Filtern
Erscheinungsjahr
- 2018 (477) (entfernen)
Dokumenttyp
- Zeitschriftenartikel (421)
- Beitrag zu einem Tagungsband (47)
- Buchkapitel (7)
- Monografie (1)
- Beitrag zu einem Sammelband (1)
Sprache
- Englisch (477) (entfernen)
Referierte Publikation
- ja (477) (entfernen)
Schlagworte
- Fluorescence (17)
- Nanoparticle (11)
- SAXS (11)
- Additive manufacturing (10)
- Residual stress (9)
- LIBS (8)
- MALDI-TOF MS (8)
- Mechanochemistry (8)
- Friction (7)
- Microstructure (7)
Organisationseinheit der BAM
- 1 Analytische Chemie; Referenzmaterialien (120)
- 8 Zerstörungsfreie Prüfung (90)
- 6 Materialchemie (89)
- 9 Komponentensicherheit (64)
- 5 Werkstofftechnik (63)
- 7 Bauwerkssicherheit (57)
- 6.3 Strukturanalytik (39)
- 4 Material und Umwelt (34)
- 8.5 Röntgenbildgebung (28)
- 9.4 Integrität von Schweißverbindungen (25)
Monitoring chemical reactions is the key to chemical process control. Today, mainly optical online methods are applied, which require excessive calibration effort. NMR spectroscopy has a high potential for direct loop process control while exhibiting short set-up times. Compact NMR instruments make NMR spectroscopy accessible in industrial and harsh environ¬ments for advanced process monitoring and control, as demonstrated within the European Union’s Horizon 2020 project CONSENS.
We present a range of approaches for the automated spectra analysis moving from conventional multivariate statistical approach, (i.e., Partial Least Squares Regression) to physically motivated spectral models (i.e., Indirect Hard Modelling and Quantum Mechanical calculations). By using the benefits of traditional qNMR experiments data analysis models can meet the demands of the PAT community (Process Analytical Technology) regarding low calibration effort/calibration free methods, fast adaptions for new reactants or derivatives and robust automation schemes.
The vulnerability of low-quality concrete of some bridges to ageing and deterioration while they are exposed to environmental conditions during their service life, influence of growing population and climate changes, is a well-known effect and requires survey. For survey, the development of a low cost, cost-efficient sensor network to be embedded for continuous or attached to the surface for periodic monitoring is essential.
Changing ground water conditions, flood or even leakage in fresh or disposal of waste water can lead to in-creased moisture content in building materials and structural elements as walls or floors. Moisture allows the transport of other adverse chemicals that might reduce the durability of structures. The paper presents a feasibility study about the capability of microwave modules as bluetooth® or ZigBee with frequency range at 2,4 GHz to create advanced Wireless Sensor Networks (WSN) for estimation and visualization of moisture distribution in infrastructure assets. It was found that the value of the received signal strength indication (RSSI) depends on the moisture content and can be the basis for the moisture distribution inside a massive structure.
The microwave modules may be used to compose networks outside and inside of building materials or structural elements. The higher the number of connections between BLE modules, the more precise and the more distant information can be obtained from the network. Mesh networking was applied to increase the quantitative information.
A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12–43 nm is presented utilizing steady-state and time-resolved fluorometry.
Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by highenergy O–H and C–H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated Population pathways of the 4F9/2 energy level of Er3+ were examined. Our results highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under “strongly quenched” conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the 4F9/2 energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels.
Cerro do Jarau is a conspicuous, circular morpho‐structural feature in Rio Grande do Sul State (Brazil), with a central elevated core in the otherwise flat “Pampas” terrain typical for the border regions between Brazil and Uruguay. The structure has a diameter of approximately 13.5 km. It is centered at 30o12′S and 56o32′W and was formed on basaltic flows of the Cretaceous Serra Geral Formation, which is part of the Paraná‐Etendeka Large Igneous Province (LIP), and in sandstones of the Botucatu and Guará formations. The structure was first spotted on aerial photographs in the 1960s. Ever since, its origin has been debated, sometimes in terms of an endogenous (igneous) origin, sometimes as the result of an exogenous (meteorite impact) event. In recent years, a number of studies have been conducted in order to investigate its nature and origin. Although the results have indicated a possible impact origin, no conclusive evidence could be produced. The interpretation of an impact origin was mostly based on the morphological characteristics of the structure; geophysical data; as well as the occurrence of different breccia types; extensive deformation/silicification of the rocks within the structure, in particular the sandstones; and also on the widespread occurrence of low‐pressure deformation features, including some planar fractures (PFs). A detailed optical microscopic analysis of samples collected during a number of field campaigns since 2007 resulted in the disclosure of a large number of quartz grains from sandstone and monomict arenite breccia from the central part of the structure with PFs and feather features (FFs), as well as a number of quartz grains exhibiting planar deformation features (PDFs). While most of these latter grains only carry a single set of PDFs, we have observed several with two sets, and one grain with three sets of PDFs. Consequently, we here propose Cerro do Jarau as the seventh confirmed impact structure in Brazil. Cerro do Jarau, together with Vargeão Dome (Santa Catalina state) and Vista Alegre (Paraná State), is one of very few impact structures on Earth formed in basaltic rocks.
In this work, a probabilistic framework for identification of traffic loads on concrete Bridge structures is presented using data from a FE structural model in combination with a finite volume approach for traffic load modelling. The identification approach uses Bayesian Inference to identify traffic loads from measured sensor data from travelling load experiments performed at BAM. The work focuses on the load identification part of the Framework utilizing global structural response measurements only. The obtained information on traffic loads can be forwarded to further analysis such as fatigue and structure state estimation or model updating.
Foreword
(2018)
The subject of this Special Issue is the fracture mechanics-based determination of the fatigue strength of weldments. Except for one, all papers were written in closer or wider relation to a methodology developed within the framework of the German Project cluster IBESS. Some of them provide background or supplementary information needed in that context but which is also relevant in a wider frame of research activities. The acronym IBESS stands for the topic of this Special Issue (in German: „Integrale Methode zu Bruchmechanischen Ermittlung der Schwingfestigkeit von Schweißverbindungen). Eight partners were involved. The cluster was cooperatively founded by the German Research Foundation (Deutsche Forschungsgemeinschaft) and by the German AiF Network (Arbeitsgemeinschaft industrieller Forschungsvereinigungen) for industrial research.
A continuum damage model for concrete is developed with a focus on fatigue under compressive stresses. This includes the possibility to model stress redistributions and capture size effects. In contrast to cycle based approaches, where damage is accumulated based on the number of full stress cycles, a strain based approach is developed that can capture cyclic degradation under variable loading cycles including different amplitudes and loading frequencies. The model is designed to represent failure under static loading as a particular case of fatigue failure after a single loading cycle. As a consequence, most of the material parameters can be deduced from statictests. Only a limit set of additional constitutive parameters is required to accurately describe the evolution under fatigue loading. Another advantage of the proposed model is the possibility to directly incorporate other multi-physics effects such as creep and shrinkage or thermal loading on the constitutive level. A multiscale approach in time is presented to enable structural computations of fatigue failure with a reduced computational effort. The damage rate within the short time scale corresponding to a single cycle is computed based on a Fourier based approach. This evolution equation is then solved on the long time scale using different implicit and explicit time integration schemes. Their performance and some limitations for specific loading regimes is discussed.
Lifetime aspects including fatigue failure of concrete structures were traditionally only of minor importance. Because of the growing interest in maxing out the capacities of concrete, its fatigue failure under compression has become an issue. A variety of interacting phenomena such as e.g. loss of prestress, degradation due to chemical reactions or creep and shrinkage influence the fatigue resistance. Failure due to cyclic loads is generally not instantaneous, but characterized by a steady damage accumulation. Therefore, a reliable numerical model to predict the performance of concrete over its lifetime is required, which accurately captures order effects and full three-dimensional stress states.
Many constitutive models for concrete are currently available, which are applicable for specific loading regimes, different time scales and different resolution scales.
However, a key limitation of those models is that they generally do not address issues related to fatigue on a structural level. Very few models can be found in the literature that reproduce deterioration of concrete under repeated loading-unloading cycles. This is due to the computational effort necessary to explicitly resolve every cycle which exceeds the currently available computational resources. The limitation can only be overcome by the application of multiscale methods in time.
The objective of the paper is the development of numerical methods for the simulation of concrete under fatigue loading using temporal multiscale methods.
First, a continuum damage model for concrete is developed with a focus on fatigue under compressive stresses [1]. This includes the possibility to model stress redistributions and capture size effects. In contrast to cycle based approaches, where damage is accumulated based on the number of full stress cycles, a strain based approach is developed that can capture cyclic degradation under variable loading cycles including different amplitudes and loading frequencies. The model is designed to represent failure under static loading as a particular case of fatigue failure after a single loading cycle. As a consequence, most of the material parameters can be deduced from static tests. Only a limit set of additional constitutive parameters is required to accurately describe the evolution under fatigue loading. Another advantage of the proposed model is the possibility to directly incorporate other multi-physics effects such as creep and shrinkage or thermal loading on the constitutive level.
Second, a multiscale approach in time is presented to enable structural computations of fatigue failure with a reduced computational effort. The damage rate within the short time scale corresponding to a single cycle is computed based on a Fourier based approach [2]. This evolution equation is then solved on the long time scale using different implicit and explicit time integration schemes. Their performance and some limitations for specific loading regimes is discussed.
Finally, the developed methods will be validated and compared to experimental data.
[1] Vitaliy Kindrachuk, Marc Thiele, Jörg F. Unger. Constitutive modeling of creep-fatigue interaction for normal strength concrete under compression, International Journal of Fatigue, 78:81-94, 2015
[2] Vitaliy Kindrachuk, Jörg F. Unger. A Fourier transformation-based temporal integration scheme for viscoplastic solids subjected to fatigue deterioration, International Journal of Fatigue, 100:215-228, 2017
The stabilization of crystal phases and nanostructured morphologies is an essential topic in application-driven design of mesoporous materials. Many applications, e.g. catalysis, require high temperature and humidity. Typical metal oxides transform under such conditions from a metastable, low crystal-line material into a thermodynamically more favorable form, i.e. from ferrihy-drite into hematite in the case of iron oxide. The harsh conditions induce also
a growth of the crystallites constituting pore walls, which results in sintering and finally collapse of the porous network. Herein, a new method to stabi-lize mesoporous templated metal oxides against sintering and pore collapse is reported. The method employs atomic layer deposition (ALD) to coat the internal mesopore surface with thin layers of either alumina or silica. The authors demonstrate that silica exerts a very strong influence: It shifts hematite formation from 400 to 600 °C and sintering of hematite from 600 to 900 °C.
Differences between the stabilization via alumina and silica are rationalized by a different interaction strength between the ALD material and the ferrihydrite film.
The presented approach allows to stabilize mesoporous thin films that require a high crystallization temperature, with submonolayer quantity of an ALD material, and to apply mesoporous materials for high temperature applications.
Geosynthetics are widely used in hydraulic engineering and within coastal protection constructions at the Baltic Sea shore, such as walls, promenades, and gabions walls. Storms influence leads to deformation of some of the protection structures and cause the release of geotextiles onto the beach. Fragments of geotextile migrate along the shore, experiencing additional degradation and destruction down to macro-, meso-, and micro-particles. During October 2017 - March 2018, the Baltic Sea shore along the Sambia Peninsula (Kaliningrad Oblast of the Russian Federation) was monitored to establish the contamination of sandy beaches by geotextiles that had degraded. Several local sources of pollution of beaches by geosynthetic materials were established.
The salinization and contamination of metal surfaces by chloride-containing aerosols is of great importance with regard to corrosion phenomena of damaged coated metal surfaces and stainless steels in the maritime sector and in offshore applications. Detailed questions have to be answered to clarify whether and to what extent salinization of the surface has an influence on the adhesion and durability of coatings in repairing applications and on pitting occurrence on stainless steels under atmospheric conditions. The questions arise which degree of salinization is reached after which period of time and how a defined and reproducible salinization can be simulated in the laboratory for further systematic investigations. The article is dedicated to these questions. Results of a field trial on the Island of Heligoland are presented and a simple procedure for a defined loading of metal surfaces with chlorides at a laboratory scale using a design of experiments (DoE) approach is introduced.
Structural design and application have always been linked to the compressive strength of concrete as the main relevant criterion. This was justifiable in the past, where concrete consisted of water, ordinary Portland cement and aggregates, but this concept is no longer relevant for modern and more sustainable cement and concrete.
Despite these new developments, existing standards, guidelines and academic curricula have not been much updated and are still used worldwide. There is a need to change this situation by proper education of the users.
This overview describes the challenges that arise at a user Level from the higher complexity of modern concrete, and defines needs and requirements for enhanced applicability of sustainable concrete concepts.
Furthermore, recommendations are given on how better concrete practice can be communicated to all the involved parties, from civil and design engineers to constructors and site-appliers on the construction site.
