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Information on the condition and reliability of an offshore jacket structure provided by a vibration-based structural health monitoring system can guide decisions on inspection and maintenance. When selecting the sensor setup, the designer of the monitoring system must assess its overall benefit compared to its costs before installation. The potential benefit of continuously monitoring the dynamic response of a jacket structure can be formally quantified through a value of information analysis from Bayesian decision theory. In this contribution, we present a framework for optimizing the placement of vibration sensors on offshore jacket structures by maximizing the value of information of the monitoring system. To solve the resulting discrete optimization problem, we adapt a genetic algorithm. The framework is demonstrated in a numerical example considering a redundant jacket-type steel frame. The numerical study shows that monitoring the vibration response of the frame is beneficial. Good sensor setups consist of relatively few sensors located towards the upper part of the
frame. The adapted genetic algorithm performs similarly well as established sequential sensor placement algorithms and holds substantial promise for application to real jacket structures.
Laser powder bed fusion is one of the most promising additive manufacturing techniques for printing complex-shaped metal components. However, the formation of subsurface porosity poses a significant risk to the service lifetime of the printed parts. In-situ monitoring offers the possibility to detect porosity already during manufacturing. Thereby, process feedback control or a manual process interruption to cut financial losses is enabled.
Short-wave infrared thermography can monitor the thermal history of manufactured parts which is closely connected to the probability of porosity formation. Artificial intelligence methods are increasingly used for porosity prediction from the obtained large amounts of complex monitoring data. In this study, we aim to identify the potential and the challenges of deep-learning-assisted porosity prediction based on thermographic in-situ monitoring.
Therefore, the porosity prediction task is studied in detail using an exemplary dataset from the manufacturing of two Haynes282 cuboid components. Our trained 1D convolutional neural network model shows high performance (R² score of 0.90) for the prediction of local porosity in discrete sub-volumes with dimensions of (700 x 700 x 40) μm³.
It could be demonstrated that the regressor correctly predicts layer-wise porosity changes but presumably has limited capability to predict differences in local porosity. Furthermore, there is a need to study the significance of the used thermogram feature inputs to streamline the model and to adjust the monitoring hardware. Moreover, we identified multiple sources of data uncertainty resulting from the in-situ monitoring setup, the registration with the ground truth X-ray-computed tomography data and the used pre-processing workflow that might influence the model’s performance detrimentally.
The bond between polymer fibers and the surrounding cementitious matrix is essential for the development of concrete reinforcement. The single fiber pull-out test (SFPT) is the standard characterization technique for testing the bond strength. However, the different phases of debonding cannot be distinguished by the SFPT. This study investigates the debonding of different polymer fibers from the surrounding cementitious matrix with a modified SFPT and proposes methods to change the SFPT setup to generate more valuable information on the debonding mechanism. The SFPT was equipped with linear variable differential transformers (LVDT), digital image correlation (DIC) and acoustic emission (AE) analysis. The results demonstrate that the modified SFPT allows a better understanding of the different phases of debonding during fiber pull-out. Furthermore, bond strength values calculated by different methods reveal that the chemical bond of the investigated polymers is not different as reported by previous studies. Deformation measurements performed using LVDTs and DIC are suitable measuring techniques to characterize the debonding mechanism in SFPT. A correlation between recorded AE and debonding phases was not found.
Iron Oxide Nanocubes as a New Certified Reference Material for Nanoparticle Size Measurements
(2023)
The rational design and increasing industrial use of nanomaterials require a reliable characterization of their physicochemical key properties like size, size distribution, shape, and surface chemistry. This calls for nanoscale reference materials (nanoRMs) for the validation and standardization of commonly used characterization methods closely matching real-world nonspherical nano-objects. This encouraged us to develop a nonspherical nanoRM of very small size consisting of 8 nm iron oxide nanocubes (BAM-N012) to complement spherical gold, silica, and polymer nanoRMs. In the following, the development and production of this nanoRM are highlighted including the characterization by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) as complementary methods for size and shape parameters, homogeneity and stability studies, and calculation of a complete uncertainty budget of the size features. The determination of the nanocubes’ edge length by TEM and SAXS allows a method comparison. In addition, SAXS measurements can also provide the mean particle number density and the mass concentration. The certified size parameters, area equivalent circular diameter and square edge length, determined by TEM with a relative expanded uncertainty below 9%, are metrologically traceable to a natural constant for length, the very precisely known (111) lattice spacing of silicon. Cubic BAM-N012 qualifies as a certified nanoRM for estimating the precision and trueness, validation, and quality assurance of particle size and shape measurements with electron microscopy and SAXS as well as other sizing methods suitable for nanomaterials. The production of this new iron oxide nanocube RM presents an important achievement for the nanomaterial community, nanomaterial manufacturers, and regulators.
