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Polysarcosine (M-n = 3650-20 000 g mol(-1), D similar to 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator.
Introducing fluorine into molecules has a wide range of effects on their physicochemical properties, often desirable but in most cases unpredictable. The fluorine atom imparts the C–F bond with low polarizability and high polarity, and significantly affects the behavior of neighboring functional groups, in a covalent or noncovalent manner. Here, we report that fluorine, present in the form of a single fluoroalkyl amino acid side chain in the P1 position of the well-characterized serine-protease inhibitor BPTI, can fully restore inhibitor activity to a mutant that contains the corresponding hydrocarbon side chain at the same site. High resolution crystal structures were obtained for four BPTI variants in complex with bovine b-trypsin, revealing changes in the stoichiometry and dynamics of water molecules in the S1 subsite. These results demonstrate that the introduction of fluorine into a protein environment can result in “chemical complementation” that has a significantly favorable impact on protein–protein interactions.
Absorption effects in total reflection X-ray fluorescence (TXRF) analysis are important to consider, especially if external calibration is to be applied. With a color X-ray camera (CXC), that enables spatially and energy resolved XRF analysis, the absorption of the primary beam was directly visualized for mL-droplets and an array of pL-droplets printed on a Si-wafer with drop-on-demand technology. As expected, deposits that are hit by the primary beam first shade subsequent droplets, leading to a diminished XRF signal. This shading effect was quantified with enhanced precision making use of sub-pixel analysis that improves the spatial resolution of the camera. The measured absorption was compared to simulated results using three different model calculations. It was found they match very well (average deviation < 10%). Thus errors in quantification due to absorption effects can be accounted for in a more accurate manner.
High loadings of carbon black (CB) are usually used to achieve the properties demanded of rubber compounds. In recent years, distinct nanoparticles have been investigated to replace CB in whole or in part, in order to reduce the necessary filler content or to improve performance. Multilayer graphene (MLG) is a nanoparticle made of just 10 graphene sheets and has recently become commercially available for mass-product nanocomposites. Three phr (part for hundred rubbers) of MLG are added to chlorine isobutyl isoprene rubber (CIIR)/CB composites in order to replace part of the CB. The incorporation of just 3 phr MLG triples the Young’s modulus of CIIR; the same effect is obtained with 20 phr CB. The simultaneous presence of three MLG and CB also delivers remarkable properties, e.g. adding three MLG and 20 phr CB increased the hardness as much as adding 40 phr CB. A comprehensive study is presented, showing the influence on a variety of mechanical properties. The potential of the MLG/CB combination is illustrated to reduce the filler content or to boost performance, respectively. Apart from the remarkable mechanical properties, the CIIR/CB/MLG nanocomposites showed an increase in weathering resistance.
DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 10^10, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.
Wedemonstrate that a single-layer graphene replicates the shape ofDNAorigami nanostructures very well. It can be employed as a protective layer for the enhancement of structural stability of DNA origami nanostructures. Using the AFM based manipulation, we show that the normal force required to damage graphene encapsulated DNA origami nanostructures is over an order of magnitude greater
than for the unprotected ones. In addition, we show that graphene encapsulation offers protection to the DNA origami nanostructures against prolonged exposure to deionized water, and multiple immersions. Through these results we demonstrate that graphene encapsulated DNA origami nanostructures are strong enough to sustain various solution phase processing, lithography and
transfer steps, thus extending the limits of DNA-mediated bottom-up fabrication.
Background: An Annex XV restriction dossier for cadmium in artists’ paints was submitted by an EU member state to the European Chemicals Agency ECHA. By cleaning used brushes under the tap cadmium can enter the food chain via waste water treatment and subsequent agricultural application of the sewage sludge. It was estimated that 110 kg Cd per year is spread on agricultural land via this exposure route. Other sources of Cd amount to almost 120 tons per year.
Results: The mobility of Cd from pigments was studied in a field-like scenario by leaching experiments using soil samples amended with sewage sludge and spiked with Cd pigments in percolation columns. The redox conditions were confirmed to be the decisive factor for the release of Cd. The release of Cd from artists’ paints was in most cases 1% or lower in the experiments performed.
Conclusions: Application of sewage sludge containing Cd from artist paints does not increase the amount of Cd leached from this soils. Furthermore the quantity of Cd from artists’ paints calculated in the restriction dossier is negligible compared to other sources of Cd to agricultural soil. Therefore ECHA did not consider the proposed restriction to be the most appropriate EU wide measure to address the negligible level of risk.
Multiple anthropogenic stressors cause worldwide amphibian declines. Among several poorly investigated causes is global pollution of aquatic ecosystems with endocrine disrupting compounds (EDCs). These substances interfere with the endocrine system and can affect the sexual development of vertebrates including amphibians. We test the susceptibility to an environmentally relevant contraceptive, the artificial estrogen 17α-ethinylestradiol (EE2), simultaneously in three deeply divergent systematic anuran families, a model-species, Xenopus laevis (Pipidae), and two non-models, Hyla arborea (Hylidae) and Bufo viridis (Bufonidae). Our new approach combines synchronized tadpole exposure to three EE2-concentrations (50, 500, 5,000 ng/L) in a flow-through-system and pioneers genetic and histological sexing of metamorphs in non-model anurans for EDC-studies. This novel methodology reveals striking quantitative differences in genetic-male-to-phenotypic-female sex reversal in non-model vs. model species. Our findings qualify molecular sexing in EDC-analyses as requirement to identify sex reversals and state-of-the-art approaches as mandatory to detect speciesspecific vulnerabilities to EDCs in amphibians.