Many ambient desorption/ionization mass spectrometry (ADI-MS) techniques rely critically on thermal desorption. Meanwhile, the analyte classes that are successfully studied by any particular ADI-MS methods are strongly dependent on the type of ionization source. Generally, spraybased ionization sources favor polar analytes, whereas plasmabased sources can be used for more hydrophobic analytes and are more suitable for molecules with small molar masses. In the present work, classic atmospheric-pressure chemical ionization (APCI) is used. To provide improved desorption performance for APCI, a surface acoustic wave nebulization (SAWN) device was implemented to convert liquid analytes into fine airborne particles. Compared to conventional SAWN that is used solely as an ionization source for liquid samples, the coupling of SAWN and APCI significantly improves ion signal by up to 4 orders of magnitude, reaching comparable ion abundances to those of electrospray ionization (ESI). Additionally, this coupling also extends the applicable mass range of an APCI source, conventionally known for the ionization of small molecules <500 Da. Herein, we discuss cursory evidence of this applicability to a variety of analytes including both polar and nonpolar small molecules and novel peptides that mimic biomolecules upward of 1000 Da. Observed species are similar to ESI-derived ions including doubly charged analyte ions despite presumably different charging mechanisms. SAWN−APCI coupling may thus involve more nuanced ionization pathways in comparison to other ADI approaches.
Raman microspectra combine information on chemical composition of plant tissues with spatial information. The contributions from the building blocks of the cell walls in the Raman spectra of plant tissues can vary in the microscopic sub-structures of the tissue. Here, we discuss the analysis of 55 Raman maps of root, stem, and leaf tissues of Cucumis sativus, using different spectral contributions from cellulose and lignin in both univariate and multivariate imaging methods. Imaging based on hierarchical cluster analysis (HCA) and principal component analysis (PCA) indicates different substructures in the xylem cell walls of the different tissues. Using specific signals from the cell wall spectra, analysis of the whole set of different tissue sections based on the Raman images reveals differences in xylem tissue morphology. Due to the specifics of excitation of the Raman spectra in the visible wavelength range (532 nm), which is, e.g., in resonance with carotenoid species, effects of photobleaching and the possibility of exploiting depletion difference spectra for molecular characterization in Raman imaging of plants are discussed. The reported results provide both, specific information on the molecular composition of cucumber tissue Raman spectra, and general directions for future imaging studies in plant tissues.
Uptake and molecular impact of aluminum-containing nanomaterials on human intestinal caco-2 cells
(2018)
Aluminum (Al) is one of the most common elements in the earth crust and increasingly used in food, consumer products and packaging. Its hazard potential for humans is still not completely understood. Besides the metallic form, Al also exists as mineral, including the insoluble oxide, and in soluble ionic forms. Representatives of these three species, namely a metallic and an oxidic species of Al-containing nanoparticles and soluble aluminum chloride, were applied to human intestinal cell lines as models for the intestinal barrier. We characterized physicochemical particle parameters, protein corona composition, ion release and cellular uptake. Different in vitro assays were performed to determine potential effects and molecular modes of Action related to the individual chemical species. For a deeper insight into signaling processes, microarray transcriptome analyses followed by bioinformatic data analysis were employed. The particulate Al species showed different solubility in biological media. Metallic Al nanoparticles released more ions than Al2O3 nanoparticles, while AlCl3 showed a mixture of dissolved and agglomerated particulate entities in biological media. The protein corona composition differed between both nanoparticle species. Cellular uptake, investigated in transwell experiments, occurred predominantly in particulate form, whereas ionic Al was not taken up by intestinal cell lines. Transcellular transport was not observed. None of the Al species showed cytotoxic effects up to 200 mg Al/mL. The transcriptome analysis indicated mainly effects on oxidative stress pathways, xenobiotic metabolism and metal homeostasis. We have shown for the first time that intestinal cellular uptake of Al occurs preferably in the particle form, while toxicological effects appear to be ion-related.
This paper presents a probabilistic methodology based on the thermo-mechanical finite elements analysis to investigate the impact of the variability of the thermal properties of the concrete in the fire safety of structures. This is meant to evaluate if characteristic values or safety factors for the conductivity and specific heat are required during the semi-probabilistic structural fire safety assessment. To illustrate the use of the proposed methodology, this work includes a case-study with a tunnel lining which considers the uncertainties related to the thermal and mechanical properties of the concrete, the soil load, and the temperatures described by the standard temperature-time curve. Two failure criteria are considered: one was the maximum temperature of 300 °C at the reinforcement and the other based on the temperature-dependent strength as provided in the Eurocode EN 1992-1-2. Several finite element analyses are performed. The design of experiments is executed by a Correlation Latin Hypercube Sampling. The calculated probability of failure has different values depending on the adopted failure criteria. A sensitivity analysis using the Spearman's rank correlation coefficient was carried out and demonstrates that the uncertainty related to the specific heat has the greatest impact on the results.
Packages for the transport of spent nuclear fuel shall meet the International Atomic Energy Agency regulations to ensure safety under different transport conditions. The physical state of spent fuel and the fuel rod cladding as well as the geometric configuration of fuel assemblies are important inputs for the evaluation of package capabilities under these conditions. In this paper, the mechanical behavior of high burn-up spent fuel assemblies (> approx. 50 GWd/tHM, value averaged over the fuel assembly) under transport conditions is analyzed with regard to the assumptions which are used in the Containment and criticality safety analysis. In view of the complexity of the interactions between the fuel rods as well as between the fuel assemblies, basket, and cask containment, the exact mechanical analysis of such phenomena is nearly impossible. Additionally, the gaps in information concerning the material properties of cladding and pellet behavior, especially for the high burn-up fuel, make the analysis more complicated. Considerations and knowledge gaps for the transport after extended interim storage are issues of growing interest. In this context, practical approaches are discussed based on the experience of BAM within the safety assessment of packages approved for transport of spent nuclear fuel.
Investigation on Wall Thickness Ranges Using Digital Radiography for Tangential Projection Technique
(2018)
X-ray testing is based on the attenuation of X-rays when passing through matter. Image detectors acquire the X-ray information which is defined by the local penetrated wall thickness of the tested sample. By X-ray absorption in the detector and following read-out and digitization steps a digital image is generated. As detectors a radiographic film and film digitization, a storage phosphor imaging plate and a special Laser scanner (Computer Radiography - CR) or a digital detector array (DDA) can be used. The digital image in the computer can then be further analyzed using many types of image processing. In the presented work the automated evaluation of wall thickness profiles are investigated using a test steel pipe with 9 different wall thicknesses and various X-ray voltages and different filter materials at the tube port and intermediate between object and detector. In this way the influence of different radiation qualities on the accuracy of the automated wall thickness evaluation depending on the penetrated wall thickness of the steel pipe was investigated.
The use of glass-fiber reinforced plastic (GRP) can reduce the weight of tanks significantly. By replacing steel with GRP in tanks for gases (propane, etc.) a weight reduction of up to 50 % was reached. In this project not only the material should be optimized, but also the design. Previous tanks consist of a double-walled structure with an insulation layer between the two shells (e.g. vacuum). Goal of this project is to realize a single-walled construction of GRP with an insulation layer on the outside.
To determine the temperature dependent material values, two different experiments are performed: In the first experiment, temperature dependent material properties of liquid nitrogen found in literature research are validated in a simple setup. The level of liquid nitrogen in a small jar is measured over the experiment time. Numerical simulation shows the change of nitrogen level with sufficient precision. In the second experiment, a liquid nitrogen is applied on one side of a GRP plate. Temperature is measured with thermocouples on top and bottom of the GRP plate, as well as in the middle of the plate. By use of numerical simulation, temperature dependent thermal conductivity is determined.
In the third experiment, a test stand is designed to examine different insulation materials. In this test stand, the insulation material can easily be changed. A numerical simulation, in which the determined material data is used, is performed as well for this test stand.
The experiments show, that GRP can be used in cryogenic environments. Multiphase simulations are a suitable tool to describe the energy absorption of thermal energy due to thermal phase change. Results on different insulation materials will follow.
We describe a lattice-based crystallographic approximation for the analysis of distorted crystal structures via Electron Backscatter Diffraction (EBSD) in the scanning electron microscope. EBSD patterns are closely linked to local lattice parameter ratios via Kikuchi bands that indicate geometrical lattice plane projections. Based on the transformation properties of points and lines in the real projective plane, we can obtain continuous estimations of the local lattice distortion based on projectively transformed Kikuchi diffraction simulations for a reference structure. By quantitative image matching to a projective transformation model of the lattice distortion in the full solid angle of possible scattering directions, we enforce a crystallographically consistent approximation in the fitting procedure of distorted simulations to the experimentally observed diffraction patterns. As an application example, we map the locally varying tetragonality in martensite grains of steel.
Test methods for efficacy assessment of antimicrobial coatings are not modelled on a hospital environment, and instead use high humidity (>90%) high temperature (37 ◦C), and no airflow. Therefore, an inoculum will not dry, resulting in an antimicrobial surface exhibiting prolonged antimicrobial activity, as moisture is critical to activity. Liquids will dry quicker in a hospital ward, resulting in a reduced antimicrobial efficacy compared to the existing test, rendering the test results artificially favourable to the antimicrobial claim of the product. This study aimed to assess how hospital room environmental conditions can affect the drying time of an inoculum, and to use this data to inform test parameters for antimicrobial efficacy testing based on the hospital ward. The drying time of different droplet sizes, in a range of environmental conditions likely found in a hospital ward, were recorded (n = 630), and used to create a model to inform users of the experimental conditions required to provide a drying time similar to what can be expected in the hospital
ward. Drying time data demonstrated significant (p < 0.05) variance when humidity, temperature, and airflow were assessed. A mathematical model was created to select environmental conditions for in vitro antimicrobial efficacy testing. Drying time in different environmental conditions demonstrates that experimental set-ups affect the amount of time an inoculum stays wet, which in turn may affect the efficacy of an antimicrobial surface. This should be an important consideration for hospitals and other potential users, whilst future tests predict efficacy in the intended end-use environment.
Increased speed, heavier loads, altered material and modern drive systems result in an increasing number of rail flaws. The appearance of these flaws also changes continually due to the rapid change in damage mechanisms of modern rolling stock. Hence, interpretation has become difficult when evaluating non-destructive rail testing results. Due to the changed interplay between detection methods and flaws, the recorded signals may result in unclassified types of rail flaws. Methods for automatic rail inspection (according to defect detection and classification) undergo continual development. Signal processing is a key technology to master the challenge of classification and maintain resolution and detection quality, independent of operation speed. The basic ideas of signal processing, based on the Glassy-Rail-Diagram for classification purposes, are presented herein. Examples for the detection of damages caused by rolling contact fatigue also are given, and synergetic effects of combined evaluation of diverse inspection methods are shown.
With the recent rise in the demand for additive manufacturing (AM), the need for reliable simulation tools to support experimental efforts grows steadily. Computational welding mechanics approaches can simulate the AM processes but are generally not validated for AM-specific effects originating from multiple heating and cooling cycles. To increase confidence in the outcomes and to use numerical simulation reliably, the result quality Needs to be validated against experiments for in-situ and post-process cases. In this article, a validation is demonstrated
for a structural thermomechanical simulation model on an arbitrarily curved Directed Energy Deposition (DED)part: at first, the validity of the heat input is ensured and subsequently, the model’s predictive quality for in-situ
deformation and the bulging behaviour is investigated. For the in-situ deformations, 3D-Digital Image Correlation measurements are conducted that quantify periodic expansion and shrinkage as they occur. The results show a strong dependency of the local stiffness of the surrounding geometry. The numerical Simulation model is set up in accordance with the experiment and can reproduce the measured 3-dimensional in-situ displacements. Furthermore, the deformations due to removal from the substrate are quantified via 3D-scanning, exhibiting considerable distortions due to stress relaxation. Finally, the prediction of the deformed shape is discussed in regards to bulging simulation: to improve the accuracy of the calculated final shape, a novel Extension of the model relying on the modified stiffness of inactive upper layers is proposed and the experimentally observed bulging could be reproduced in the finite element model.
We investigated the growth of β-phase NaYF4:Yb3+,Er3+ upconversion nanoparticles synthesized by the thermal decomposition method using a combination of in situ and offline analytical methods for determining the application-relevant optical properties, size, crystal phase, and chemical composition. This included in situ steady state luminescence in combination with offline time-resolved luminescence spectroscopy as well as small-angle X-ray scattering (SAXS) transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), and inductively coupled Plasma optical emission spectrometry (ICP-OES). For assessing the suitability of our optical monitoring approach, the in situ-collected spectroscopic data, which reveal the luminescence evolution during nanocrystal synthesis, were compared to measurements done after cooling of the reaction mixture of the as-synthesized particles. The excellent correlation of the in situ and time-resolved upconversion luminescence with the nanoparticle sizes determined during the course of the reaction provides important insights into the various stages of nanoparticle growth. This study highlights the capability of in situ luminescence monitoring to control the efficiency of UCNP synthesis, particularly the reaction times at elevated temperatures and the particle quality in terms of size, shape, and crystal structure, as well as luminescence lifetime and upconversion quantum yield.