The rational design of next generation molecular and nanoscale reporters and the comparison of different emitter classes require the determination of the fluorometric key performance parameter fluorescence quantum yield (Φf), i.e., the number of emitted photons per number of absorbed photons. Main prerequisites for reliable Φf measurements, which are for transparent luminophore solutions commonly done relative to a reference, i.e., a fluorescence quantum yield standard of known Φf, are reliable and validated instrument calibration procedures to consider wavelength-, polarization-, and time-dependent instrument specific signal contributions, and sufficiently well characterized fluorescence quantum yield standards. As the standard’s Φf value directly contributes to the calculation of the sample’s Φf, its accuracy presents one of the main sources of uncertainty of relative Φf measurements. To close this gap, we developed a first set of 12 fluorescence quantum yield standards, which absorb and emit in the wavelength region of 330−1000 nm and absolutely determined their Φf values with two independently calibrated integrating sphere setups.
Criteria for standard selection and the configuration of these novel fluorescence reference materials are given, and the certification procedure is presented including homogeneity and stability studies and the calculation of complete uncertainty budgets for the certified Φf values. The ultimate goal is to provide the community of fluorescence users with available reference materials as a basis for an improved comparability and reliability of quantum yield data since the measurement of this spectroscopic key property is an essential part of the characterization of any new emitter.
Die Anwendung von Zuggliedern aus Carbon ist durch die außergewöhnlich gute Ermüdungs- sowie hohe Zugfestigkeit des Werkstoffs motiviert. Ferner ergibt sich gegenüber Stahl eine deutliche Reduzierung des Querschnitts. Perspektivisch sollen damit u. a. Stahlzugglieder im Netzwerkbogenbrückenbau ersetzt werden. Das Tragverhalten von Carbonzuggliedern im Brandfall ist jedoch bislang unbekannt. Daher wurden mittels Bauteilbrandversuchen die Versagensmechanismen untersucht sowie anhand gewonnener Versuchsdaten eine exemplarische Einschätzung zur Gleichwertigkeit gegenüber konventionellen Stahlzuggliedern vorgenommen. Der Beitrag beschreibt realmaßstäbliche Brandversuche an mechanisch belasteten Carbonzuggliedern, die im Rahmen des Verbundforschungsvorhabens NeZuCa durchgeführt wurden. Das Versuchsprogramm umfasste vier Carbonzugglieder mit kreisrunden Querschnitten in zwei verschiedenen Durchmessern, 36 mm und 51 mm. In Ermangelung eines präskriptiven Brandszenarios für den im Projekt vorgesehenen Anwendungsfall und aus Gründen der Vergleichbarkeit erfolgte die Brandbeanspruchung nach Einheitstemperaturzeitkurve (ETK). Neben den Längsverformungen der Zugglieder wurden auch die Bauteil und Brandraumtemperaturen aufgezeichnet.
Contamination of natural bodies of water or soil with oils and lubricants (or generally, hydrocarbon derivatives such as petrol, fuels, and others) is a commonly found phenomenon around the world due to the extensive production, transfer, and use of fossil fuels. In this work, we develop a simple system for the on-field detection of total petroleum hydrocarbons (TPHs) in water and soil. The test is based on the measurement of the fluorescence signal emitted by the molecular rotor 2-[ethyl[4-[2-(4-nitrophenyl)ethenyl]phenyl]amino]ethanol (4-DNS-OH). This dye is embedded in a hydrophobic polymeric matrix (polyvinylidene fluoride), avoiding interactions with water and providing a robust support for use in a test strip fashion. Together with the strips, an embedded optical system was designed for fluorescence signal read-out, featuring a Bluetooth low-energy connection to a commercial tablet device for data processing and analysis. This system works for the detection and quantification of TPHs in water and soil through a simple extraction protocol using a cycloalkane solvent with a limit of detection of 6 ppm. Assays in surface and sea waters were conclusive, proving the feasibility of the method for in-the-field operation.