A great number of Central Asian wall paintings, archeological materials, architectural fragments, and textiles, as well as painting fragments on silk and paper, make up the so called Turfan Collection at the Asian Art Museum in Berlin. The largest part of the collection comes from the Kucha region, a very important cultural center in the third to ninth centuries. Between 1902 and 1914, four German expeditions traveled along the northern Silk Road. During these expeditions, wall paintings were detached from their original settings in Buddhist cave complexes. This paper reports a technical study of a wall painting, existing in eight fragments, from the Buddhist cave no. 40 (Ritterhöhle). Its original painted surface is soot blackened and largely illegible. Grünwedel, leader of the first and third expeditions, described the almost complete destruction of the rediscovered temple complex and evidence of fire damage. The aim of this case study is to identify the materials used for the wall paintings. Furthermore, soot deposits as well as materials from conservation interventions were of interest. Non-invasive analyses were preferred but a limited number of samples were taken to provide more precise information on the painting technique. By employing optical and scanning electron microscopy, energy dispersive X-ray spectroscopy, micro X-ray fluorescence spectroscopy, X-ray diffraction analysis, and Raman spectroscopy, a layer sequence of earthen render, a ground layer made of gypsum, and a paint layer containing a variety of inorganic pigments were identified.
Abstract Investigations on metal halide systems carried out by Knudsen effusion mass spectrometry in the period 1990-2014 are reviewed in the present paper.163 original papers were published focused on metal halides showing still considerable activity in this area. The fundamentals of the Knudsen effusion mass spectrometry method and thermodynamic background of the investigation are briefly reported. Data to the system studied, temperature ranges, Knudsen cell materials, vapor species identified in the equilibrium vapors and the thermodynamic properties obtained in the study are presented. The important issues of metal halide vaporization studies are briefly discussed and commented. The studies of the vaporization of metal halogens by Knudsen effusion mass spectrometry aimed firstly atthe determination of gaseous complexes species in the vapor and determination of its thermodynamic data like sublimation enthalpy etc. and secondly at the determination of negative ions formation and various ion-molecule equilibria reactions of metal halide systems. Many of the studied materials have a crucial role for modern technologies, for example metal halide lamps, hot corrosion caused by halide salts, phosphorus recovery technologies or gas assisted separation of lanthanides. The investigation of such systems gives information on mechanisms of vaporization, volatility of the systems under various conditions (temperature, pressure etc.), reactivity, thermal stability, resistance etc. that could be further applied for various calculations and to predict the behavior of various components under various technological aspects.
Dietary supplements high in isolated isoflavones are commercially available for human consumption primarily to alleviate menopausal symptoms in women. The isoflavone composition, quantity and importantly their estrogenic potency are poorly standardised and can vary considerably between different products. The aim of this study was to analyse the isoflavone composition of 11 dietary supplements based on soy or red clover using the HPLC/MS/MS technique. Furthermore, we investigated the transactivational potential of the supplements on the estrogen receptors (ER), ERα and ERβ, performing luciferase reporter gene assays. As expected, we found that the isoflavone composition varies between different products. The measured total isoflavone contents in various supplements were mostly comparable to those claimed by the manufacturers in their product information. However expressing the isoflavone content as isoflavone aglycone equivalents, soy-based supplements had a clearly lower quantity compared to the manufacturer information. All supplements transactivated more or less ERα and ERβ with a preference for ERβ. The transactivational efficiency exceeded partly the maximal 17β-estradiol induced ER activation. While the different soy-based supplements revealed similar transactivation potential to both ERs, red clover-based supplements differed considerably. We conclude that different commercial dietary supplements based on soy or red clover vary in their isoflavone composition and quantity. They are estrogenically active, although especially the red clover-based supplements show considerable differences in their estrogenic potential to ERα and ERβ. Thus, different isoflavone-rich products cannot be necessarily compared regarding possible biological effects.
In 2011, the German Association of Engineers (VDI) started working on a set of guidelines dealing with the improvement of resource efficiency. These guidelines represent a framework that defines resource efficiency and outlines proposals for the producing industry. A special guideline for small and medium-sized enterprises (SMEs) is included as well as guidelines on methodologies for evaluating resource use indicators, such as the cumulative raw material demand of products and production systems. The work on resource use indicators is still in progress. The evaluation of raw materials expenditure will include water, soil and land use. The model will include the availability of raw materials (criticality). Improving resource efficiency at the end-of-life stage is illustrated in this paper by the example of materials recovery from waste, here from residues out of municipal solid waste incineration (MSWI). With mechanical treatment valuable materials like ferrous and non-ferrous metals and secondary construction material can be extracted from MSWI bottom ash. The potential contribution on the resource efficiency is discussed.
According to several recent studies, an unexpectedly high number of landmark papers seem to be not reproducible by Independent laboratories. Nontherapeutic antibodies used for research, diagnostic, food analytical, environmental, and other purposes play a significant role in this matter. Although some papers have been published offering suggestions to improve the situation, they do not seem to be comprehensive enough to cover the full complexity of this issue. In addition, no obvious improvements could be noticed in the field as yet. This article tries to consolidate the remarkable variety of conclusions and suggested activities into a more coherent conception. It is concluded that funding agencies and journal publishers need to take first and immediate measures to resolve these problems and lead the way to a more sustainable way of bioanalytical research, on which all can rely with confidence.