Territories of rock-inhabiting fungi: Survival on and alteration of solid air-exposed surfaces
(2018)
Subaerial biofilms that are omnipresent at the interface between all solid substrates and the atmosphere are composed of a unique and widespread group of ascomycetes called rock-inhabiting fungi or microcolonial fungi (MCF), typically in communities with other microorganisms. While subaerial biofilms in toto have important roles in mineral weathering and biodeterioration of materials, methodological approaches to subaerial biofilm communities are diverse and frequently focussed on MCF. Here, we review the historical development of the research methods applied in the field and consider perspectives to increase our understanding of the biofilm-induced changes of solid substrate surfaces.
The fluorescence lifetime is a key property of fluorophores that can be utilized for microenvironment probing, analyte sensing, and multiplexing as well as barcoding applications. For the rational design of lifetime probes and barcodes, theoretical methods have been developed to enable the ab initio prediction of this parameter, which depends strongly on interactions with solvent molecules and other chemical species in the emitters' immediate environment. In this work, we investigate how a conductor-like screening model (COSMO) can account for variations in fluorescence lifetimes that are caused by such fluorophore−solvent interactions. Therefore, we calculate vibrationally broadened fluorescence spectra using the nuclear ensemble method to obtain distorted molecular geometries to sample the electronic transitions with time-dependent density functional theory (TDDFT). The influence of the solvent on fluorescence lifetimes is accounted for with COSMO. For example, for 4-hydroxythiazole fluorophore containing different heteroatoms and acidic and basic moieties in aprotic and protic solvents of varying polarity, this approach was compared to experimentally determined lifetimes in the same solvents. Our results demonstrate a good correlation between theoretically predicted and experimentally measured fluorescence lifetimes except for the polar solvents Ethanol and acetonitrile that can specifically interact with the heteroatoms and the carboxylic acid of the thiazole derivative.
A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12–43 nm is presented utilizing steady-state and time-resolved fluorometry.
Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by highenergy O–H and C–H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated Population pathways of the 4F9/2 energy level of Er3+ were examined. Our results Highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under “strongly quenched” conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the 4F9/2 energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels.
Producing active polymer optical fibers (POFs) is a key step towards new applications such as fluorescent fiber solar concentrators (FFSCs), sensors, contactless coupling devices, or fiber integrated light sources and lasers. Therefore, integration of fluorescent nanoparticles into the polymer matrix is necessary and becomes accessible via in situ polymerization. For optical applications, the polymer has to fulfill various requirements such as chemical and physical stability, optical transparency in the application-relevant spectral region as well as a good synthetic accessibility. A common material for these is poly(methyl methacrylate) (PMMA). The beta-phase NaYF4 : Yb3+, Er3+ upconversion nanoparticles (UCNP) were synthesized from the rare earth salts via thermal decomposition method in high-boiling point solvent 1-octadecene and capping agent oleic acid. Current results show hazy samples of the polymer with integrated nanoparticles made from monomer solution of methyl methacrylate. However, further optical tuning such as increasing the transparency of the bulk samples by changing the monomer solution to non-polar n-butyl methacrylate (nButMA) or cyclohexyl methacrylate (CHMA) or further optimization of the UCNP shell could lead to more suitable polymer bulk samples.
Optical and thermal analysis of PVB encapsulant polymer functionalized with luminescent organic dyes
(2018)
This work focused on the technology of luminescent down shift (LDS), with a primary aim to identify and investigate a methodology to introduce the luminescent organic dye into PVB polymer encapsulant as emergent material for photovoltaic application. For this goal, we propose to study the feasibility to implement the LDS functionality and to identify suitability of available luminescent to be incorporated into the host polymer encapsulant material. The first step to this direction was through a comprehensive optical study of Violet 570 (V) organic dye in ethanol solvent. The methodology and experimental conditions such as laboratory polymer preparation and luminescence dye concentration were presented. Also, the emergent polymer encapsulant sheets were characterized by using optical and thermal analysis techniques. The absorption spectrum of the prepared PVB material shifts towards longer wavelengths, with increasing organic dye concentration.
The design of anion-sensitive probes with sufficient sensitivity and selectivity is a demanding task in analytical sciences and chemical sensor technology. The reversible binding of Anions to lanthanide centers is a possible approach for the development of molecular anion sensors, as reversibility is a prerequisite for continuous sensing and monitoring of enzymatic reactions. Some anion species lead to a strong increase of luminescence intensities and lifetimes by the replacement of luminescence quenching water molecules, though the selectivity of the luminescence response is still a major problem. We synthesized a series of positively charged pyridyl-based multidentate europium complexes (five-, four- and three dentate) including sensitizing chromophores and studied their luminescence intensity and lifetime responses to different polyphosphates, pyrophosphate, phosphate anions, and carboxyanions.
The results revealed that the number and symmetry of the binding sites have a significant impact on the response. The five-dentate complex was used for the real-time monitoring of the activity of the ATP hydrolyzing enzyme apyrase.
Hepcidin-25 concentrations measured by various methods differ considerably, complicating interpretation. Here, a previously identified plasma-based candidate secondary reference material (csRM) was modified into a serum-based two-leveled sRM. We validated its functionality to increase the equivalence between methods for international standardization. We applied technical procedures developed by the International Consortium for Harmonization of Clinical Laboratory Results. The sRM, consisting of lyophilized serum with cryolyoprotectant, appeared commutable among nine different measurement procedures using 16 native human serum samples in a first round robin (RR1). Harmonization potential of the sRM was simulated in RR1 and evaluated in practice in RR2 among 11 measurement procedures using three native human plasma samples. Comprehensive purity analysis of a candidate primary RM (cpRM) was performed by state-of-the-art procedures. The sRM was value assigned with an isotope dilution mass spectrometry-based candidate reference method calibrated using the certified pRM. The inter-assay CV without harmonization was 42.1% and 52.8% in RR1 and RR2, respectively. In RR1, simulation of harmonization with sRM resulted in an inter-assay CV of 11.0%, whereas in RR2 calibration with the material resulted in an inter-assay CV of 19.1%. Both the sRM and pRM passed international homogeneity criteria and showed long-term stability. We assigned values to the low (0.95 ± 0.11 nmol/L) and middle concentration (3.75 ± 0.17 nmol/L) calibrators of the sRM. Standardization of hepcidin is possible with our sRM, which value is assigned by a pRM. We propose the implementation of this material as an international calibrator for hepcidin-25.
Microstructure characterisation of advanced materials via 2D and 3D X-ray refraction techniques
(2018)
3D imaging techniques have an enormous potential to understand the microstructure, its evolution, and its link to mechanical, thermal, and transport properties. In this conference paper we report the use of a powerful, yet not so wide-spread, set of X-ray techniques based on refraction effects. X-ray refraction allows determining internal specific surface (surface per unit volume) in a non-destructive fashion, position and orientation sensitive, and with a nanometric detectability. We demonstrate showcases of ceramics and composite materials, where microstructural parameters could be achieved in a way unrivalled even by high-resolution techniques such as electron microscopy or computed tomography. We present in situ analysis of the damage evolution in an Al/Al2O3 metal matrix composite during tensile load and the identification of void formation (different kinds of defects, particularly unsintered powder hidden in pores, and small inhomogeneity’s like cracks) in Ti64 parts produced by selective laser melting using synchrotron X-ray refraction radiography and tomography.
Invited for this month’s cover picture is the group of Dr. Knut Rurack at the Department of Analytical Chemistry; Reference Materials at the Bundesanstalt fuer Materialforschung und -pruefung (BAM) in Berlin (Germany). The cover picture shows how differences in color and fluorescence on a test strip can be easily read out with a mobile device. Two reference spots Frame the sensitive spot that indicates the presence of trace amounts of HgII below the threshold in a natural water sample. This dipstick contains a hybrid material that combines boron-dipyrromethene (BODIPY) probes sterically loaded into specifically tailored mesoporous silica particles, allowing for ultrasensitive HgII detection through enhanced fluorescence in a few seconds. The applicability in real water samples and fish extracts are also studied.
The age hardening response of a high-purity Al–4Cu–1Li–0.25Mn alloy (wt. %) during isothermal aging without and with an applied external load was investigated. Plate shaped nanometer size T1 (Al2CuLi) and θ′ (Al2Cu) hardening phases were formed. The precipitates were analyzed with respect to the development of their structure, size, number density, volume fraction and associated transformation strains by conducting transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) studies in combination with geometrical Phase analysis (GPA). Special attention was paid to the thickening of T1 phase. Two elementary types of single-layer T1 precipitate, one with a Li-rich (Type 1) and another with an Al-rich (Defect Type 1) central layer, were identified. The results show that the Defect Type 1 structure can act as a precursor for the Type 1 structure. The thickening of T1 precipitates occurs by alternative stacking of These two elementary structures. The thickening mechanism was analyzed based on the magnitude of strain associated with the precipitation transformation normal to its habit plane. Long-term aging and aging under load resulted in thicker and structurally defected T1 precipitates. Several types of defected precipitates were characterized and discussed. For θ′ precipitates, a ledge mechanism of
thickening was observed. Compared to the normal aging, an external load applied to the peak aged state leads to small variations in the average sizes and volume fractions of the precipitates.
Pulse and flash thermography are experimental techniques which are widely used in the field of non-destructive testing for materials characterization and defect detection. We recently showed that it is possible to determine quantitatively the thickness of semitransparent polymeric solids by fitting of results of an analytical model to experimental flash thermography data, for both transmission and reflection configuration. However, depending on the chosen experimental configuration, different effective optical absorption coefficients had to be used in the model to properly fit the respective experimental data, although the material was always the same. Here, we show that this effect can be explained by the wavelength dependency of the absorption coefficient of the sample material if a polychromatic light source, such as a flash lamp, is used. We present an extension of the analytical model to describe the decay of the heating irradiance by two instead of only one effective absorption coefficient, greatly extending its applicability. We show that using this extended model, the experimental results from both measurement configurations and for different sample thicknesses can be fitted by a single set of parameters. Additionally, the deviations between experimental and modeled surface temperatures are reduced compared to a single optimized effective absorption coefficient.
Pores in additive manufactured metal parts occur due to different reasons and affect the part Quality negatively. Few investigations on the origins of porosity are available, especially for Ni-based super alloys. This paper presents a new study to examine the influence of common processing Parameters on the Formation of pores in parts built by laser metal Deposition using Inconel 718 powder. Further, a comparison between the computed tomography (CT) and the Archimedes method was made. The Investigation Shows that CT is able to identify different kinds of pores and to give further Information about their distribution. The identification of some pores as well as their shape can be dependent on the Parameter Setting of the Analysis tool. Due to limited measurement Resolution, CT is not able to identify correctly pores with Diameters smaller than 0.1 mm, which leads to a false decrease on Overall porosity. The applied Archimedes method is unable to differentiate between gas porosity and other Kinds of holes like internal cracks or lack of Fusion, but it delivered a proper value for Overall porosity. The method was able to provide suitable data for the statistical Evaluation with design of Experiments, which revealed significant Parameters ont he Formation of pores in LMD.
The sensitive detection of the mycotoxin citrinin (CIT) utilizing ist fluorescence requires approaches to enhance the emission. In this respect, we studied the complexation of CIT and ochratoxin A (OTA) with Al3+ in methanol using absorption and fluorescence spectroscopy. In this context, an isocratic high performance liquid chromatography (HPLC) method using a polymer column and a fluorescence detector was also developed that enables the separation of the metal ion complexes from the free ligands and non-complexed Al3+. CIT and OTA showed distinct changes in their absorption and fluorescence properties upon Al3+-coordination, and the fluorescence of CIT was considerably enhanced. Analysis of the photometrically assessed titration of CIT and OTA with Al3+ using the Job plot method revealed 1:2 and 1:1 stoichiometries for the Al3+ complexes of CIT (Al:CIT) and OTA (Al:OTA), respectively. In the case of CIT, only one -diketone moiety participates in Al3+ coordination. These findings can be elegantly exploited for signal amplification and provide the base to reduce the limit of detection for CIT quantification by about an order of magnitude, as revealed by HPLC measurements using a fluorescence detector.
The meeting was organised by the European Commission’s Joint Research Centre and held at the JRC-Geel site on 22–23 February 2018. It was a follow-up of a similar meeting held in 2009. The objective of the meeting was to exchange information about ongoing publicly funded reference material (RM) production, identify areas of interest for future specific RMs, including certified reference material (CRM) developments, investigate potential areas of collaboration, and to identify areas which may be of a lower importance in the future for a specific RM producer. The benefit of exchanging such information is to avoid duplication of efforts in RM production, make better use of public funds by potentially matching competencies, and to address problems that are common to publicly funded RM producers.