The microstructure of an apatite-wollastonite (code name AP40) glass-ceramic is analyzed in this study by combining 2D microscopy, phase analysis, X-ray absorption and synchrotron X-ray refraction computed tomography (XCT and SXRCT, respectively). It is shown that this combination provides a useful toolbox to characterize the global microstructure in a wide scale range, from sub-micrometer to millimeter. The material displays a complex microstructure comprising a glassy matrix with embedded fluorapatite and wollastonite small crystals. In this matrix, large (up to 200 μm) spike-shaped structures are distributed. Such microstructural features are oriented around a central sphere, thereby forming a structure resembling a sea urchin. A unique feature of SXRCT, in contrast to XCT, is that internal interfaces are visualized; this allows one to show the 3D distribution of these urchins with exceptionally good contrast. Furthermore, it is revealed that the spike-shaped structures are not single crystals, but rather composed of sub-micrometric crystals, which are identified as fluorapatite and diopside phases by SEM-EDX analysis.
In this study, we compare analytical methods for PFAS determination–target analysis, non-target screening (NTS), direct total oxidizable precursor assay (dTOPA) and extractable organically bound fluorine (EOF). Therefore, suspended particulate matter (SPM) samples from German rivers at different locations in time series from2005 to 2020 were analyzed to investigate temporal and spatially resolved trends. In this study 3 PFAS mass balances approaches were utilized: (i) PFAA target vs. PFAS dTOPA, (ii) PFAS target vs. EOF and (iii) PFAS target vs. PFAS dTOPA vs. organofluorines NTS vs. EOF. Mass balance approach (i) revealed high proportions of precursor substances in SPM samples. For the time resolved analysis an increase from 94% (2005) to 97% in 2019 was observable. Also for the spatial resolved analysis precursor proportions were high with >84% at all sampling sites. Mass balance approach (ii) showed that the unidentified EOF (uEOF) fraction increased over time from82% (2005) to 99% (2019). Furthermore, along the river courses the uEOF increased. In the combined mass balance approach (iii) using 4 different analytical approaches EOF fractions were further unraveled. The EOF pattern was fully explainable at the sampling sites at Saar and Elbe rivers. For the time resolved analysis, an increased proportion of the EOF was now explainable. However, still 27% of the EOF for the time resolved analysis and 25% of the EOF for the spatial resolved analysis remained unknown. Therefore, in a complementary approach, both the EOF and dTOPA reveal unknown gaps in the PFAS mass balance and are valuable contributions to PFAS risk assessment. Further research is needed to identify organofluorines summarized in the EOF parameter.
Optimizing the Green Synthesis of ZIF-8 by Reactive Extrusion Using In Situ Raman Spectroscopy
(2023)
We report the scale-up of a batch solid synthesis of zeolitic imidazolate framework-8 (ZIF-8) for reactive extrusion. The crystalline product forms in the extruder directly under the mixture of solid 2-methylimidazole and basic zinc carbonate in the presence of a catalytic amount of liquid. The process parameters such as temperature, liquid type, feeding rate, and linker excess were optimized using the setup specifically designed for in situ Raman spectroscopy. Highly crystalline ZIF-8 with a Brunauer–Emmett–Teller (BET) surface area of 1816 m2 g–1 was quantitatively prepared at mild temperature using a catalytic amount of ethanol and a small excess of the linker. Finally, we developed a simple and comprehensive approach to evaluating the environmental friendliness and scalability of metal–organic framework (MOF) syntheses in view of their large-scale production.
Lithium-ion batteries are a key technology to achieve the goals of limiting climate change due to the important role as traction technology for Electric Vehicles and in stationary energy storage systems. Over(dis) charge, mechanical damage due to accidents or thermal abuse such as fires can initiate an accelerated self-heating process of the batteries, called thermal runaway. A thermal runaway can propagate from cell to cell within a larger assembly of cells such as modules or battery packs and can cause rapid heat and toxic gas emissions. The resulting battery fire can spread to adjacent facilities, e.g. other cars in underground car parks or to a whole building in case of a large stationary energy storage.