This review article comprises of three parts. Firstly, reports of brake manufacturers on the beneficial impact of solid lubricants for pad formulations are surveyed. Secondly, since tribofilms were identified to play a crucial role in friction stabilization and wear reduction, the knowledge about tribofilm structures formed during automotive braking was reviewed comprehensively. Finally, a model for simulating the sliding behavior of tribofilms is suggested and a review on modelling efforts with different model structures related to real tribofilms will be presented. Although the variety of friction composites involved in commercial brake systems is very broad, striking similarities were observed in respect to tribofilm nanostructures. Thus a generalization of the tribofilm nanostructure is suggested and prerequisites for smooth sliding performance and minimal wear rates have been identified. A minimum of 13 vol.% of soft inclusions embedded in an iron oxide based tribofilm is crucial for obtaining the desired properties. As long as the solid lubricants or their reaction products are softer than magnetite, the main constituent of the tribofilm, the model predicts smooth sliding and a minimum of wear.
Advances in scanning electron microscopy (SEM) enable the high-resolution imaging of single nanoparticles (NPs) with sizes well below 10 nm. The SEM analysis in transmission mode (T-SEM) of NPs on thin film supports has many benefits when compared to the analysis of NPs on bulk substrates. The enhanced material (mass – thickness) contrast of the T-SEM imaging mode is well suited for in-depth and, particularly valuable, to very accurate, traceable, lateral dimensional measurements of NPs. Compared to samples prepared on bulk substrates, T-SEM with energy dispersive X-ray spectroscopy (EDS) achieves a drastically improved spatial resolution of the emitted X-rays. The poor signal-to-noise ratio of the X-ray spectra emitted by a single nanoparticle (NP) can be improved by the use of high-sensitivity (high collection solid angle) silicon drift (SDD), energy-dispersive X-ray spectrometers (EDS). The EDS spectral imaging of a single NP with a spatial resolution below 10 nm has become possible. This is demonstrated by means of various examples of nanostructures. Advanced data processing of T-SEM/EDS results sets the stage for the automated classification of NPs by feature analysis. This method combines the detection of morphological structures of interest by image processing of T-SEM micrographs with the chemical classification by EDS.
Here we present the fabrication of a solid-core microstructured polymer optical fiber (mPOF) made of polycarbonate (PC), and report the first experimental demonstration of a fiber Bragg grating (FBG) written in a PC optical fiber. The PC used in this work has a glass transition temperature of 145°C. We also characterize the mPOF optically and mechanically, and further test the sensitivity of the PC FBG to strain and temperature. We demonstrate that the PC FBG can bear temperatures as high as 125°C without malfunctioning. In contrast, polymethyl methacrylate-based FBG technology is generally limited to temperatures below 90°C.
An unusually fast and effective synthesis procedure for a host guest system consisting of a metal organic framework (MOF) and a polyoxometalate (POM) is described. The material was synthesised mechanochemically and the evolution of the structure was monitored ex and in situ using synchrotron X-ray diffraction (XRD).
We present paper-based test strips for chemical sensing with surface enhanced Raman scattering as detection method. The test strips are prepared on glass fibre paper with silver nanoparticles and a spray method with an airbrush spray setup as a low cost fabrication approach. The properties of the test strips are investigated with three classical Raman analytes rhodamine 6G, 4-aminothiophenol and adenine and optimized for a good reproducibility of the intensity measurements. All test analytes can be identified at low concentrations. For adenine, a concentration series from 10⁻⁴ M to 10⁻⁸ M is measured and the calibration data can be fitted and evaluated with a Langmuir isotherm model. The optimized test strips are applied for the identification of two antibiotics enoxacin and enrofloxacin.
We use a dynamic scanning electron microscope (DySEM) to map the spatial distribution of the vibration of a cantilever beam. The DySEM measurements are based on variations of the local secondary electron signal within the imaging electron beam diameter during an oscillation period of the cantilever. For this reason, the surface of a cantilever without topography or material variation does not allow any conclusions about the spatial distribution of vibration due to a lack of dynamic contrast. In order to overcome this limitation, artificial structures were added at defined positions on the cantilever surface using focused ion beam lithography patterning. The DySEM signal of such high-contrast structures is strongly improved, hence information about the surface vibration becomes accessible. Simulations of images of the vibrating cantilever have also been performed. The results of the simulation are in good agreement with the experimental images.
Background: Biocidal products can be sources of active substances in surface waters caused by weathering of treated articles. Marketing and use of biocidal products can be limited according to the European Biocidal Products Regulation if unacceptable risks to the environment are expected. Leaching of active substances from treated articles was observed in field experiments to obtain information on leaching processes and investigate the suitability of a proposed test method.
Results: Leaching under weathering conditions proceeds discontinuously and tends to decrease with duration of exposure. It mainly depends on the availability of water, but is also controlled by transport processes within the materials and stability of the observed substances. Runoff amount proved to be a suitable basis to compare results from different experiments. Concentrations of substances are higher in runoff collected from vertical surfaces compared to horizontal ones, whereas the leached amounts per surface area are higher from horizontal surfaces. Gaps in mass balances indicate that additional processes such as degradation and evaporation may be relevant to the fate of active substances in treated articles. Leached amounts of substances were considerably higher when the materials were exposed to intermittent water contact under laboratory conditions as compared to weathering of vertically exposed surfaces.