Grazing incidence SANS and reflectometry combined with simulation of adsorbed microgel particles
(2018)
Adsorbed ethylene glycol based microgel particles on a Silicon surface were studied. Neutron reflectometry (NR) and grazing incidence small-angle neutron scattering (GISANS) were performed to investigate their internal structure. Scattering experiments on soft matter systems such as adsorbed microgels often give only partial Information about the inner structure of the polymer system. In this contribution, we discuss how the detailed inner structure of adsorbed microgel particles can be reconstructed by a combination of the specular Neutron Reflectivity (NR), Grazing Incidence Small Angle Neutron Scattering (GISANS), Atomic Force Microscopy (AFM) and a simulation in the framework of the Distorted Wave Born Approximation.
Micro-concentrator solar cells offer an attractive way to further enhance the efficiency of planar-cell technologies while saving absorber material. Here, two laser-based bottom-up processes for the fabrication of regular arrays of CuInSe2 and Cu(In,Ga)Se2 microabsorber islands are presented, namely one approach based on nucleation and one based on laser-induced forward transfer.
Additionally, a procedure for processing these microabsorbers to functioning micro solar cells connected in parallel is demonstrated. The resulting cells show up to 2.9% efficiency and a significant efficiency enhancement under concentrated Illumination.
Microfluidic electrochemical immunosensor for the trace analysis of cocaine in water and body fluids
(2018)
Quick but accurate testing and on‐the‐spot monitoring of cocaine in oral fluids and urine continues to be an important toxicological issue. In terms of drug testing, a number of devices have been introduced into the market in recent decades, notably for workplace inspection or roadside testing. However, these systems do not always fulfill the requirements in terms of reliability, especially when low cut‐off levels are required. With respect to surface water, the presence of anthropogenic small organic molecules such as prescription and over‐the‐counter pharmaceuticals as well as illicit drugs like cannabinoids, heroin, or cocaine, has become a challenge for scientists to develop new analytical tools for screening and on‐site analysis because many of them serve as markers for anthropogenic input and consumer behavior. Here, a modular approach for the detection of cocaine is presented, integrating an electrochemical enzyme‐linked immunosorbent assay (ELISA) performed on antibody‐grafted magnetic beads in a hybrid microfluidic sensor utilizing flexible tubing, static chip and screen‐printed electrode (SPE) elements for incubation, recognition, and cyclic voltammetry measurements. A linear response of the sensor vs. the logarithm of cocaine concentration was obtained with a limit of detection of 0.15 ng/L. Within an overall assay time of 25 minutes, concentrations down to 1 ng/L could be reliably determined in water, oral fluids, and urine, the system possessing a dynamic working range up to 1 mg/L.
Accident safe packages for the transport of spent nuclear fuel and high-level waste shall fulfil international IAEA safety requirements. Compliance is shown by consecutive mechanical and thermal testing. Additional numerical analysis are usually part of the safety evaluation. For damage protection some package designs are equipped with wood filled impact limiters encapsulated by steel sheets. The safety of these packages is established in compliance with IAEA regulations. Cumulative mechanical and fire tests are conducted to achieve safety standards and to prevent loss of containment. Mechanical reliability is proven by drop tests. Drop testing might cause significant damage of the impact limiter steel sheets and might enable sufficient oxygen supply to the impact limiter during the fire test to ignite the wood filling. The boundary conditions of the fire test are precisely described in the IAEA regulatory. During the test the impact limiter will be subjected to a 30 minute enduring fire phase. Subsequent to the fire phase any burning of the specimen has to extinguish naturally and no artificial cooling is allowed. At BAM a large-scale fire test with a real size impact limiter and a wood volume of about 3m3 was conducted to investigate the burning behaviour of wood filled impact limiters in steel sheet encapsulation. The impact limiter was equipped with extensive temperature monitoring equipment. Until today burning of such impact limiters is not sufficiently considered in transport package design and more investigation is necessary to explore the consequences of the impacting fire. The objective of the large scale test was to find out whether a self-sustaining smouldering or even a flaming fire inside the impact limiter was initiated and what impact on the cask is resulting. The amount of energy, transferred from the impact limiter into the cask is of particular importance for the safety of heavy weight packages. With the intention of heat flux quantification a new approach was made and a test bench was designed.
Tunable microwave devices will play an important role in future wireless systems, in which high-frequency bands, e.g. millimeter waves, will become promising, due to its huge spectrum availability. At such frequency bands, liquid crystals (LCs) exhibit low microwave loss, which is excellent compared with the other tuning elements. In this paper, LC-based microwave components are fabricated by using low temperature co-fired ceramic technology, allowing the integration of the LC into microwave structures. The first component, the Amplitude tuner, controls the signal’s amplitude by using the interference concept, which exhibits a tunable attenuation range from 11 dB to 30 dB at 30 GHz. The second component is a 3-pole tunable bandpass filter, which is realized by using a substrate integrated waveguide topology, enabling a device with comparatively high-quality factors (Q-factors). The measurement results show Q-factors in the range of 68 to 100 for a frequency tuning of 29.4–30.1 GHz, i.e. a tuning range of 700 MHz, accompanied by an insertion loss 2 dB to 4 dB.
The development of fast and cheap highthroughput platforms for the detection of environmental contaminants is of particular importance to understand the human-related impact on the environment. The application of DNA-directed immobilization (DDI) of IgG molecules is
currently limited to the clinical diagnostics scenario, possibly because of the high costs of production of such addressable platforms. We here describe the efficient and specific hybridization of an antibody−oligonucleotide conjugate to a short 12-mer capture probe. The specific antibody used is a monoclonal antibody against caffeine, a stimulant and important anthropogenic marker. With this work, we hope to contribute to broadening the application potential of DDI to environmental markers in order to develop cheaper and more stable high-throughput screening platforms for standard Routine analysis of pollutants in a variety of complex matrices.
Damage detection systems (DDS) provide information of the structural system integrity in contrast to e.g. local information by inspections or non-destructive testing techniques. In this paper, an approach is developed and demonstrated to utilize DDS information to update the structural system reliability and to integrate this information in structural system risk and utility analyses. For this aim, a novel performance modelling of DDS building upon their system characteristics and non-destructive testing reliability is introduced. The DDS performance modelling accounts for a measurement system in combination with a damage detection algorithm attached to a structural system in the reference and damage states and is modelled with the probability of indication accounting for type I and II errors. In this way, the basis for DDS performance comparison and assessment is provided accounting for the dependencies between the damage states in a structure. For updating of the structural system reliability, an approach is developed based on Bayesian updating facilitating the use of DDS information on structural system level and thus for a structural system risk analysis. The structural system risk analysis encompasses the static, dynamic, deterioration, reliability and consequence models, which provide the basis for the system model for calculating the direct risks due to component failure and the indirect risks due to system failure. Two case studies with the developed approach demonstrate a high Value of DDS Information due to risk and expected cost reduction.
The influence of starting materials and synthesis route on the properties and the structure of cementitious sodium aluminosilicate gels is not fully understood, partly due their amorphous nature and the fact that they often contain residual reactants, which can make the results of single-pulse NMR spectroscopy applied to these materials difficult to interpret or ambiguous. To overcome some of these limitations, 29Si{27Al} TRAPDOR NMR as well as 27Al{29Si} and 27Al{1H} REDOR NMR spectroscopy were applied to materials synthesized by the one-part alkali-activation route from three different amorphous silica starting materials, including rice husk ash. The latter led to formation of a fully amorphous sodium aluminosilicate gel (geopolymer), while the materials produced from the other silicas contained amorphous phase and crystalline zeolites. Application of the double-resonance NMR methods allowed to identify hydrous alumina gel domains in the rice husk ash-based material as well as significantly differing amounts of residual silica in the three cured materials. Four-coordinated Al existed not only in the aluminosilicate gel framework but also in a water-rich chemical environment with only a small amount of Si in proximity, likely in the alumina gel or possibly present as extra-framework Al in the aluminosilicate gel. The results demonstrate how the employment of different silica starting materials determines the phase assemblage of one-part alkali-activated materials, which in turn influences their engineering properties such as the resistance against chemically/biologically aggressive media.
: Simvastatin is one of the most widely used active pharmaceutical ingredients for the treatment of hyperlipidemias. Because the compound is employed as a solid in drug formulations, particular attention should be given to the characterization of different polymorphs, their stability domains, and the nature of the phase transitions that relate them. In this work, the phase transitions delimiting the stability domains of three previously reported simvastatin forms were investigated from structural, energetics, and dynamical points of view based on single crystal X-ray diffraction (SCXRD), hot stage microscopy (HSM), and differential scanning calorimetry (DSC) experiments (conventional scans and heat capacity measurements), complemented with molecular dynamics (MD) simulations. Previous assignments of the crystal forms were confirmed by SCXRD: forms I and II were found to be orthorhombic (P212121, Z′/Z = 1/4) and form III was monoclinic (P21, Z′/Z = 2/4). The obtained results further indicated that (i) the transitions between different forms are observed at 235.9 ± 0.1 K (form III → form II) and at 275.2 ± 0.2 K (form II → form I) in DSC runs carried out at 10 K min−1 and close to these values when other types of techniques are used (e.g., HSM). (ii) They are enantiotropic (i.e., there is a transition temperature relating the two phases before fusion at which the stability order is reversed), fast, reversible, with very little hysteresis between heating and cooling modes, and occur under single crystal to single crystal conditions. (iii) A nucleation and growth mechanism seems to be followed since HSM experiments on single crystals evidenced the propagation of an interface, accompanied by a change of birefringence and crystal contraction or expansion (more subtle in the case of form III → form II), when the phase transitions are triggered. (iv) Consistent with the reversible and small hysteresis nature of the phase transitions, the SCXRD results indicated that the molecular packing is very similar in all forms and the main structural differences are associated with conformational changes of the “ester tail”. (v) The MD simulations further suggested that the tail is essentially “frozen” in two conformations below the III → II transition temperature, becomes progressively less hindered throughout the stability domain of form II, and acquires a large conformational freedom above the II → I transition. Finally, the fact that these transitions were found to be fast and reversible suggests that polymorphism is unlikely to be a problem for pharmaceutical formulations employing crystalline simvastatin because, if present, the III and II forms will readily convert to form I at ambient temperature.
A gray cast iron disc, which had been submitted to a heavy duty automotive brake test, was examined with energy filtered transmission electron microscopy. A graphite flake in a convenient angular position showed the shear interaction of graphite layers with the iron matrix in nano-scale resolution. Atomic layers of graphite were wedged into the ferritic bulk, allowing the entrance of oxygen and the subsequent formation of magnetite. The exfoliated few-layer graphene batches deformed heavily when forced into the matrix. When Raman spectra from the disc surface, which show distinctive carbonaceous bands, were compared with Raman spectra from graphite subjected to deformation in a shaker mill with different milling times, it could be seen that the shear stress on the brake surface was much more effective to induce disorder than the milling, where compressive and impact forces had been additionally exerted on the sample. During shear load the high anisotropy of elastic modulus in the graphite crystalline structure and the low adhesion between graphite basal planes allowed the exfoliation of wrinkled few-layer grapheme batches, causing the formation of more defect related Raman bands than the mechanical stress during high-energy milling.
We present naproxen/proline cocrystals discovered when combining enantiopure and racemic naproxen and proline. Using liquid-assisted grinding as the main method to explore the variety of crystal forms in this system, we found 17 cocrystals, of which the structures of only four of them were previously known. The naproxen/proline system exhibited multiple polymorphs of 1 : 1 stoichiometry as well as more rare cocrystals with 1 : 2 and 2 : 3 stoichiometries, two cocrystal hydrates and one cocrystal solvate. In situ ballmilling, used to monitor liquid-assisted grinding reactions, revealed that the solvent dictates the reaction intermediates even if the final reaction product stays the same. Synchrotron X-ray diffraction data collected in situ upon heating allowed us to monitor directly the phase changes upon heating and gave access to pure diffraction patterns of several cocrystals, thus enabling their structure determination from powder X-ray diffraction data; this method also confirmed the formation of a conglomerate in the RS-naproxen/DL-proline system. Proline in cocrystals kept its ability to form charge-assisted head-to-tail
N-H⋯O hydrogen bonds, typical of pure crystalline amino acids, thus increasing the percentage of strong chargeassisted interactions in the structure and consequently providing some of the cocrystals with higher melting points as compared to pure naproxen. The majority of drugs are chiral, and hence, these data are of importance to the pharmaceutical industry as they provide insight into the challenges of chiral cocrystallization.