For proof of fire protection requirements or to design suitable fire protection systems, Computational Fluid Dynamic (CFD) simulations are getting more and more important. The aim of CFD fire simulations is to predict the global hazards of a fire to its surroundings, that is mainly characterized by the release of heat and smoke and its spread in the fire environment. There are many numerical investigations of lithium-ion batteries in the literature. One class of models is used to simulate the charge and discharge process of lithium-ion batteries and to predict the temperature or voltage evolution inside the battery. On the other hand, there are models describing batteries under abuse conditions to predict the consequences of a thermal runaway event to the local environment, like the temperatures inside a battery or at the battery surface. Henriksen et al. use a generic battery gas mixture to simulate an explosion of vented gases from a Lithium Iron Phosphate battery and compare experimental results for the explosion pressure and the position of the flame front to the outcomes of a simulation with Xifoam. Larsson et al. used a combination of CFD simulations with FDS and thermal model with COMSOL to predict the temperature development of neighboring cells in a thermal runaway propagation. Truchot et al. use a design Heat Release Rate (HRR) curve for a battery based on experimental measurements to build up an overall HRR curve for a truck loaded with 100 lithium-ion batteries. This summed up HRR and corresponding smoke production curve is then used as an input for a simulation of a truck fire in a tunnel with Fire Dynamics Simulator (FDS). The pre-definition of the HRR curve is a frequently used method in fire engineering. It has the disadvantage, that the heat release cannot be influenced by physical processes, such as changed ventilation conditions or extinguishing measures. In this paper, a model is presented that determines the release of heat and gases based on the thermal runaway mechanisms of the battery, which can be used in CFD fire simulations with focus on prediction of fire hazards to nearby environment.
The combination of acoustically levitated droplets, mid-IR laser evaporation, and subsequent post-ionization by secondary electrospray ionization was applied for monitoring the enzymatic digestion of various proteins. Acoustically levitated droplets are an ideal, wall-free model reactor, readily allowing compartmentalized microfluidic trypsin digestions. Time-resolved interrogation of the droplets yielded real-time information on the progress of the reaction and thus provided insights into reaction kinetics. After 30 min of digestion in the acoustic levitator, the obtained protein sequence coverages were identical to the reference overnight digestions. Importantly, our results clearly demonstrate that the applied experimental setup can be used for the real-time investigation of chemical reactions. Furthermore, the described methodology only uses a fraction of the typically applied amounts of solvent, analyte, and trypsin. Thus, the results exemplify the use of acoustic levitation as a green analytical chemistry alternative to the currently used batch reactions.
The soil-feeding habit is an evolutionary novelty found in some advanced groups of termites. The study of such groups is important to revealing interesting adaptations to this way-of-life. The genus Verrucositermes is one such example, characterized by peculiar outgrowths on the head capsule, antennae and maxillary palps, which are not found in any other termite. These structures have been hypothesized to be linked to the presence of a new exocrine organ, the rostral gland, whose structure has remained unexplored.
We have thus studied the ultrastructure of the epidermal layer of the head capsule of Verrucositermes tuberosus soldiers.We describe the ultrastructure of the rostral gland, which consists of class 3 secretory cells only. The dominant secretory organelles comprise rough endoplasmic reticulum and Golgi apparatus, which provide secretions delivered to the surface of the head, likely made of peptide-derived components of unclear function. We discuss a possible role of the rostral gland of soldiers as an adaptation to the frequent encounter with soil pathogens during search for new food resources.
As most of polymeric materials are inherently flammable, flame retardants (FR) are commonly used to reduce their fire risks. Nevertheless, these flame retardant materials are often detrimental to smoke parameters like specific optical density or smoke toxicity. The influence of several smoke suppressants (SP)-zinc stannate, zinc phosphate, titanium oxide and hydrotalcite-were investigated with respect to flame retardancy, smoke emission, particle emission and smoke toxicity in a diethyl aluminum phosphinate (AlPi) flame retardant polyamide 6.6 (PA6.6). It was shown that the interaction between SP, FR and polymer is crucial for smoke and fire properties and can change the mode of action of the FR as well the decomposition mechanism of the polymer. Small amounts of SP show less effect on forced flaming behavior and the optical density, but they can influence flammability and the particle size distribution of the soot particles. The flame retardancy was significantly enhanced by 5 wt.-% zinc stannate in PA6.6 under forced flaming conditions. The charring mechanism was improved, and the mode of action of AlPi switched from the gas to the condensed phase. This resulted of in a reduced PHRR and TSP and an increase in residue yield. The smoke toxicity and optical density were reduced in the smoke density chamber as well. The smoke particles shifted to smaller sizes as the time in the pyrolytic zone increased. The formation of a dense char is assumed to be the key factor to enhance smoke suppression and flame retardancy properties.
