvents and non-toxic chemicals. The materials obtained from low temperature carbonization (700 °C) exhibit considerable and stable catalytic performance for ORR in alkaline medium. A catalyst obtained
from iron hydroxide, tryptophan, dicyandiamide, and ammonium nitrate shows the best electrocatalytic Performance with an overpotential of 921 mV vs. RHE at 0.1 mA/cm2 and an electron transfer number of 3.4.
In additive manufacturing the powder bed based processes binder jetting and powder bed fusion are increasingly used also for the production of ceramics. Final part properties depend to a high percentage on the powder bed density. Therefore, the aim is to use the best combination of powder deposition method and powder which leads to a high packing of the particles. The influence of flowability, powder properties and deposition process on the powder bed density is discussed and the different deposition processes including slurry-based ones are reviewed.
It turns out that powder bed density reached by slurry-based layer deposition exceeds conventional powder deposition, however, layer drying and depowdering are extra steps or more time-consuming for the slurry route.
Depending on the material properties needed the most suitable process for the part has to be selected.
Bitumen is a crucial building material in road construction, which is exposed to continuously higher stresses due to higher traffic loads and changing climatic conditions. Therefore, various additives are increasingly being added to the bitumen complicating the characterisation of the bituminous binder, especially concerning the reuse of reclaimed asphalt.
Therefore, this work aimed to demonstrate that the combination of Fourier transform infrared (FTIR) spectroscopy with attenuated total reflexion (ATR) technique and multivariate evaluation is a very wellsuited method to reliable identify and quantify additives in bituminous binders. For this purpose, various unmodified and modified binders, directly and extracted from laboratory and reclaimed asphalts, were investigated with FTIR-ATR spectroscopy. The determined spectra, pre-processed by standard normal variate (SNV) transformation and the determination of the 1st derivation, were evaluated using factor Analysis (FA), linear discriminant analysis (LDA) and partial least square regression (PLSR). With this multivariate evaluation, first, a significant model with a very high hit rate of over 90% was developed allowing for the identification of styrene-butadiene copolymers (SBC), ethylene-copolymer bitumen (ECB) and different waxes (e.g. amide and Fischer-Tropsch wax) even if the additives do not show any additional peaks or the samples are multi-modified. Second, a quantification of the content is possible for SBC, ECB, and Amide wax with a mean error of RMSE B 0.4 wt% and a
coefficient of determination of R2[90%. Based on these results, FTIR identification and quantification of additives in bituminous binders is a very promising method with a great potential.
Layer-by-layer additive manufacturing (AM) by means of laser-powder bed Fusion (L-PBF) offers many prospects regarding the design of lattice structures used, for example, in gas turbines. However, defects such as bulk porosity, Surface roughness, and re-entrant features are exacerbated in nonvertical structures, such as tilted struts. The characterization and quantification of these kinds of
defects are essential for the correct estimation of fracture and fatigue properties.
Herein, cylindrical struts fabricated by L-PBF are investigated by means of X-ray computed tomography (XCT), with the aim of casting light on the dependence of the three kinds of defects (bulk porosity, surface roughness, and re-entrant features) on the build angle. Innovative analysis methods are proposed to correlate shape and position of pores, to determine the angular-resolved Surface roughness, and to quantify the amount of re-entrant surface features, q. A meshing of the XCT surface enables the correlation of q with the classical Surface roughness Pa. This analysis leads to the conclusion that there is a linear correlation between q and Pa. However, it is conjectured that there must be a threshold of surface roughness, below which no re-entrant features can be build.
While structural ceramics usually display a brittle mechanical behavior, their composites may show nonlinearities, mostly due to microcracking. Herein, the stiffness evolution of a sandwich-like laminate of an Al2O3 15%vol. ZrO2 matrix reinforced with Nextel 610 fibers is studied as a function of number of cycles N in tension. The stiffness of the composite degrades with increasing N, indicating microcracking. However, synchrotron X-ray refraction radiography shows that the internal specific surface of such cracks varies differently. A modeling strategy is developed for the calculation of the equivalent stiffness of mixtures (first the matrix and then the sandwich), based on the Voigt and Reuß schemes. The Bruno–Kachanov model is then used to estimate the initial microcrack density in the matrix (due to the thermal expansion mismatch) and the amount of microcracking increase upon cyclic loading. The stiffness in the composite degrades dramatically already after 20 000 cycles but then remains nearly constant. The combination of mechanical testing, quantitative imaging analysis, and modeling provides insights into the damage mechanisms acting: microcrack propagation is more active than microcrack initiation upon cyclic loading, but the second also occurs. This scenario is similar but not equal to previous results on porous and microcracked ceramics.
The trafficking of illegal drugs by criminal networks at borders, harbors, or airports is an increasing issue for public health as these routes ensure the main supply of illegal drugs. The prevention of drug smuggling, including the installation of scanners and other analytical devices to detect small traces of drugs within a reasonable time frame, remains a challenge. The presented immunosensor is based on a monolithic affinity column with a large excess of immobilized hapten, which traps fluorescently labeled antibodies as long as the analyte cocaine is absent. In the presence of the drug, some binding sites of the antibody will be blocked, which leads to an immediate breakthrough of the labeled protein, detectable by highly sensitive laser-induced fluorescence with the help of a Peltier-cooled complementary metal-oxide-semiconductor (CMOS) camera. Liquid handling is performed with high-precision syringe pumps and microfluidic chip-based mixing devices and flow cells. The biosensor achieved limits of detection of 7 ppt (23 pM) of cocaine with a response time of 90 s and a total assay time below 3 min. With surface wipe sampling, the biosensor was able to detect 300 pg of cocaine. This immunosensor belongs to the most sensitive and fastest detectors for cocaine and offers near-continuous analyte measurement.
High-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GF-MAS) was employed for determining adsorbable organic chlorine (AOCl) in water. Organic chlorine was indirectly quantified by monitoring the molecular absorption of the transient aluminum monochloride molecule (AlCl) around a wavelength of 261.42 nm in a graphite furnace. An aluminum solution was used as the molecularforming modifier. A zirconium coated graphite furnace, as well as Sr and Ag solutions were applied as modifiers for a maximal enhancement of the absorption signal. The pyrolysis and vaporization temperatures were 600 °C and 2300 °C, respectively. Non-spectral interferences were observed with F, Br, and I at concentrations higher than 6 mg L-1, 50 mg L-1, and 100 mg L-1, respectively. Calibration curves with NaCl, 4-chlorophenol, and trichlorophenol present the same slope and dynamic range, which indicates the chlorine atom specificity of the method. This method was evaluated and validated using synthetic water samples, following the current standard DIN EN ISO 9562:2004 for the determination of the sum parameter adsorbable organic halides (AOX) for water quality. These samples contain 4-chlorophenol as the chlorinated organic standard in an inorganic chloride matrix. Prior to analysis, organic chlorine was extracted from the inorganic matrix via solid-phase extraction with a recovery rate >95%. There were no statistically significant differences observed between measured and known values and for a t-test a confidence level of 95% was achieved. The limits of detection and characteristic mass were found to be 48 and 22 pg, respectively. The calibration curve was linear in the range 0.1–2.5 ng with a correlation coefficient R2 = 0.9986.