Conclusions: Experiences from the field experiments were used to define parameters of a procedure that is now provided to fulfil requirements of the Biocidal Products Regulation. The experiments confirmed that the amount of water which is in contact with exposed surfaces is the crucial parameter determining leaching of substances.
Real Time Imaging of Deuterium in a Duplex Stainless Steel Microstructure by Time-of-Flight SIMS
(2016)
For more than one century, hydrogen assisted degradation of metallic microstructures has been identified as origin for severe technical component failures but the mechanisms behind have not yet been completely understood so far. Any in-situ observation of hydrogen transport phenomena in microstructures will provide more details for further elucidation of these degradation mechanisms. A novel experiment is presented which is designed to elucidate the permeation behaviour of deuterium in a microstructure of duplex stainless steel (DSS). A hydrogen permeation cell within a TOF-SIMS instrument enables electrochemical charging with deuterium through the inner surface of the cell made from DSS. The outer surface of the DSS permeation cell exposed to the vacuum has been imaged by TOF-SIMS vs. increasing time of charging with subsequent chemometric treatment of image data. This in-situ experiment showed evidently that deuterium is permeating much faster through the ferrite phase than through the austenite phase. Moreover, a direct proof for deuterium enrichment at the austenite-ferrite interface has been found.
The preparation and characterization of poly(ionic liquid)s (PILs) bearing a polystyrene backbone via reversible addition fragmentation chain transfer (RAFT) polymerization and their photolithographic patterning on silicon wafers is reported. The controlled radical polymerization of the styrenic ionic liquid (IL) monomers ([BVBIM]X, X = Cl− or Tf2N−) by RAFT polymerization is investigated in detail. We provide a general synthetic tool to access this class of PILs with controlled molecular weight and relatively narrow molecular weight distribution (2000 g mol−1 ≤ Mn ≤ 10 000 g mol−1 with dispersities between 1.4 and 1.3 for p([BVBIM]Cl); 2100 g mol−1 ≤ MP ≤ 14 000 g mol−1 for p([BVBIM]Tf2N)). More importantly, we provide an in-depth characterization of the PILs and demonstrate a detailed mass spectrometric analysis via matrix-assisted laser desorption ionization (MALDI) as well as – for the first time for PILs – electrospray ionization mass spectrometry (ESI-MS). Importantly, p([BVBIM]Cl) and p([DMVBIM]Tf2N) were photochemically patterned on silicon wafers. Therefore, a RAFT agent carrying a photoactive group based on ortho-quinodimethane chemistry – more precisely photoenol chemistry – was photochemically linked for subsequent controlled radical polymerization of [BVBIM]Cl and [DMVBIM]Tf2N. The successful spatially-resolved photografting is evidenced by surface-sensitive characterization methods such as X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The presented method allows for the functionalization of diverse surfaces with poly(ionic liquid)s.
We report an appropriate preparation of binary isotope calibration mixtures of the three stable isotopes of magnesium to be used in the ab initio calibration of multicollector mass spectrometers (ICPMS and TIMS). For each of the three possible combinations of binary mixtures ("24Mg" + "25Mg", "24Mg" + "26Mg", and "25Mg" + "26Mg"), three individual setups have been prepared under gravimetric control, each of them with an isotope ratio close to unity, and a total magnesium mass fraction close to 20 mg kg-1. The preparation was designed to occur via an intermediate dilution of a parent solution of a highly purified specimen of the isotopically enriched magnesium materials. For the application as calibration mixtures, a complete uncertainty budget was set up, and is presented and discussed in detail, including the aspects that went into the design of the dilution and mixing approach to minimize uncertainty. The principle parameters for the purpose of the later calibration of the mass spectrometers are the absolute masses of isotopically enriched magnesium materials in the primary calibration mixtures. For the first time relative expanded uncertainties U (k = 2) for these masses of ≤0.005% could be achieved for all mixtures.
Various plant compartments of a single bell pepper plant were studied to verify the variability of boron isotope composition in plants and to identify possible intra-plant isotope fractionation. Boron mass fractions varied from 9.8 mg/kg in the fruits to 70.0 mg/kg in the leaves. Boron (B) isotope ratios reported as δ11B ranged from -11.0 to +16.0 (U ≤ 1.9, k=2) and showed a distinct trend to heavier δ11B values the higher the plant compartments were located in the plant. A fractionation of Δ11Bleaf-roots = 27 existed in the studied bell pepper plant, which represents about about 1/3 of the overall natural boron isotope variation (ca. 80). Two simultaneous operating processes are a possible explanation for the observed systematic intra-plant δ11B variation: 1) B is fixed in cell walls in its tetrahedral form (borate), which preferentially incorporates the light B isotope and the remaining xylem sap gets enriched in the heavy B isotope and 2) certain transporter preferentially transport the trigonal 11B-enriched boric acid molecule and thereby the heavy 11B towards young plant compartments which were situated distal of the roots and typically high in the plant. Consequently, an enrichment of the heavy 11B isotope in the upper young plant parts located at the top of the plant could explain the observed isotope systematic. The identification and understanding of the processes generating systematic intra-plant δ11B variations will potentially enable the use of B isotope for plant metabolism studies.