ABSTRACT: A collection of thioimidazolium salts were synthesized and used as a new class of nonvolatile alkylating agents. Their nonvolatility prevents exposure during use or handling and are thus drastically safer than conventional alkylating agents. We discovered that thioimidazolium Iodide salts cannot release volatile compounds in the solid state, but instead only decompose when molten. Since decomposition proceeds via alkyl iodide elimination, SN2 of iodide on the thioimidazolium cation is constrained in the solid state, and instead can occur only upon melting when ions are mobile. By smart design of these alkylators, the melting point and thus the decomposition temperature of these salts can be increased from 106 to 169 °C and release negligible volatile organic compounds prior to melting. Thioimidazolium-bis(trifluoromethanesulfonyl)imide (TFSI) ionic liquids act as a completely nonvolatile and air-stable TFSI-based alkylating agent and can be used for high-throughput Synthesis of TFSI ionic liquids without solvent. Alkyl groups from methyl to dodecyl can be transferred to a nucleophile and the product purified by sublimation of the thione byproduct, which can then be recycled. We also found that thioimidazolium salts with a dodecyl chain are bactericidal, yet can hydrolyze in water to form benign neutral products, and thus wont accumulate in the environment. These results demonstrate that thioimidazolium salts are a designable platform for the pursuit of safer and more environmentally friendly alkylating and antiseptic agents.
The research focus of this study was set on the corrosion process of condensate as droplets on the surface of carbon steels (X52, X70) martensitic steel UNS S41500, and super austenite UNS N08031 in CO2 atmosphere with impurities at 278 K (to simulate the offshore transportation condition in a buried pipeline). The possibility of dew/droplet formation on the steel surface and wetting behavior of corresponding materials were evaluated by contact angle measurement in dense CO2 at 278 K. To observe the effect of impurities (SO2 and O2) on droplet corrosion process, exposure tests were carried out in the mixed atmosphere with a drop, 1 ‑ 10 µL in volume, of CO2 saturated ultra-pure water on steel surface. Comparable exposure tests were carried out with the same gas mixture and the same volume of water, as vapor, to observe the droplet formation and the corrosion process that follows. Effects of surface roughness on the droplet formation and its corrosion process were further studied and showed no significant role upon long time exposure. The results from droplet experiments were compared to those from the bulk electrolyte for the further recommendation on the quality control of gas stream along with the use of carbon steels as transport pipelines in CCS - Carbon Capture and Storage system.
Estrone (E1), a metabolite of the estrogenic hormones 17β-estradiol (β-E2) and 17α-estradiol (α-E2), is itself a potent estrogen which can have a significant impact on the hormonal balance. Due to ist high potential for adverse effects on human health and aquatic life even at pg/L to ng/L levels, its appearance in water should be monitored. E1 has also been considered a marker substance for the presence of other estrogens. This study presents a newly developed direct competitive enzymelinked immunosorbent assay (ELISA) for quantification of E1 in environmental water samples using new monoclonal antibodies.
The quantification range of the ELISA is 0.15 μg/L to 8.7 μg/L E1, and the limit of detection is around 60 ng/L for not pre-concentrated water samples. A pre-concentration step after careful selection of suitable phases for SPE was developed, too. The influence of organic solvents and natural organic matter on the ELISA was assessed. The high selectivity of the monoclonal antibody was demonstrated by determining the cross-reactivity against 20 structurally related compounds.
For the assessment of matrix effects, a concept (“LC–ELISA”) is thoroughly exploited, i.e., separating complex samples by HPLC into 0.3 min fractions and determination of the apparent E1 concentration. Furthermore, fractions with interferences for nontarget/suspected-target analysis can be assigned. A dilution approach was applied to distinguish between specific interferences (cross-reactants) and non-specific interferences (matrix effects). In the determination of 18 environmental samples, a good agreement of the E1 concentration in the respective fractions was obtained with mean recoveries of 103 % to 132 % comparing ELISA to LC–MS/MS.
Hydrogen is an attractive energy carrier that requires high effort for safe storage. For ensuring safety, they must undergo a challenging approval process. Relevant standards and regulations for composite cylinders used for the transport of hydrogen and for its onboard storage are currently based on deterministic (e.g. ISO 11119-3) or semi-probabilistic (UN GTR No. 13) criteria. This paper analysis the properties of such methods with respect to the evaluation of load cycle strength. Their characteristics are compared with the probabilistic approach of the BAM. Based on Monte-Carlo simulations, the available design range (mean value and scatter of strength criteria) of current concepts was exemplarily estimated. The aspect of small sample sizes is analysed and discussed with respect to the evaluation procedures.
The cyclic J-integral (∆J-integral) is a crack tip parameter of elastic-plastic fracture mechanics which can be used as governing parameter for the description of fatigue crack growth (FCG) in metallic structures. In this contribution, it is applied for modelling FCG in weldments. The ∆J-integral is determined by means of analytical approximation formulas as well as numerical methods. An analytical solution, which takes into account effects of the local ligament plasticity, was derived. This solution is based on well established methods such as R6, BS7910 and SINTAP which were modified for cyclic loading. It incorporates methods for the description of short crack closure behaviour as well as the well known analytical (long) crack closure function of Newman. A specific code was written to evaluate the ∆J-integral numerically in the course of finite element based crack growth simulations. The code was first validated for an infinite plate with centre crack by applying elastic and elastic-plastic material behaviour. Next, the ∆J-integral was calculated for cracks in various butt and cruciform welded joints. The results were compared with the results of the derived analytical approximation formula. A good accordance was achieved between the results.
The paper provides an application of the IBESS approach to the investigation of the influence of various parameters of the global and local weld geometry as well as material defects on the fatigue strength of weldments. For this purpose, the global weld parameters, such as the weld toe radius, the flank angle, the excess weld metal, local secondary notches (in the present study as a measure of surface imperfections) and inclusions sizes have been determined as statistical distributions for different joint types and geometries and two steels of different strengths. The results are in line with literature data and reveal the potential of the theoretical approach to predict the correct trends. The combination with an advanced weld quality system has been demonstrated to be possible.
Welding residual stresses have an impact on the performance of welded structures, on their fracture resistance, their resistance against fatigue crack propagation and, most important, their fatigue strength and fatigue lifetime. The present paper provides an overview on the issue mainly from the point of view of the application of fracture mechanics to the determination of the fatigue strength as the topic of this Special issue. Besides own experimental and theoretical data a comprehensive discussion is provided in that context which includes the definition and interaction of short- and long-range (or reaction) residual stresses, the effect of cyclic mechanical loading and its treatment in fracture and fatigue analyses.
Common fracture mechanics based fatigue considerations are usually limited to the residual lifetime determination of so-called long cracks. The extension of this concept to the total lifetime, as in the S-N curve approach, requires an adequate description of short crack propagation which cannot be based on the Delta K concept, and it must consider the crack closure phenomenon as well as its gradual build-up at the short crack stage. Further, it has to provide a meaningful definition of initial crack dimensions and a solution for the multiple crack problem at stress levels higher than the fatigue limit as it is specific for some configurations such as weldments. This paper aims at a discussion of all these points and offers possible solutions which are illustrated by examples taken from the German IBESS project on fracture mechanics based determination of the fatigue strength of weldments, the results of which will be discussed in more detail in this Special issue.
The so-called cyclic R curve, i.e. the crack size dependence of the fatigue crack propagation threshold in the physically short crack regime, is a key parameter for bringing together fatigue strength and fracture mechanics concepts. Its adequate determination is of paramount importance. However, notwithstanding this relevance, no test guideline is available by now and only very few institutions have spent research effort on cyclic R curves so far. The aim of the present paper is to give an overview on the state-of-the-art. Besides an introduction into the basic principles, the discussion will concentrate on the experimental determination on the one hand and questions of its application on the other hand.
Any fracture mechanics based determination of the fatigue strength of weldments requires different input information such as the local weld geometry and material data of the areas the crack is passing through during its propagation. The latter is so far not a trivial task as the fatigue crack is usually initiated at the weld toe at the transition from the weld metal to the heat affected zone and it subsequently propagates through the different microstructures of the latter to eventually grow into the base material and to cause final fracture. This paper describes how the material input information has gained particularly for heat affected zone material by thermo-mechanically simulated material specimens for two steels of quite different static strength. The data comprise the cyclic stress-strain curve, the crack closure effect-corrected crack growth characteristics, long crack fatigue crack propagation thresholds, the dependency of the parameter on the crack length and monotonic fracture resistance. The substantial experimental effort was necessary for the validation exercises of the IBESS approach, however, within the scope of practical application more easily applicable estimating methods are required. For that purpose the paper provides a number of appropriate proposals in line with its check against the reference data from the elaborate analyses.
The work presents the procedure developed within the German research project IBESS, which allows for the fracture mechanics-based prediction of the fatigue strength of welded joints under constant amplitude loading. Based on the experimental observations of the crucial failure mechanisms, the approach focuses on the short crack propagation, where elastic-plastic fracture mechanics and the build-up of closure effects must be considered as well as the variability of the local geometry at the weld toe and the modelling of multiple crack interaction. Analytical solutions are provided for the approximation of the through-thickness stress profiles at the weld toe and for the determination of the crack driving force in the form of a plasticity-corrected stress intensity factor range ∆K_p. Proposals for the determination of the initial crack size and the crack closure factor are also included.
The approach is validated against a large number of experimental data, which comprises fatigue tests on individual cracks monitored by heat tinting and beach-marking techniques, as well as stress life curves. Three kinds of welded joints, two steels of significant different strengths and three stress ratios are considered. The results show that the procedure provides good estimations of the statistical distribution of the fatigue strength of welded joints both for the finite and infinite life regime. Furthermore, the predictions are compared with available benchmark data for structural steels.
Bulk enstatite chondrites (EC) and their achondritic counterpart, the aubrites, have the lightest measured Si isotope composition of all rocks in the solar system. Some authors proposed that the enrichment of 28Si in EC metal by equilibrium or kinetic isotope fractionation processes in the solar nebula may have led to the negative δ30/28Si of bulk EC. Because EC are also depleted in refractory elements, loss of a heavy Si component with refractory elements might be an alternative explanation. To further constrain their genesis, we analysed for the first time in situ Si-isotope ratios simultaneously with major- and trace element abundances in silicate and metal phases of Sahara 97072 (EH3) and Indarch (EH4).
THz and mid IR spectroscopy of high-molecular PE (HMW) and ultra high-molecular PE (UHMW) reveals modifications of the molecular structure. Characteristic absorption bands are changed if the two materials are exposed by γ-Co60 radiation up to 600 kGy and subsequently stored at an annealing temperature of 398 K until for 729 days.
Microbial activity and functioning in soils are strongly limited by carbon (C) availability, of which a great proportion is released by living roots. Rhizodeposition and especially root exudates stimulate microbial activity and growth, and may shift the stoichiometric balance between C, N, and P. Thereby, exudates heighten microbial nutrient demand and acquisition of N and P from organic matter, leading to an increase in enzyme production. Aim of this study was to determine environmental controls of extracellular enzyme production, and hence on potential enzyme activities (Vmax) and substrate affinities (Km). To determine the controlling factors, we worked on four spatial scales from the microscale (i.e. rhizosphere) through the mesoscale (i.e. soil depth) and landscape scale (relief positions), and finally to the continental scale (1200 km transect within the Coastal Cordillera of Chile). Kinetics of seven hydrolyzing enzymes of the C, N, and P cycles (cellobiohydrolase, β‑glucosidase, β‑xylosidase, β‑N‑acetylglucosaminidase, leucine‑aminopeptidase, tyrosine‑aminopeptidase, and acid phosphatase) were related to soil texture, C and N contents, pH, and soil moisture via redundancy analysis (RDA). Potential activities of C, N, and P acquiring enzymes increased up to 7-times on the continental scale with rising humidity of sites and C and N contents, while substrate affinities simultaneously declined. On the landscape scale, neither Vmax nor Km of any enzyme differed between north and south slopes. From top- to subsoil (down to 120 cm depth) potential activities decreased (strongest of aminopeptidases under humid temperate conditions with up to 90%). Substrate affinities, however, increased with soil depth only for N and P acquiring enzymes. Affinities of cellobiohydrolase and β‑xylosidase, on the contrary, were 1.5- to 3-times higher in top- than in subsoil. Potential activities of N and P acquiring enzymes and β‑glucosidase increased form bulk to roots. Simultaneously, substrate affinities of N and P acquiring enzymes declined, whereas affinities of β‑glucosidase increased. These trends of activities and affinities in the rhizosphere were significant only for acid phosphatase. The RDA displayed a strong relation of potential activities of C and P acquiring enzymes and β‑N‑acetylglucosaminidase to C and N contents in soil as well as to the silt and clay contents. Aminopeptidase activity was mainly dependent on soil moisture and pH. We conclude that substrate availability for microorganisms mainly determined enzyme activity patterns on the continental scale by the humidity gradient. Patterns on the meso- and microscale are primarily controlled by nutrient limitation, which is induced by a shift of the stoichiometric balance due to input of easily available C by roots in the rhizosphere.