Prolonging structural integrity—Fatigue of scarf repairs for wind turbine blade shell applications
(2023)
The influence of scarf repair variables on the mechanical properties of glass fiber reinforced polymer sandwich structures is examined for the application of wind turbine blade shell repairs. Reference shell specimens are tested under fully-reversed cyclic loading to understand the fatigue behavior of the sub-component structure within a range of in-service loads, to which shell specimens with a scarf joint repair are compared. A fatiguesuperior repair material is shown to improve the fatigue behavior of the repaired structures compared to the reference specimens. In separating layup and geometry, damage development is examined on the subcomponent scale for a structural understanding of a scarf repair using in-situ digital image correlation-based strain field measurements as well as passive thermography. Within scarf repair variables, the geometry is shown to play a larger role than layup in the fatigue performance of the repaired structure.
Aero-engine turbine disks are safety-relevant components which are operated under high thermal and mechanical stress conditions. The actual part qualification and certification procedures make use of spin-tests conducted on production-similar disks. While these tests provide, on the one hand, a reliable definition of the critical conditions for real components, on the other hand they represent a relevant cost item for engine manufacturers. The aim of this work is to present two alternative burst speed assessment methods under development based on the Failure Assessment Diagram (FAD) and a global stability criterion, respectively. In the scope of the fracture mechanics assessment, the failure modes hoop-burst and rim-peeling are investigated with semicircular surface cracks modelled at the critical regions on the turbine disk. The comparison of the predicted critical rotational speed shows good agreement between the assessment methods.
This paper presents an erosion interpretation of cohesive granular materials stressed by an impinging jet based on the results of a micromechanical simulation model. The numerical techniques are briefly described, relying on a two-dimensional Lattice Boltzmann Method coupled with a Discrete Element Methods including a simple model of solid intergranular cohesion.
These are then used to perform a parametric study of a planar jet in the laminar regime impinging the surface of granular samples with different degrees of cohesive strength. The results show the pertinence of using a generalized form of the Shields criterion for the quantification of the erosion threshold, which is valid for cohesionless samples, through empirical calibration, and also for cohesive ones. Furthermore, the scouring kinetics are analysed here from the perspective of a selfsimilar expansion of the eroded crater leading to the identification of a characteristic erosion time and the quantification of the classical erosion coefficient. However, the presented results also challenge the postulate of a local erosion law including erodibility parameters as intrinsic material properties. The paper then reviews the main limitations of the simulation and current interpretation models, and discusses the potential causes for the observed discrepancies, questioning the pertinence of using time-averaged macroscopic relations to correctly describe soil erosion. The paper concludes addressing this question with a complementary study of the presented simulations re-assessed at the particle-scale. The resulting local critical shear stress of single grains reveals a very wide dispersion of the data but nevertheless appears to confirm the general macroscopic trend derived for the cohesionless samples, while the introduction of cohesion implies a significant but systematic quantitative deviation between the microscopic and macroscopic estimates. Nevertheless, the micro data still shows consistently that the critical shear stress does actually vary approximately in linear proportion of the adhesive force.
There is no applicable existing standard for the determination of safety characteristics for hybrid mixtures. While developing a new standard in a joint research project in Germany first results from parameter studies led to a standard procedure that can be adopted by laboratories that are already testing dusts in the so called 20L-sphere with as little additional effort as necessary. In fact, one of the main objectives of this research project was to keep modifications and adjustments from the generally accepted dust testing procedures as easy and minimal as possible so as to limit potential deviations from one laboratory to another.
In this first round robin test on hybrid mixtures ever, with methane as gas component and a specific corn starch as dust sample, the practicality of the whole procedure, the scattering of the results and the deviation between the testing apparatuses is investigated. This paper summarizes the experimental procedure adopted and objectives of the first round-robin phase involving three of the four original German companies, plus volunteering laboratories from Australia, Belgium, Czech Republic, France, Poland and P.R. China. The results will have an impact on the new standard and may lead to robust data for later simulation purposes.
The ISO 16000-6 standard gives directions to adapt the analysis of volatile organic compounds (VOCs) in indoor and test chamber air to very volatile organic compounds (VVOCs). The same techniques with sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (TD-GC/MS) should be used. However, VVOCs require gaseous standards, an adapted GC column and a reliable sampling adsorbent. This work presents experimental results to tackle those three experimental gaps. A stable standard gas mixture containing 47 VVOCs, 13 VOCs and an internal standard was successfully generated. It was employed to study the suitability of seven types of chromatography columns. The use of PLOT (Porous Layer Open Tubular) columns such as PoraBOND Q is well suitable for VVOC analysis. The recoveries of the 60 analytes on a total of 16 adsorbents and their combinations were determined: A combination of the graphitized carbon black Carbograph 5TD 40/60 and the carbon molecular sieve CarbosieveTM SII showed great recoveries for all analytes. Carbon molecular sieves adsorb water which can impair the analysis. A dry purge of the multi-sorbent in the sampling direction led to a complete water removal and promising recoveries of the analytes.