Lewis and Brønsted sites were quantified in a series of weak acidic hydroxylated magnesium fluorides by Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance spectroscopy (NMR) with pyridine as probe molecule. Molar extinction coefficients, which are necessary for quantitative FTIR measurements, were calculated by an easy approach. It utilizes the fact that both signals, used for the quantification by FTIR, are caused by the same deformation vibration mode of pyridine. Comparison of quantitative FTIR experiments and quantification by NMR shows that concentrations of acidic sites determined by FTIR spectroscopy have to be interpreted with caution. Furthermore, it is shown that the transfer of molar extinction coefficients from one catalyst to another may lead to wrong results. Molar extinction coefficients and concentrations of acidic sites determined by FTIR spectroscopy are affected by grinding and probably the particle size of the sample. High temperature during FTIR experiments has further impact on the quantification results.
Starch is one of the most common and easily obtained natural polymers, making it attractive as a potential bio-based alternative to synthetic polymers. This study shows that a simple quaternary ammonium salt combined with urea or glycols forms effective modifiers that produce flexible plastics with good mechanical properties that are comparable to some polyolefin plastics. The processing conditions are shown to significantly affect the structure of the polymer which has a concomitant effect upon the mechanical and physical properties of the resulting plastic. Using a glycerol based modifier results in a totally sustainable and biodegradable material which can be injection moulded.
Micro structured reactors are attractive candidates for further process intensification in heterogeneous catalysis. However, they require catalytic coatings with significantly improved space-time yields compared to traditional supported catalysts. We report the facile synthesis of homogeneous nanocrystalline Pt coatings with hierarchical pore structure by electrochemical dealloying of amorphous sputter-deposited platinum silicide layers. Thickness, porosity and surface composition of the catalysts can be controlled by the dealloying procedure. XPS analysis indicates that the catalyst surface is primarily composed of metallic Pt. Catalytic tests in gas-phase hydrogenation of butadiene reveal the typical activity, selectivity and activation energy of nanocrystalline platinum. However, space time yields are about 13 to 200 times higher than values reported for Pt-based catalysts in literature. The highly open metallic pore structure prevents heat and mass transport limitations allowing for very fast reactions and reasonable stability at elevated temperatures.
The need for technological progress in bio-diagnostic assays of high complexity requires both fundamental research and constructing efforts on nano-scaled assay recognition elements that can provide unique selectivity and design-enhanced sensitivity features. Nanoparticle induced sensitivity enhancement and its application related to multiplexed capability Surface-Enhanced InfraRed Absorption (SEIRA) assay formats are well suitable for these purposes. The potential of diverse fluorophore–antibody conjugates, being chemisorbed onto low-cost gold nanoparticulate SEIRA substrates, has been explored with respect to their spectral discriminability. These novel biolabels deliver molecular SEIRA fingerprints that have been successfully analyzed by both uni- and multivariate analyzing tools, to discriminate their multiplexing capabilities. We show that this robust spectral encoding via SEIRA fingerprints opens up new opportunities for a fast, reliable and multiplexed high-end screening in biodiagnostics.
The reaction of iron chlorides with an alkaline reagent is one of the most prominent methods for the synthesis of iron oxide nanoparticles. We studied the particle formation mechanism using triethanolamine as reactant and stabilizing agent. In situ fast-X-ray absorption near edge spectroscopy and small-angle X-ray scattering provide information on the oxidation state and the structural information at the same time. In situ data were complemented by ex situ transmission electron microscopy, wide-angle X-ray scattering and Raman analysis of the formed nanoparticles. The formation of maghemite nanoparticles (γ-Fe2O3) from ferric and ferrous chloride was investigated. Prior to the formation of these nanoparticles, the formation and conversion of intermediate phases (akaganeite, iron(II, III) hydroxides) was observed which undergoes a morphological and structural collapse. The thus formed small magnetite nanoparticles (Fe3O4) grow further and convert to maghemite with increasing reaction time.
Within the scope of a DIN INS project, a flash thermography round robin test that evaluates reliability, comparability and efficiency of different testing situations is organized. The results give information about the detectability of defects e.g. by their size and depth, the evaluation method and by the materials used. Besides, the influence of equipment and parameters used by the participants on the results were analysed. All of the quantitative results as well as the feedback given by the participants will be presented in a DIN committee in order to contribute to a flash thermography standard.
We present the results of several machine learning (ML)- inspired data fusion algorithms applied to multi-sensory nondestructive testing (NDT) data. Our dataset consists of Impact-Echo (IE), Ultrasonic Pulse Echo (US) and Ground Penetrating Radar (GPR) data collected on large-scale concrete specimens with built–in simulated honeycombing defects. The main objective is to improve the detectability of honeycombs by fusing the information from the three different sensors. We describe normalization, feature detection and optimal feature selection. We have used unsupervised and supervised ML, i.e., classification and clustering, for data fusion. We demonstrate the advantage of data fusion in reducing the false positives up to 10% compared to the best single sensor, thus, improving the detectability of the defects. The methods were evaluated on a concrete specimen. The effectiveness of the proposed approach was demonstrated on a separate full-scale concrete specimen. The results indicate the transportability of the conclusions from one specimen to the other.