In a controlled growth experiment we found that the cyanobacterium Nostoc punctiforme has a bulk cell 26Mg/24Mg ratio (expressed as δ26Mg) that is −0.27‰ lower than the growth solution at a pH of ca. 5.9. This contrasts with a recently published δ26Mg value that was 0.65‰ higher than growth solution for the black fungus Knufia petricola at similar laboratory conditions, interpreted to reflect loss of 24Mg during cell growth. By a mass balance model constrained by δ26Mg in chlorophyll extract we inferred the δ26 Mg value of the main Mg compartments in a cyanobacteria cell: free cytosolic Mg (−2.64‰), chlorophyll (1.85‰), and the nonchlorophyll-bonded Mg compartments like ATP and ribosomes (−0.64‰). The lower δ26Mg found in Nostoc punctiforme would thus result from the absence of significant Mg efflux during cell growth in combination with either (a) discrimination against 26Mg during uptake by desolvation of Mg or transport across protein channels or (b) discrimination against 24Mg in the membrane transporter during efflux. The model predicts the preferential incorporation of 26Mg in cells and plant organs low in Mg and the absence of isotope fractionation in those high in Mg, corroborated by a compilation of Mg isotope ratios from fungi, bacteria, and higher plants.
Hybrid laser-arc welding of thick-walled ferromagnetic steels with electromagnetic weld pool support
(2018)
The hybrid laser-arc welding (HLAW) process provides many advantages over laser welding and arc welding alone, such as high welding speed, gap bridgeability, and deep penetration. The developments in hybrid laser-arc welding technology using modern high-power lasers allow single-pass welding of thick materials. This technology can be used for the heavy metal industries such as shipbuilding, power plant fabrication, and line-pipe manufacturing. The obvious problem for single-pass welding is the growth of the hydrostatic pressure with increasing thickness of materials leading to drop-out of molten metal. This phenomenon is aggravated at slow welding velocities because of increasing weld seam width followed by a decrease of Laplace pressure compensating the hydrostatic pressure. Therefore, weld pool support is necessary by welding of thick materials with slow welding velocities. The innovative electromagnetic weld pool support system is contactless and has been used successfully for laser beam welding of aluminum alloys and austenitic and ferromagnetic steels. The support system is based on generating Lorentz forces within the weld pool. These are produced by an oscillating magnetic field orientated perpendicular to the welding direction. The electromagnetic weld pool support facilitates a decrease in the welding speed without a sagging and drop-out of the melt thus eliminating the limitations of weldable material thickness.
The interaction of hydrogen with various tungsten-inert-gas-welded austenitic stainless steels’ (AUSS) microstructure is studied by means of desorption/absorption analysis and microstructure observations. One of the limitations of welding is created by the presence of hydrogen in the weld, which can shorten the steel’s service life. The local hydrogen concentration, trapping, and its distribution along the welded samples were studied by thermal desorption spectrometry and were supported by X-ray diffraction (XRD) and electronic microstructural observations. Hydrogen content demonstrated a dependence on the welding zone. It was found that hydrogen distribution, and accepted microstructure during welding, played a significant role in the trapping mechanism of 316L AUSS. XRD analysis revealed residual stresses which were caused due to the presence of hydrogen in c-phase. It was shown that the austenite microconstituents inside 316L can have a crucial effect in preventing hydrogen-assisted cracking phenomenon. The effects of AUSS microstructure on hydrogen absorption and desorption behavior are discussed in detail.
Iron nanoparticles (NPs) metabolism is directly associated to human health due to their use as anemia treatment and should be studied in detail in cells. Here we present a speciation strategy for the determination of the metabolic products of iron oxide nanoparticles coated by tartaric and adipic acids in enterocytes-like cell models (Caco-2 and HT-29). Such methodology is based on the use of SDS-modified reversed phase high performance liquid chromatography (HPLC) separation using inductively coupled plasma-mass spectrometry (ICP-MS) as Fe selective detector. Post-column isotope dilution analysis is used as quantification tool by adding Fe-57 as isotopically enriched standard. To assess the separation capability of the method, two different iron nanostructures: iron sucrose nanoparticles -Venofer®- used as model suspension and iron tartrate/adipate-modified nanoparticles, both of about 4 nm (core size) were evaluated. The two nanostructures were injected into the system showing good peak profiles and quantitative elution recoveries (>80%) in both cases. In addition, both nanoparticulate fractions could be based-line separated from ionic iron species, which needed to be complexed with 1mM citrate to elute from the column. Exposed cells up to 0.5mM of iron tartrate/adipate-modified nanoparticles were specifically treated to extract the internalized NPs and the extracts examined using the proposed strategy. The obtained results revealed the presence of three different fractions corresponding to nanoparticle aggregates, dispersed nanoparticles and soluble iron respectively in a single chromatographic run. Quantitative experiments (column recoveries ranging from 60 to 80%) revealed the presence of the majority of the Fe in the nanoparticulated form (>75%) by summing up the dispersed and aggregate particles. Such experiments point out the high uptake and low solubilization rate of the tartrate/adipate NPs making these structures highly suitable as Fe supplements in oral anemia treatments.
This work describes a vibration-based structural health monitoring of a prestressed-concrete box girder bridge on the A100 Highway in Berlin by applying statistical pattern recognition technique to a huge amount of data continuously collected by an integrated monitoring system during the period from 2000 to 2013. Firstly, the general condition and potential damage of the bridge is described. Then, the dynamic properties are extracted from 20 velocity sensors. Environmental variability captured by five thermal transducers and traffic intensity approximately estimated by strain measurements are also reported. Nonlinear influences of temperature on natural frequencies are observed. Subsequently, the measurements during the first year are used to build a baseline health index. The multiple linear regression (MLR) method is used to characterize the nonlinear relationship between natural frequencies and temperatures. The Euclidean distance of the residual errors is calculated to build a statistical health index. Finally, the indices extracted from the following years gradually deviate; which may indicate structural deterioration due to loss of prestress in the prestressed tendons.
In this paper, a contact problem between two bodies, discretized by finite elements, is solved by adding an auxiliary NURBS layer between the bodies. The advantages of a smooth contact formulation in a NURBS approach are combined with simple mesh generation procedures for the bodies discretized with finite elements. Mesh tying conditions are used to couple the NURBS layer with the finite element discretization. The NURBS layer is the master side for contact and mesh tying. Mesh tying is enforced either using pointwise or mortar type approaches. Frictionless 2D and 3D contact problems are considered using small deformations. The contact problem is discretized with the mortar method and a penalty approach is used to enforce the contact constraints. A robust element-based quadrature is applied for mortar tying and contact discretizations, thus avoiding computationally expensive Segmentation.
The adsorption of water in one-dimensional channels in porous aluminophosphate material AlPO4-5 has been studied by a combination of gravimetric Analysis techniques, neutron and X-ray diffraction and Neutron spectroscopy. Molecular structure of AlPO4-5 consists of 12-membered rings of alternating, corner-sharing AlO4 and PO4 tetrahedra connected by oxygen bridges into sheets in the (a, b) plane. The sheets are connected by oxygen bridges along the c crystal axis and form onedimensional channels of which the largest, formed by the 12-membered rings, have a van der Waals Diameter of about 8.3 Å. Gradually increasing the amount of adsorbed water we could follow the evolution of the confined water mobility in a systematic way and identify the molecular mechanism of water adsorption. We focused particularly on the range of low and medium relative pressures up to p/p0=0.32, where a Change from a hydrophobic behavior to a steep, capillary condensation like water intake has been observed. At the Initial adsorption stages water occupies positions close to the pore walls causing the contraction of channels in the (a, b) plane and the prolongation of the channels along c axis in AlPO4-5. With the progressing intake water molecules form chains along the main channels. The cooperative interactions between water molecules lead to the onset of phonon-like cooperative modes and, surprisingly, to the increase of diffusive-like motion, which slow down only in the final adsorption stages when AlPO4-5 channels are completely filled.
Reliability assessment of existing bridge constructions based on results of non-destructive testing
(2018)
The non-destructive testing methods available for civil engineering (NDT-CE) enable the measurements of quantitative parameters, which realistically describe the characteristics of existing buildings. In the past, methods for quality evaluation and concepts for validation expanded into NDT-CE to improve the objectivity of measured data. Thereby, a metrological foundation was developed to collect statistically sound and structurally relevant information about the inner construction of structures without destructive interventions. More recently, the demand for recalculations of structural safety was identified. This paper summarizes a basic research study on structural analyses of bridges in combination with NDT. The aim is to use measurement data of nondestructive testing methods as stochastic quantities in static calculations. Therefore, a methodical interface between the guide to the expression of uncertainty in measurement and probabilistic approximation procedures (e.g. FORM) has been proven to be suitable. The motivation is to relate the scientific approach of the structural analysis with real information coming from existing structures and not with those found in the literature. A case study about the probabilistic bending proof of a reinforced concrete bridge with statistically verified data from ultrasonic measurements shows that the measuring results fulfil the requirements concerning precision, trueness, objectivity and reliability.
The mechanism of action of zirconium permanent modifiers on graphite surfaces was investigated in order to understand its influence on the analytical signal in atomic and molecular absorption spectrometry (AAS/MAS). For this, the molecule formation of CaF was studied, which is used for the indirect analytical determination of fluorine in high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). The kinetics of this reaction was established by monitoring its molecular spectrum at different atomisation temperatures. An Arrhenius plot showed a pseudo-first order reaction with respect to fluorine (n = 1). An intermediate state was isolated, and its structure was elucidated by spectroscopic methods: scanning electron microscopy with energy dispersive X-ray spectroscopy (SEMEDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XANES and EXAFS), and Raman microspectroscopy. We propose here a mechanism, where ZrO2 acts as a heterogeneous catalyst: after a pyrolytic step, an intermediate state of ZrO(OCaF) is activated, and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. No evidence of the formation of zirconium carbide was found. Consequently, as the CaF formation is catalysed by a heterogeneous catalyst, surface modifications with ZrO2 nanoparticles and ZrO xerogels were investigated in order to increase the surface area. Their influence was evaluated in the molecule formation of CaF, CaCl, CaBr, and CaI. Graphite furnace modification with zirconium oxide nanoparticles proves to be the best choice for fluorine analysis with a signal enhancement of more than eleven times with respect a non-coated graphite furnace. However, the influence of zirconium modifications in the analytical signals of Cl, and I is lower than the F signals or even negative in case of the Br. Understanding zirconium modifiers as heterogeneous catalysts offers a new perspective to AAS and MAS, and reveals the potential of surface analytical methods for development of improved permanent modifiers and graphite furnace coatings.
Noninvasive blood glucose assays have been promised for many years and various molecular spectroscopy-based methods of skin are candidates for achieving this goal. Due to the small spectral signatures of the glucose used for direct physical detection, moreover hidden among a largely variable background, broad spectral intervals are usually required to provide the mandatory analytical selectivity, but no such device has so far reached the accuracy that is required for self-monitoring of blood glucose (SMBG). A recently presented device as described in this journal, based on photoplethysmographic fingertip images for measuring glucose in a nonspecific indirect manner, is especially evaluated for providing reliable blood glucose concentration predictions.
The purpose of this study is to shed more light on the transesterification processes in alcohol-initiated and tin(II) 2-ethylhexanoate (SnOct2)-catalyzed polymerizations of lactides at low or moderate temperatures. Ethanol-initiated polymerizations are conducted in concentrated solutions at 80 °C and a strong dependence of even/odd equilibration on the alcohol/Sn ratio. Around or above 120 °C cyclization of poly(l-lactide) via “backbiting” occurs as a third mechanism. However, poly(m-lactide) shows a higher cyclization tendency and yields cyclics even at 100 °C. Combinations of ethanol and certain cyclic dibutyltin(IV) catalysts also yield cyclic oligomers of l-lactide at 80 °C. Reaction conditions allowing for a total suppression of all transesterification reactions are not found, but even-numbered poly(m-lactide)s with a purity >95% are obtained at 70 or 60 °C.
Two-dimensional residual stress mapping of multilayer LTT weld joints using the contour method
(2018)
Low transformation temperature (LTT) weld filler materials offer an attractive alternative to cost intensive postweld treatments as they can mitigate detrimental welding residual stresses during the welding process. Compared to conventional weld filler materials, LTT alloys are characterized by a delayed martensite transformation at low temperatures, which can result in compressive residual stresses in the weld. The high strength of these filler materials makes them potentially applicable to high-strength steels as well as for a large amount of requested repair works in steel structures. The focus of the study is on the confirmation of the LTT idea with regard to the residual stress state for multipass weld lines processed by metal active gas welding. It is demonstrated that the contour method is a well-suited technique for measuring the residual stress in the weld joint as it gives an entire two-dimensional map of the residual stress state in the weld line, heat affected zone (HAZ), and base material. The technique was applied at different LTT alloys with varying chemical compositions. Additionally, the results are compared to residual stress maps that were determined by Neutron diffraction using the Strain Analyzer for Large Scale Engineering Applications, an
instrument referred to as SALSA, at the Institut Laue-Langevin in Grenoble. For all investigated specimens, compressive residual stress distributions were determined in the area of the weld joint and the HAZ. They are balanced by tensile residual stresses in the surrounding base material. However, it is shown that the size of theregion exhibiting compressive residual stresses and the absolute values of the compressive residual stresses depend on the chemical composition of the weld filler material.