The development of the microbiologically influenced corrosion ( MIC ) -specific inductively coupled plasma-time of flight-mass spectrometry ( ICP-ToF-MS ) analytical method presented here, in combination with the investigation of steel-MIC interactions, contributes significantly to progress in instrumental MIC analysis. For this, a MIC-specific staining procedure was developed, which ensures the analysis of intact cells. It allows the analysis of archaea at a single cell level, which is extremely scarce compared to other well-characterized organisms. The detection method revealed elemental selectivity for the corrosive methanogenic strain Methanobacterium -affiliated IM1. Hence, the possible uptake of individual elements from different steel samples was investigated and results showed the cells responded at a single-cell level to the different types of supplemented elements and displayed the abilities to uptake chromium, vanadium, titanium, cobalt, and molybdenum from solid metal surfaces. The methods developed and information obtained will be used in the future to elucidate underlying mechanisms, compliment well-developed methods, such as SEM-EDS, and develop novel material protection concepts.
Grain boundaries (GBs)’s role in determining the functional and mechanical properties of polycrystalline materials is inscribed in both their structure and chemistry. Upon solute segregation, the structure and composition of a GB can change concurrently. We study the co-evolution of GB’s structure and segregation by enhancing the density-based phase-field model to account for the in-plane structural variations in the GB. Significant mutual coupling is revealed between the GB’s chemical and structural states during Mn segregation in Fe-Mn alloys. We found that the structural degrees of freedom in a GB (the ability of the GB structure to respond to the chemical variation) amplifies Mn segregation transition, even when the GB structure stays unchanged. When the GB structure is not uniform, that is the usual case, the coupling between GB structure and segregation evolution also enables the spinodally formed low- and high-Mn phases (upon segregation transition) to co-exist within the GB region. These findings explain the stabilizing mechanism of pronounced interfacial segregation fluctuations, experimentally evidenced in Fe-Mn GBs, and give new insights on the structural sensitivity of GBs’ segregation phenomena and the mutual chemo-structural interplay.
The environmental fate of the frequently used broad-spectrum β-lactam antibiotic amoxicillin (AMX) is of high concern regarding the potential evolution of antimicrobial resistance (AMR). Moreover, it is known that AMX is prone to hydrolysis, yielding a variety of hydrolysis products (HPs) with yet unknown effects. Studies to identify those HPs and investigate their formation mechanisms have been reported but a long-term study on their stability in real water samples was missing. In this regard, we investigated the hydrolysis of AMX at two concentration levels in four distinct water types under three different storage conditions over two months. Concentrations of AMX and four relevant HPs were monitored by an LC-MS/MS method revealing pronounced differences in the hydrolysis rate of AMX in tap water and mineral water on the one hand (fast) and surface water on the other(slow). In this context, the occurrence, relative intensities, and stability of certain HPs are more dependent on the water type than on the storage condition. As clarified by ICP-MS, the main difference between the water types was the content of the metals copper and zinc which are supposed to catalyze AMX hydrolysis demonstrating an effective method to degrade AMX at ambient conditions.
MIKE III apparatus tests were conducted to investigate the minimum ignition energy (MIE) of coal dusts in air and O2/CO2 atmospheres with and without small amount of CH4/H2. The O2 mole fraction (XO2) in the gas mixtures varied from 21% to 50% with the CH4/H2 mole fraction from 0 to 2%. Experimental result showed that MIE of coal dusts significantly decreases even by three orders of magnitude in mJ with increasing XO2 and the addition of CH4/H2. Compared with CH4, H2 had a relatively strong promotion effect on the spark ignition of coal dusts. The inhibiting effect of CO2 was found to be much stronger than N2, but this inhibiting effect of CO2 could be eliminated by 9% increment of XO2. The effect on MIE of coal dusts thus followed by the order: 9% increment of XO2 > CO2 replacing N2 > 2% CH4 or H2 addition. Moreover, two empirical models were used to estimate the MIE of hybrid dust-gas mixture (HMIE), and the results showed that calculated data can well reflect the promoting effect of elevated XO2 and flammable gas addition, and the inhibiting effect of inert gas
The leaching behavior of scandium (Sc) from bauxite residues can differ significantly when residues of different geological backgrounds are compared. The mineralogy of the source rock and the physicochemical environment during bauxitization affect the association of Sc in the bauxite i.e., how Sc is distributed amongst different mineral phases and whether it is incorporated in and/or adsorbed onto those phases. The Sc association in the bauxite is in turn crucial for the resulting Sc association in the bauxite residue. In this study systematic leaching experiments were performed on three different bauxite residues using a statistical design of experiments approach. The three bauxite residues compared originated from processing of lateritic and karstic bauxites from
Germany, Hungary, and Russia. The recovery of Sc and Fe was determined by ICP-OES measurements. Mineralogical changes were analyzed by X-ray-diffraction and subsequent Rietveld refinement. The effects of various parameters including temperature, acid type, acid concentration, liquid-to-solid ratio and residence time were studied. A response surface model was calculated for the selected case of citric acid leaching of Hungarian bauxite residue. The investigations showed that the type of bauxite residue has a strong influence. The easily leachable fraction of Sc can vary considerably between the types, reaching ~20–25% in German Bauxite residue and ~50% in Russian bauxite residue. Mineralogical investigations revealed that a major part of this fraction was released from secondary phases such as cancrinite and katoite formed during Bayer processing of the bauxite.