Effect of fluorescent staining on size measurements of polymeric nanoparticles using DLS and SAXS
(2015)
The influence of fluorescence on nanoparticle size measurements using dynamic light scattering (DLS) and small angle X-ray scattering (SAXS) was investigated. For this purpose, two series of 100 nm-sized polymer nanoparticles stained with different concentrations of the fluorescent dyes DY555 and DY680 were prepared, absorbing/emitting at around 560 nm/590 nm and 695 nm/715 nm, respectively. SAXS measurements of these particle series and a corresponding blank control (without dye) revealed similar sizes of all particles within an uncertainty of 1 nm. DLS measurements carried out at three different laboratories using four different DLS instruments and two different laser wavelengths, i.e., 532 nm and 633 nm, revealed also no significant changes in size (intensity-weighted harmonic mean diameter, ZAverage) and size distribution (polydispersity index, PI) within and between the two dye-stained particle series and the blank sample. Nevertheless, a significant decrease of the detected correlation coefficients was observed with increasing dye concentration, due to the increased absorption of the incident light and thus, less coherent light scattering. This effect was wavelength dependent, i.e. only measurable for the dye-stained particles that absorb at the laser wavelength used for the DLS measurements.
This paper describes the production and characteristics of the nanoparticle test materials prepared for common use in the collaborative research project NanoChOp (Chemical and optical characterization of nanomaterials in biological systems), in casu suspensions of silica nanoparticles and CdSe/CdS/ZnS quantum dots (QDs). This paper is the first to illustrate how to assess whether nanoparticle test materials meet the requirements of a "reference material" (ISO Guide 30, 2015) or rather those of the recently defined category of "representative test material (RTM)" (ISO/TS 16195, 2013). The NanoChOp test materials were investigated with small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), and centrifugal liquid sedimentation (CLS) to establish whether they complied with the required monomodal particle size distribution. The presence of impurities, aggregates, agglomerates, and viable microorganisms in the suspensions was investigated with DLS, CLS, optical and electron microscopy and via plating on nutrient agar. Suitability of surface functionalization was investigated with attenuated total reflection Fourier transform infrared spectrometry (ATR-FTIR) and via the capacity of the nanoparticles to be fluorescently labeled or to bind antibodies. Between-unit homogeneity and stability were investigated in terms of particle size and zeta potential. This paper shows that only based on the outcome of a detailed characterization process one can raise the status of a test material to RTM or reference material, and how this status depends on its intended use.
Neutron tomography has been applied to investigate the mechanism of hydrogen assisted cracking in technical iron and supermartensitic steel. Rectangular technical iron block samples showed blistering due to intense hydrogen charging and the tomographic method revealed in situ the spatial distribution of hydrogen and cracks. Hydrogen accumulated in a small region around cracks and the cracks are filled with hydrogen gas. Cracks close to the surface contained no hydrogen. Hydrogenous tensile test samples of supermartensitic steel were pulled until rupture and showed hydrogen accumulations at the notch base and in the plastically deformed region around the fracture surface.
A multifunctional fluorescence platform has been constructed based on gold nanoparticle (AuNP)-catalyzed uranine reduction. The catalytic reduction of uranine was conducted in aqueous solution using AuNPs as nanocatalyst and sodium borohydride as reducing reagent, which was monitored by fluorescence and UV-vis spectroscopy. The reaction rate was highly dependent on the concentration, size and dispersion state of AuNPs. When AuNPs aggregated, their catalytic ability decreased, and thereby a label-free fluorescent assay was developed for the detection of melamine, which can be used for melamine determination in milk. In addition, a fluorescent immunoassay for aflatoxin B1 (AFB1) was established using the catalytic reaction for signal amplification based on target-induced concentration change of AuNPs, where AFB1-BSA-coated magnetic beads and anti-AFB1 antibody-conjugated AuNPs were employed as capture and signal probe, respectively. The detection can be accomplished in 1 h and acceptable recoveries in spiked maize samples were achieved. The developed fluorescence system is simple, sensitive and specific, which could be used for the detection of a wide range of analytes.
Moisture and salt loads of concrete can significantly change its microstructure and consequently lead to chemical and mechanical degradation. However, the non-destructive investigation of moisture and salt present in concrete is still difficult. In order to address and compare the sensitivity of different methods concrete samples with different pore systems realized by varying the w/z ratios have been fabricated. The focus of this study was put on the analysis of ultrasonic long and trans waves measured on the surface and in transmission mode. The results show clear dependencies of all applied methods. With the radar and microwave methods predominantly changes in the concrete moisture could be detected, whereas the different pore systems were not observed to alter the signals. In contrast for the ultrasound method also the ongoing hydration as well as the nature of the pore system strongly influenced the signals. As a consequence in a subsequent drying experiment it was also tried to delineate the effects of moisture and hydration. All specimens have been re-saturated under pressure and the drying experiment was repeated using the same multi-sensor approach.
Measuring the moisture content of floor screeds is usually done with minor destructive testing methods like Darr drying or the Calcium Carbid (CM) method. These require small samples, deliver only punctual information and still have proven not to be very reliable. Hence, a study has been made using the standard destructive tests as well as a suite of non-destructive testing methods working out their use for moisture determination. In this study five partners from research institutes and industry worked together and intensively researched different technologies. The main focus was put on the varying sensitivity of the measuring techniques in different moisture ranges. Especially for low moisture contents ( or ‘critical’ moisture contents when the screed is dry enough to be covered with the final floor finish), several commercial devices including the most commonly used CM-method failed to determine the correct moisture content for cementitious samples. Hence the need for more accurate, if possible non-destructive methods is high, taking also into account that the chemistry (and physical properties) of screeds may vary strongly depending on their origin and purpose.