Limited data exist on the pharmacokinetic profile of novel direct acting antivirals in kidney transplant recipients. Daclatasvir is primarily eliminated via the biliary route and sofosbuvir via the renal route; here we report the pharmacokinetic profile of combined treatment with these compounds in a prospective study of hepatitis C virus positive kidney transplant recipients (EudraCT: 2014-004551-32). In this study plasma samples of 16 HCV positive kidney transplant recipients receiving daclatasvir and sofosbuvir were collected at 4 time points at day 1, 7, 14, 21, 56, and 84 after start of treatment. Inclusion criteria were stable graft function and an estimated GFR (eGFR) > 30mL/min/1.73m. Daclatasvir, sofosbuvir and GS-331007 (inactive metabolite of sofosbuvir) plasma concentrations were determined using ultra-performance liquid chromatography quadrupole time of flight mass spectrometry. All patients showed a rapid virological response with HCV RNA below the detection limit 21 days after the start of therapy (medium time to viral clearance). No difference of the areas under the concentration-time curve (AUC) of daclatsavir, sofosbuvir and GS-331007 was observed between patients with an eGFR below or ≥ 60mL/min. For GS-331007, no relevant changes of trough levels were observed over time. Mean GS-331007 trough levels were 339.5±174.9 ng/mL in patients with an eGFR ≥ 60mL/min and 404.3±226 ng/mL in patients with an eGFR < 60mL/min at day 7 (p=0.52). At day 84, GS-331007 trough levels were 357.8±200.8 ng/mL and 404.2±70.2 ng/mL in patients with an eGFR ≥ 60 mL/min and in patients with an eGFR < 60 mL/min, respectively (p=0.51). The accumulation ratios of renally eliminated GS-331007 for AUC and Cmax did not significantly differ between the two eGFR groups at day 7. An impaired eGFR (30-60 mL/min) does not lead to a dose accumulation of daclatasvir, sofosbuvir and GS-331007. This study provides the rationale for future studies investigating the pharmacokinetic profile of sofosbuvir based HCV treatment in kidney transplant recipients with an eGFR < 30 mL/min.
The GERG-2008 equation of state is the approved ISO standard (ISO 20765-2) for the calculation of thermophysical properties of natural gas mixtures. The composition of natural gas can vary considerably due to the diversity of origin. Further diversification was generated by adding hydrogen, biogas, or other non-conventional energy gases. In this work, high-precision experimental (p, rho, T) data for two gravimetrically prepared synthetic natural gas mixtures are reported. One mixture resembled a conventional natural gas of 11 components (11 M) with a nominal mixture composition (amount-of-substance fraction) of 0.8845 for methane as the matrix compound with the other compounds being 0.005 for oxygen, 0.04 for nitrogen, 0.015 for carbon dioxide, 0.04 for ethane, 0.01 for propane, 0.002 each for n- and isobutane, and ultimately 0.0005 each for isopentane, n-pentane, and nhexane. The other mixture was a 13-component hydrogen-enriched natural gas with a low calorific value featuring a nominal composition of 0.7885 for methane, 0.03 for hydrogen, 0.005 for helium, 0.12 for nitrogen, 0.04 for carbon dioxide, 0.0075 for ethane, 0.003 for propane, 0.002 each for n- and isobutane, and 0.0005 each for neopentane, isopentane, npentane, and n-hexane. Density measurements were performed in an isothermal operational mode at temperatures between 260 and 350 K and at pressures up to 20 MPa by using a single-sinker densimeter with magnetic suspension coupling. The data were compared with the corresponding densities calculated from both GERG-2008 and AGA8-DC92 equations of state to test their performance on real mixtures. The average absolute Deviation from GERG-2008 (AGA8-DC92) is 0.027% (0.078%) for 11 M and 0.095% (0.062%) for the 13-component H2-enriched mixture, respectively. The corresponding maximum relative Deviation from GERG-2008 (AGA8-DC92) amounts to 0.095% (0.127%) for 11 M and 0.291% (0.193%) for the H2-enriched mixture.
One of the major challenges in chemical synthesis is to trigger and control a specific reaction route leading to a specific final product, while side products are avoided. Methodologies based on resonant processes at the molecular level, for example, photochemistry, offer the possibility of inducing selective reactions. Electrons at energies below the molecular ionization potential (<10 eV) are known to dissociate molecules via resonant processes with higher cross sections and specificity than photons. Here we show that even subexcitation electrons with energies as low as 1 eV produce ethylene and acetylene from dimethyl sulfide in competing reactions. However, the production of ethylene can specifically be targeted by controlling the energy of electrons (∼3 to 4 eV). Finally, pure ethylene is selectively desorbed by heating the substrate from 90 to 105 K. Beyond the synthesis of these versatile hydrocarbons for various industrial applications from a biogenic sulfur compound, our findings demonstrate the feasibility of electron-induced selective chemistry applicable on the nanoscale.
The residual stress distribution in IN718 elongated prisms produced by Selective Laser Melting was studied by means of neutron (bulk) and laboratory X-ray (surface) diffraction.
Two deposition hatch lengths were considered. A horizontal plane near the top surface (perpendicular to the building direction) and a vertical plane near the lateral surface (parallel to the building direction) were investigated. Samples both in as-built (AB) condition and removed (RE) from the base plate were characterized.
While surface stress fields seem constant for AB condition, X-ray diffraction shows stress gradients along the hatch direction in the RE condition. The stress profiles correlate with the distortion maps obtained by tactile probe measurements.
Neutron diffraction shows bulk stress gradients for all principal components along the main sample directions. We correlate the observed stress patterns with the hatch length, i.e. with its effect on temperature gradients and heat flow. The bulk stress gradients partially disappear after removal from the baseplate.
Residual stresses are crucial when assessing the performance of welded components. The present work deals with the possibilities of transferring the real-life boundary conditions of welding, which influence the residual stress, into the laboratory. The possibilities of a test system specifically developed for this purpose with a maximum capacity of 2 MN are shown. Due to the structural design, global process, geometry and material-dependent stresses are induced, which can be simulated and quantified within the system. Additionally, X-ray diffraction can be applied to determine the resulting local residual stress distribution precisely with high spatial resolution. Two examples are presented how the conditions to be found during production are simulated in the laboratory. It is shown how welding residual stresses in high-strength steels are affected by the heat control. It was possible to clarify why elevated working temperatures significantly increase the bending stresses in the welded joint and therefore the tensile residual stresses in the heat affected zone (HAZ). The effect of a heat treatment applied under mechanical stress resulting from welding is demonstrated by the example of a creep resistant steel. Reheat cracking is significantly increased in this case compared to small scale laboratory based tests.
Air‑coupled ferroelectret ultrasonic transducers for nondestructive testing of wood‑based materials
(2018)
Air-coupled ultrasound (ACU) is used in through transmission to detect delamination, rot, and cracks in wood without altering the structure permanently. Novel ferroelectret transducers with a high signal-to-noise ratio enable high-precision structure recognition. Transducers made of cellular polypropylene are quite suitable for ACU testing due to their extremely low Young’s modulus and low density resulting in a favorable acoustic impedance for the transmission of ultrasonic waves between the transducer and air. Thus, structures with great dimensions, with a thickness of up to 300 mm and material densities below 500 kg/m3, can be inspected. Promising results were obtained under laboratory conditions with frequencies ranging from 90 to 200 kHz. The advantage of ACU transducers is that they do not equire contact to the sample; they are accurate and cost-effective. Ultrasonic quality assurance for wood is an important avenue to increase the acceptance of wooden structures and toward sustainability in civil engineering in general.
Commidities and rail damage
(2018)
A roll-plane simplified model, representing the suspended body-cargo of a railway car, was developed to simulate thedynamic response of a railway car while subjectedto lateral acceleration derived from its traveling along curved tracks. The model provides the means to calculate the suspension forces, which are supposed to be transmitted to the bogie´s wheelset. For the analysis of the potential effect of such forces on the railway fatigue life, different performance measures were considered, under different concepts. A family of curves were produced to analyze the effect of the height of the center of gravity of the body-cargo system, on the different performance measures. The resultingdiagramswereused to assess the rail damage potentials offour different railway cars. Results suggest that the height of the center of gravity, associated to the different types of railway cars, nonlinearly and strongly affects the fatigue lifeof the rail, with the double stack car being the moreinfrastructure-aggressive. In this respect, experimental evidence should be provided about such remarkable effects, so as to supportsome operational recommendationsthat shouldbe taken to mitigate these effects, including, for example, the regulation of the traveling speed of some vehicles.
Identifying the fate of agrochemicals is important to understand their potential risk for living organisms. We report here new photodegradation products (PPs) of the fungicide fluopyram. The PPs were produced by irradiating a fluopyram standard in 0.1% acetonitrile aqueous media by a 150-W medium pressure Hg-lamp that emits wavelengths between 200–280 nm. The structural elucidation of PPs was achieved by combining the retention time, isotopic pattern, targeted fragmentation, and accurate mass measurements using liquid chromatography-tandem mass spectrometry (LC-MS/MS) and high resolution-MS (HRMS). In addition to previously known PPs, seven new PPs of fluopyram were identified in this work: mainly dihydroxyl and hydroxylimide fluopyram as well as mono, di, and trihydroxyl lactam. Additionally, two PPs were found to be formed by rearrangement after the loss of H2C=CH2. Hence, the results of the work contribute to extending the current knowledge regarding the photoinduced fate of agrochemicals, and fluopyram in particular.
Relation between crack opening and extent of the damage induced at the steel/mortar interface
(2018)
Cracks are inevitable in reinforced concrete structures and promote the diffusion of aggressive agents towards the reinforcement. In Eurocodes, for some exposure conditions, a threshold not to be exceeded for crack width near the rebar is recommended in order to limit risks of corrosion development and ensure structure durability. On the other hand, several studies show that the steel/mortar interface quality at the intersection with a crack strongly influences corrosion development. The aim of this study was therefore to test whether a relation exists between the extent of mechanical damage at the interface and the corresponding residual crack opening. To this end, specimens were cracked using three point bending test apparatus and the evolution of crack opening was determined on the outer surface and deep within the specimen. It was observed that the crack opening measured on the outer surface of the specimen was very close to that measured at various depths within the specimen at the same height level. In addition, the length of the mechanically damaged interface was determined for each residual crack opening.
It was deduced that cracks induced significant steel/mortar Interface damage independently of the size of their openings. The length of the mechanically damaged interface increased proportionally to the residual crack opening without showing marked variation after a certain crack opening value.
Based on the observed results, it is deduced that defining thresholds on crack openings is logical for esthetic reasons but is not articularly relevant for corrosion risk assessment.
Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site, e.g. heat, pressure, salinity of the aquifer, CO2-partial pressure. Samples of different mild and high alloyed stainless injection-pipe steels partially heat treated: 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 as well as X5CrNiCuNb16-4 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CO2-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Main corrosion products are FeCO3 and FeOOH. Corrosion rates obtained at 100 bar are generally much lower than those measured at ambient pressure. Highest surface corrosion rates are 0.8 mm/year for 42CrMo4 and lowest 0.01 mm/year for X5CrNiCuNb16-4 in the vapour phase at ambient pressure. At 100 bar the highest corrosion rates are 0.01 mm/year for 42CrMo4, X20Cr13 (liquid phase), X46Cr13 and less than 0.01 mm/year for X35CrMo4 and X5CrNiCuNb16-4 after 8000 h of exposure with no regard to atmosphere. Martensitic microstructure offers good corrosion resistance.
Here we demonstrate that by applying exclusively Martian resources a processing route involving suspensions of mineral particles called slurries or slips can be established for manufacturing ceramics on Mars. We developed water-based slurries without the use of additives that had a 51 wt. % solid load resembling commercial porcelain slurries in respect to the particle size distribution and rheological properties. These slurries were used to slip cast discs, rings and vases that were sintered at temperatures between 1000 and 1130 °C using different sintering schedules, the latter were set-up according the results of hot-stage microscopic characterization. The microstructure, porosity and the mechanical properties were characterized by SEM, X-ray Computer tomography and Weibull analysis. Our wet processing of minerals yields ceramics with complex shapes that show similar mechanical properties to porcelain and could serve as a technology for future Mars colonization. The best quality parts with completely vitrificated matrix supporting a few idiomorphic crystals are obtained at 1130 °C with 10 h dwell time with volume and linear shrinkage as much as ~62% and ~17% and a characteristic compressive strength of 51 MPa.