The effect of temperature on Sc and Fe recovery is strong especially when citric acid is used. Based on the exponential relationship between temperature and Fe-recovery it was found to be particularly important for the selectivity of Sc over Fe. Optimization of the model for a maximum Sc recovery combined with a minimum Fe
recovery yielded results of ~28% Sc recovery at <2% Fe recovery at a temperature of 60 ◦C, a citric acid normality of 1.8, and a liquid-to-solid ratio of 16 ml/g. Our study has shown that detailed knowledge about the Sc association and distribution in bauxite and bauxite residue is key to an efficient and selective leaching of Sc
from bauxite residues.
Antimicrobial resistance (AMR) is a global health problem with the environment being an important compartment for the evolution and transmission of AMR. Previous studies showed that de-novo mutagenesis and horizontal gene transfer (HGT) by conjugation or transformation – important processes underlying resistance evolution and spread - are affected by antibiotics, metals and pesticides. However, natural microbial communities are also frequently exposed to biocides used as material preservatives, but it is unknown if these substances induce mutagenesis and HGT. Here, we show that active substances used in material preservatives can increase rates of mutation and conjugation in a species- and substance-dependent manner, while rates of transformation are not increased. The bisbiguanide chlorhexidine digluconate, the quaternary ammonium compound didecyldimethylammonium chloride, the metal copper, the pyrethroid-insecticide permethrin, and the azole-fungicide propiconazole increase mutation rates in Escherichia coli, whereas no increases were identified for Bacillus subtilis and Acinetobacter baylyi.
Benzalkonium chloride, chlorhexidine and permethrin increased conjugation in E. coli. Moreover, our results show a connection between the RpoS-mediated general stress and the RecA-linked SOS response with increased rates of mutation and conjugation, but not for all biocides. Taken together, our data show the importance of assessing the contribution of material preservatives on AMR evolution and spread.
Large-scale nanoimprinted metasurfaces based on silicon photonic crystal slabs were produced and coated with a NaYF4:Yb3+/Er3+ upconversion nanoparticle (UCNP) layer. UCNPs on these metasurfaces yield a more than 500-fold enhanced upconversion emission compared to UCNPs on planar surfaces. It is also demonstrated how the optical response of the UCNPs can be used to estimate the local field energy in the coating layer. Optical simulations using the finite element method validate the experimental results and the calculated spatial three-dimensional field Energy distribution helps us to understand the emission enhancement mechanism of the UCNPs closely attached to the metasurface. In addition, we analyzed the spectral shifts of the resonances for uncoated and coated metasurfaces and metasurfaces submerged in water to enable a prediction of the optimum layer thicknesses for different excitation wavelengths, paving the way to applications such as electromagnetic field sensors or bioassays.
The reliable measurement of very volatile organic compounds (VVOC) in indoor air by use of thermal desorption gas chromatography (TD-GC) in order to include them into evaluation schemes for building products even nowadays is a great challenge. For capturing these small molecules with carbon numbers ranging from C 1 –C 6 , strong adsorbents are needed. In the present study, recovery rates of nine suitable adsorbents of the groups of porous polymers, graphitised carbon blacks (GCB) and carbon molecular sieves (CMS) are tested against a complex test gas standard containing 29 VVOC. By consideration of the recovery and the relative humidity (50% RH), combinations of the GCB Carbograph 5TD, the two CMS Carboxen 1003 and Carbosieve SII as well as the porous polymer Tenax® GR were identified to be potentially suitable for sampling the majority of the VVOC out of the gas mix. The results reveal a better performance of the adsorbents in combination than being used alone, particularly under humid sampling conditions. The recovery rates of the chosen compounds on each adsorbent should be in the range of 80–120%.