Non-destructive testing methods are mostly applied and established for the detection of embedded mounting parts or structural defects in building elements. The assessment of the concrete microstructure or microstructural changes like chemical alterations or the formation of microcracks, e.g. due to material aging, freeze-thaw cycles, alkali-silica reaction and ettringite, is not in the focus of ndt research though. Concrete moisture and enhanced salt contents, which usually trigger all chemical microstructural changes, are other material properties, lacking reliable ways of measuring. But, the assessment of such material properties, on the long term also in a depth resolved manner, is definitely important, when the sustainability of our concrete infrastructure buildings shall be evaluated.
New consideration like the potential use of ndt, in particular the combination of different methods and alternate ways of data analysis are subject of research currently undertaken at BAM. These approaches involve for example working towards (i) a deeper understanding of how to measure moisture distributions reliably and follow transport phenomena, (ii) the use of stray phenomena in radar and ultrasound to locate material inhomogeneities or (iii) the application of LIBS for the delineation of diffusion and migration processes but also (iv) the use of new tools for data analysis like data fusion. First results are presented and new ideas discussed.
Sealing and strengthening of the subsoil by injection is a major issue in the field of geotechnical engineering. One commonly applied method is jet grouting, which allows creating columns of grouted soil by eroding and mixing the in-situ soil with a thin cement suspension. A general difficulty linked with this method is to predict the resulting column diameter and its material strength. In this paper we illustrate the application of a newly developed non-destructive quality assurance testing tool used to determine the diameter of jet grout columns. This approach incorporates standard crosshole and downhole seismic measurements. To demonstrate its effectiveness, we tested the new approach within two-dimensional finite-difference numerical simulations. Additional field tests showed that this tool is also applicable in real site conditions. For this purpose, three jet grout columns were produced with different process parameters in a depth between 3.0 and 10 m. The evaluated diameters were within 1.0 and 1.5 m, slightly deviating from the previously predicted range by the jet grouting contractor. Moreover, we were able to detect the base of the columns at 10 m depth with no significant difficulties. On the other hand, unsaturated, partly unconsolidated sands between ground water level and surface considerably affected the seismic data, hence complicating the detection of the top of the columns.
Ultrasonic measurement evaluation methods have been proven to be effective for detection of subtle changes, caused by temperature, load or moisture. However, for its application outdoors it is necessary to analyse unavoidable influences, such as weather. Therefore an ultrasonic monitoring system with 40 ultrasonic sensors (20 transmitters, 20 receivers; 25 kHz central frequenzy) has been implemented on a concrete specimen (4×5×0.8m3), that is exposed to weather conditions. Data from 400 sensor combinations was collected over a period of six months with an interval of two hours. The data was evaluated by both qualitative (correlation techniques) and quantitative (ultrasonic velocity changes via Coda Wave Interferometry and time of flight method) evaluation methods and compared to the temperature changes caused by weather.
Ultrasonic measurement evaluation methods have been proven to be effective for detection of subtle changes, caused by temperature, load or moisture. To detect and localize temperature changes, a concrete block of 4 × 5 × 0.8 m3, including a heating cartridge and multiple temperature sensors, has been set up to change the temperature and monitor the temperature distribution in a certain area inside the specimen. An ultrasonic monitoring system with 40 ultrasonic sensors (20 transmitters, 20 receivers, 25 kHz central frequency) has been implemented on the specimen. Data from 400 sensor combinations was collected over the whole period of the experiment in an interval of 30 minutes. Quantitative methods (CodaWave Interferometry and Time of Flight method) were used to evaluate the changes in ultrasonic travel-time caused by the heating period, when the cartridge was active, and the cooling period after turning off the cartridge. Furthermore the travel-time changes from all 400 sensor combinations were used to locate the heating cartridge.
The paper addresses beech wood as well as vulcanized fiber and discusses the results obtained when using acoustic emission and thermography as non-destructive testing techniques along tensile and load increase fatigue tests to characterize the wooden material’s behavior under increasing fatigue loads to get enhanced information regarding the fatigue behavior of both materials. Reference is mainly made to the materials’ anisotropic and microstructural behavior and what implications this has with respect to the materials’ strength. The influence of moisture is discussed, as well as parameters that may deserve monitoring in the sense of structural health monitoring to be applied in timber structures in general.
For the closure of radioactive waste disposal facilities engineered barriers- so called “drift seals” are used. The purpose of these barriers is to constrain the possible infiltration of brine and to prevent the migration of radionuclides into the biosphere. In a rock salt mine a large scale in-situ experiment of a sealing construction made of salt concrete was set up to prove the technical feasibility and operability of such barriers. In order to investigate the integrity of this structure, non-destructive ultrasonic measurements were carried out.