The performance and safety of welded high-strength low-alloyed steel (HSLA) components are substantially affected by the stresses occurring during and after welding fabrication, especially if welding shrinkage and distortion are severely restrained. The surrounding structure of the whole component affects loads in the far-field superimposing with welding stresses in the near-field of the weld. In this study a unique testing facility was used to restrain shrinkage and bending while analyse multiaxial far-field loads (max. 2 MN) during assembly of thick-walled component. A novel approach for the assessment of the in-situ-measured far-field data in combination with the actual weld geometry was elaborated. For the first time, analyses of the global bending moments of restrained welds based on the neutral axis of the actual weld load bearing section were achieved. Hence, far-field measurements offered the possibility to determine critical near-field stresses of the weld crosssections for the entire joining process. This work presents the approach for far-to-near field in-situ determination of stresses in detail for the 2-MN-testing system based on an extensive experimental work on HSLA steel welds, which demonstrates sources and consequences of these high local welding stresses. Thus, it was clarified, why the first weld beads are crucial regarding welding stresses and cold cracking, which is well known, but has never been measured so far. Accompanying analyses using X-ray diffraction (XRD) after welding show effects on local residual stress distributions. These analyses indicated viable prospects for stress reduction during assembly of thick-walled HSLA steel components.
Today, an expanding application of high-strength steels in modern welded constructions can be observed. The economical use of these steel grades largely depends on the strength and reliability of the weldments. Therefore, the special microstructure and mechanical properties of these grades have to be taken into account by keener working ranges regarding the welding parameters.
However, performance and safety of welded components are strongly affected by the stresses occurring during and after welding fabrication locally in the weld seam and globally in the whole component, especially if the shrinkage and distortion due to welding are restrained. Some extensive studies describe the optimization of the welding stresses and the metallurgical effects regarding an adapted welding heat control. Lower working temperatures revealed to be particularly effective to reduce the local and global welding-induced residual stresses of the complete weld significantly. However, decreased interpass temperatures cause concurrently higher stresses during welding fabrication. This work shows strategies to reduce these in-process stresses.
With help of multi-axial welding stress analyses in component-related weld tests, using a special 2-MN-testing facility, differences in stress build-up are described in detail for root welds, filler layers and subsequent cooling to ambient temperature.
In this paper perfluorinated graded-index polymer optical fibers are characterized with respect to the influence of relative humidity changes on spectral transmission absorption and Rayleigh backscattering. The hygroscopic and thermal expansion coefficient of the fiber are determined to be CHE = (7.4 +/- 0.1) 10^-6 %r.h.^-1 and CTE = (22.7 +/- 0.3) 10^-6 K^-1, respectively. The influence of humidity on the Brillouin backscattering power and linewidth are presented for the first time to our knowledge. The Brillouin backscattering power at a pump wavelength of 1319 nm is affected by temperature and humidity. The Brillouin linewidth is observed to be a function of temperature but not of humidity. The strain coefficient of the BFS is determined to be CS = (146.5 +/- 0.9) MHz/% for a wavelength of 1319 nm within a strain range from 0.1 % to 1.5 %. The obtained results demonstrate that the humidity-induced Brillouin frequency shift is predominantly caused by the swelling of the fiber over-cladding that leads to fiber straining.
A facile and convenient approach for the synthesis of core–shell particles via emulsion polymerization is presented. The shell consists of poly(vinylidene fluoride) (PVDF) and the core of poly(methyl methacrylate) (PMMA), poly(glycidyl methacrylate) (PGMA) or poly(methyl acrylate) (PMA). In a first step, a non-fluorinated (meth)acrylate monomer is polymerized in the emulsion to produce poly(meth)acrylate core particles. Secondly, vinylidene fluoride (VDF) is directly added to the reactor and polymerized for shell formation. Small-angle X-ray scattering (SAXS) was employed to characterize the structure of the core–shell particles. Interestingly, the particles’ core contains fluorinated and non-fluorinated polymers, whereas the shell of the particles consists only of PVDF. The resulting particles with a diameter of around 40 nm show a significantly higher PVDF β phase content than the PVDF homopolymer obtained by emulsion polymerization
Time-resolved flow cytometry represents an alternative to commonly applied spectral or intensity multiplexing in bioanalytics. At present, the vast majority of the reports on this topic focuses on phase-domain techniques and specific applications. In this report, we present a flow cytometry platform with time-resolved detection based on a compact setup and straightforward time-Domain measurements utilizing lifetime-encoded beads with lifetimes in the nanosecond range. We provide general assessment of time-domain flow cytometry and discuss the concept of this platform to address achievable resolution limits, data analysis, and requirements on suitable encoding dyes. Experimental data are complemented by numerical calculations on photon count numbers and impact of noise and measurement time on the obtained lifetime values.
Abstract While classically used to visualise the magnetic microstructure of functional materials (e.g., for magnetic applications), in this study, the Bitter technique was applied for the first time to visualise macroscopic deformation gradients in a polycrystalline low-carbon steel. Spherical indentation was chosen to produce a multiaxial elastic–plastic deformation state. After removing the residual imprint, the Bitter technique was applied, and macroscopic contrast differences were captured in optical microscopy. To verify this novel characterisation technique, characteristic “hemispherical” deformation zones evolving during indentation were identified using an analytical model from the field of contact mechanics. In addition, near-surface residual stresses were determined experimentally using synchrotron radiation diffraction. It is established that the magnetic domain distribution contrast provides deformation-related information: regions of different domain wall densities correspond to different “hemispherical” deformation zones (i.e., to hydrostatic core, plastic zone and elastic zone, respectively). Moreover, the transitions between these three zones correlate with characteristic features of the residual stress profiles (sign changes in the radial and local extrema in the hoop stress). These results indicate the potential of magnetic domain distribution imaging: visualising macroscopic deformation gradients in fine-grained ferromagnetic material with a significantly improved spatial resolution as compared to integral, mean value-based measurement methods.
Three fluorescent molecular rotors of 4-dimethylamino-4-nitrostilbene (4-DNS) were investigated for their potential use as viscosity probes to indicate the content of kerosene in diesel/kerosene blends, a wide-spread activity to adulterate fuel. In solvents with low viscosity, the dyes rapidly deactivate via a so-called twisted intramolecular charge transfer state, efficiently quenching the fluorescence. Measurements of diesel/kerosene blends revealed a good linear correlation between the decrease in fluorescence and the increase of the fraction of the less viscous kerosene in diesel/kerosene blends. Immobilization of the hydroxy derivative 4-DNS-OH in cellulose paper yielded test strips that preserve the fluorescent indicator's behavior. Combination of the strips with a reader based on a smartphone and a controlling app allowed to create a simple field test. The method can reliably detect the presence of kerosene in diesel from 7 to 100%, outperforming present standard methods for diesel adulteration.
The determination of chloride is still one of the main tasks for the evaluation of reinforced concrete structures.
The corrosion of the reinforcement induced by the penetrating chlorides is the dominant damage process affecting the lifetime of concrete structures. In the recent years different research groups demonstrated that LIBS can be a fast and reliable method to quantify chlorine in cement-bound materials. Because chlorine in concrete can only occur as solved ions in the pore solution or bound in salts or hydrated cement phases, the detected emission of chlorine can be correlated with the chloride concentration determined e.g. with potentiometric titration. This work inter alia describes the production of reference samples and possible side effects during the production process. Due to transport processes in the porous matrix of the cement a misinterpretation of the concentrations is possible. It is shown how to overcome these effects and higher precisions of the single measurements can be realised. Using the calibration method, blank sample method and noise method, three different ways of calculating the limit of detection (LOD) and limit of quantification (LOQ) are compared. Due to the preparation of the reference samples a precision of the whole calibration model of sx0 = 0.023 wt% is determined.
The validation of the model is based on different test sets, which are varying in their composition
(different Cl-salts, water-to-cement ratios and additives). The determined mean error of the validation is
0.595 ± 0.063 wt%, which is comparable to standardised methods like potentiometric titration, direct potentiometry
or photometry (0.40 ± 0.06 wt%) [1].
Rigid polyurethane foams (RPUFs) typically exhibit low thermal inertia, resulting in short ignition times and rapid flame spread. In this study, the fire phenomena of RPUFs were investigated using a multi-methodological approach to gain detailed insight into the fire behaviour of pentaneand water-blown polyurethane (PUR) as well as pentane-blown polyisocyanurate Polyurethane (PIR) foams with densities ranging from 30 to 100 kg/m3. Thermophysical properties were studied using thermogravimetry (TG); flammability and fire behaviour were investigated by means of the limiting oxygen index (LOI) and a cone calorimeter. Temperature development in burning cone calorimeter specimens was monitored with thermocouples inside the foam samples and visual investigation of quenched specimens’ cross sections gave insight into the morphological changes during burning. A comprehensive investigation is presented, illuminating the processes taking place during foam combustion. Cone calorimeter tests revealed that in-depth absorption of radiation is a significant factor in estimating the time to ignition. Cross sections examined with an electron scanning microscope (SEM) revealed a pyrolysis front with an intact foam structure underneath, and temperature measurement inside burning specimens indicated that, as foam density increased, their burning behaviour shifted towards that of solid materials. The superior fire performance of PIR foams was found to be based on the cellular structure, which is retained in the residue to some extent.
This paper describes a wireless mobile prototype able to perform optical measurements by means of a miniatur-ized spectrometer for low light analysis, e.g. fluorescent sensors. Evaluations, calculations, calibration management and result display are performed by a computer or a standard tablet. The device was designed primarily to detect traces of oil in drinking or ground water and for the analyses of crude oils. However, it can also address a wide range of fluorescent sensors. The fast and user-friendly inspection of water quality or oil properties, as well as the adaptability and mobility, make the device attractive for a variety of users. Further application areas could be easily imple-mented by adapting the optics and the software (database, data processing and calibration plots, etc.)
The water management in proton exchange membrane fuel cells (PEMFC) is strongly influenced by the design of the gas diffusion layers (GDL). Limiting current measurements in small-scale cells operating at high stoichiometries are useful to determine the oxygen transport resistance. The oxygen transport resistance increases, once water condenses inside the GDL. In this study a new electrochemical method for voltage loss estimation of GDL induced oxygen transport losses are presented. This new method, referred to as “transient limiting current” (TLC), is compared with the literature method. TLC allows a direct estimation of oxygen transport resistance at an arbitrarily conditioned state. This study also presents a case study of liquid water visualization of a PEM fuel cell with varying GDLs types.
With the help of quasi in-situ synchrotron X-ray computed tomography and time resolved radiography measurements we investigate appearance and distribution of liquid water inside the GDLs under limiting current conditions.
Soils are essential components of terrestrial ecosystems that experience strong pollution pressure. Microplastic contamination of soils is being increasingly documented, with potential consequences for soil biodiversity and function. Notwithstanding, data on effects of such contaminants on fundamental properties potentially impacting soil biota are lacking. The present study explores the potential of microplastics to disturb vital relationships between soil and water, as well as its consequences for soil structure and microbial function. During a 5-weeks garden experiment we exposed a loamy sand soil to environmentally relevant nominal concentrations (up to 2%) of four common microplastic types (polyacrylic fibers, polyamide beads, polyester fibers, and polyethylene fragments). Then, we measured bulk density, water holding capacity, hydraulic conductivity, soil aggregation, and microbial activity. Microplastics affected the bulk density, water holding capacity, and the functional relationship between the microbial activity and water stable aggregates. The effects are underestimated if idiosyncrasies of particle type and concentrations are neglected, suggesting that purely qualitative environmental microplastic data might be of limited value for the assessment of effects in soil. If extended to other soils and plastic types, the processes unravelled here suggest that microplastics are relevant long-term anthropogenic stressors and drivers of global change in terrestrial ecosystems.
Numerical approach to determine the correct puncture bar length for the IAEA puncture bar drop test
(2018)
Among other mechanical tests the 1 meter drop onto a steel puncture bar shall be considered for accident safe packages for the transport of radioactive material. According with the IAEA regulations “the bar shall be of solid mild steel of circular section, 15.0 ± 0.5 cm in diameter and 20 cm long, unless a longer bar would cause greater damage…”. The most damaging puncture bar length can be estimated by iterative processes in numerical simulations. On the one hand, a sufficient puncture bar length has to guarantee that shock absorbers or other attachments do not prevent or reduce the local load application to the package, on the other hand, a longer and thus less stiff bar causes a smaller maximum contact force. The contrary influence of increasing puncture bar length and increasing effective drop height shall be taken into account if a shock absorber is directly placed in the target area. The paper presents a numerical approach to identify the bar length that causes maximum damage to the package. Using the example of two typical package masses the sensitivity of contact forces and puncture bar deformations to the initial length are calculated and assessed with regard to the international IAEA package safety requirements.
The containment systems of transport casks for spent fuel and high radioactive waste usually include bolted lids with metallic or elastomeric seals.
The mechanical and thermal loadings associated with the routine, normal and accident conditions of transport can have a significant effect on the leak tightness of such containment system.
Scaled cask models are often used for providing the required mechanical and thermal tests series. Leak tests have been conducted on those models.
It is also common practice to use scaled component tests to investigate the influence of deformations or displacements of the lids and the seals on the standard leakage rate as well as to study the temperature and time depending alteration of the seals.
In this paper questions of the transferability of scaled test results to the full size design of the containment system will be discussed.