A sedimented freshwater suspended organic matter fortified with particles of polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET) was employed in an interlaboratory comparison of thermoanalytical methods for microplastics identification and quantification. Three laboratories performed pyrolysis gas chromatography-mass spectrometry (Py-GC-MS), three others provided results using thermal extraction desorption followed by gas chromatography coupled to mass spectrometry (TED-GC-MS). One participant performed thermogravimetry-infrared spectroscopy (TGA-FTIR) and two participants used thermogravimetry coupled to mass spectrometry (TGA-MS). Further participants used differential scanning microscopy (DSC), a procedure based on micro combustion calorimetry (MCC) and a procedure based on elemental analysis.
Each participant employed a different combination of sample treatment, calibration and instrumental Settings for polymer identification and quantification. Though there is obviously room for improvements regarding the between-laboratory reproducibility and the harmonization of procedures it was seen that the participants Performing Py-GC-MS, TED-GC-MS, and TGA-FTIR were able to correctly identify all polymers and to report reasonable quantification results in the investigated concentration range (PE: 20.0 μg/mg, PP: 5.70 μg/mg; PS: 2.20 μg/mg, PET: 18.0 μg/mg). Although for the other methods limitations exists regarding the detection of specific polymers, they showed potential as alternative approaches for polymer quantification in solid environmental matrices.
This paper analyses the suitability of the Sensible Enthalpy Rise Approach for measuring the heat release rate of electric-vehicle-scale lithium-ion batteries. An apparatus is designed that meets the conditions of an electric-vehicle-scale lithium-ion battery fire by using cement board as wall material. Modifications of the Sensible Enthalpy Rise Methodology are presented due to the high emissivity and inhomogeneous temperature distribution of the apparatus wall material: a power 4 approach for the heat flow from the walls to the ambient air and an alternative determination methodology for the wall temperature. A one factor at a time parameter study is performed with Computational Fluid Dynamics simulations, investigating a new calibration method based on a fit approach compared to common methods, the wall temperature determination, the approach for the ambient heat flow, the calibration power and the volume flow at the outlet. The simulations show, that suitable estimations of the heat release rate are obtained by using the modifications for wall temperature determination and the power 4 approach for the ambient heat flow. The three calibration methods provide suitable constants, if the calibration power in the same order of magnitude as the mean of the heat release rate profile of the test object.
The complex effects of nanoparticles on a thermosetting material based on an anhydride cured DGEBA/Boehmite nanocomposite with different particle concentrations is considered. A combination of X-ray scattering, calorimetry, including fast scanning calorimetry as well as temperature modulated calorimetry and dielectric spectroscopy, was employed to study the structure, the vitrification kinetics and the molecular dynamics of the nanocomposites. For the first time in the literature for an epoxy-based composite a detailed analysis of the X-ray data was carried out. Moreover, the unfilled polymer was found to be intrinsically heterogeneous, showing regions with different crosslinking density, indicated by two separate dynamic glass transitions. The glass transition temperature decreases with increasing nanoparticle concentration, resulting from a change in the crosslinking density. Moreover, on the one hand, for nanocomposites the incorporation of nanofiller increased the number of mobile segments for low nanoparticle concentrations, due to the altered crosslinking density. On the other hand, for higher loading degrees the number of mobile segments decreased, resulting from the formation of an immobilized interphase (RAF). The simultaneous mobilization and immobilization of the segmental dynamics cannot be separated unambiguously. Taking the sample with highest number of mobile segments as reference state it was possible to estimate the amount of RAF.
The most common method for determination of the carbonation depth is the sprayed application of indicator solutions, Phenolphthalein in particular. Since the aerosols of Phenolphthalein are suspected to be carcinogenic, efforts have been intensified to use alternative indicators for the determination of carbonation depth. The subject and aim of this research paper are to examine indicator solutions from Alizarin Yellow R, Thymol Blue and a Mixed Indicator. These indicator solutions are commercially available and are not suspected to be carcinogenic.
For the purpose of this research, samples previously stored under accelerated carbonation conditions (1% CO2) were examined by thermogravimetric analysis (TGA) and examination of the pH value. Additionally, the electrolytic back-titration for determination of total CO2 amount was carried out comparatively to TGA.