Therefore two different methods were applied at the front side of the test-barrier:
1 Reflection measurements from boreholes
2 Ultrasonic imaging by means of scanning ultrasonic echo methods This extended abstract is a short version of an article to be published in a special edition of ASCE Journal that will briefly describe the sealing construction, the application of the non-destructive ultrasonic measurement methods and their adaptation to the onsite conditions -as well as parts of the obtained results. From this a concept for the systematic investigation of possible contribution of ultrasonic methods for quality assurance of sealing structures may be deduced.
LIBS is on the step from a laboratory application to on-site analysis. A validated mobile LIBS-system for on-site application on building materials is under development at BAM in cooperation with industrial partners (system developers and companies), who will use this technique for investigation on building structures like bridges and parking decks. The system is designed to measure the content of harmful species like chlorine, sulfur or alkalis, to give the engineer a tool for the estimation of the condition of concrete structures and for quality assurance during concrete repair work on-site. In these work results of on-site measurements on a chloride contaminated bridge are shown. Further work will focus on providing guidelines to establish LIBS as a standard procedure for chemical investigations of building materials.
Cracks perpendicular to the surface may be initial indicators for a deterioration process of concrete structures. Moisture penetrates inside the structure and transports adverse chemicals. The paper presents an investigation about the reliability of available commercial non-destructive evaluation techniques to reliably estimate the depth of surface-breaking cracks in reinforced concrete structures. Aim of the study was the investigation of surface-braking cracks under laboratory conditions. Commercial acoustic devices as impact echo equipment, single ultrasonic transducers and arrays were applied even if they have not been developed for this purpose. The commercial software and descriptions for application was followed strictly to compare the function, precision and repeatability of the measurements. Both, perpendicular notches and cracks have been considered. The study was completed with a discussion about reference specimens. The study was the basis for formulation of gaps in research. The Electric Power Research Institute (EPRI) has initiated and funded a Project.
Recently developed new transducers for ultrasonic transmission, which can be embedded right into concrete, are now used for non-destructive permanent monitoring of concrete. They can be installed during construction or thereafter. Large volumes of concrete can be monitored for changes of material properties by a limited number of transducers. The transducer design, the main properties as well as installation procedures are presented. It is shown that compressional waves with a central frequency of 62 kHz are mainly generated around the transducer's axis. The transducer can be used as a transmitter or receiver. Application examples demonstrate that the transducers can be used to monitor concrete conditions parameters (stress, temperature,
) as well as damages in an early state or the detection of acoustic events (e.g., crack opening). Besides application in civil engineering our setups can also be used for model studies in geosciences.
A Large Aperture UltraSonic (LAUS) system has been designed and built for testing thick concrete structures. The scalable system consists of twelve ultrasonic units, each hosting 32 individual shear wave transducers with mechanical dry point contact (DPC) to the concrete surface. The twelve units are attached to the concrete surface using a vacuum case which holds them in place during operation. Each LAUS unit can be placed individually depending on the surface condition and optimal ultrasonic condition, e.g. rebar position. Air pressure is supplied to each unit through an air hose. The following extended abstract is a short version of an article to be published in the special edition of ASCE JIS that will describe the outline of the system, the principle of functioning, the data processing and adapted reconstruction calculation based on SAFT as well as the system performance during first applications.
Elastic wave propagation of ultrasound in bituminous road surfaces - simulations and measurements
(2015)
Maintenance costs of road infrastructure are increasing steadily. The main cause of this is the nearly exponential increase of traffic during the last decades. Adverse environmental impacts on infrastructure get more and more important as well. Therefore, it is important to determine how limited financial resources can be directed with an optimum pay-out. Often a decision has to be made whether existing structures have to be rebuilt or repaired based on the condition of the structures. The present study takes first steps towards the usage of low-frequency ultrasound as a tool to evaluate the road condition. The overall aim is to derive a prediction model for future road conditions. In order to better understand and interpret recorded wave fields simulations of elastic wave propagation in layered and scattering road models have been performed. The study combined investigations in the laboratory with field measurements. In a series of extensive laboratory tests with different asphalt mixtures characteristic wave properties have been derived. Travel time (resp. velocity) as important material parameter has been investigated for different wave types, different centre frequencies and at various temperatures. An investigation of the directivity of wave radiation in the heterogeneous asphalt bodies led to an estimate of the related disturbing influences. Based on the laboratory results field measurements were performed on a real road and the records were processed to identify layers, propagation speeds and attenuation. The results were verified by a series of simulations.
A novel synthetic strategy toward highly fluorinated BODIPY dyes with exceptional photostabilities relying on sustainable gold catalysis has been developed. A key to the tailored pyrrole precursors is the gold catalysis performed in ionic liquids as the reaction medium, allowing a facile recycling of the catalysts. The dyes prepared are well-matching with the spectral windows of popular rhodamine dyes and possess high brightness while showing a distinctly higher photostability than the rhodamines especially in aprotic solvents.
The demands for the assessment of water quality are increasing steadily, making it necessary to routinely monitor multiple contaminants in water samples. For this application a hapten microarray was developed. In order to reach the required low detection limits a design of experiments (DoE) approach was used to optimize the assay performance. Here we show that a Box-Behnken design plan is an adequate choice for the straightforward exploration of hapten microarray assay parameters. For both read-out systems studied (fluorophore-labelled detection antibodies or enzymatic signal development followed by reflectometric scan, respectively), it was possible to significantly extend the measurement ranges. Furthermore, it could be shown that multivariate data analysis, here partial least squares regression (PLS), can improve the prediction accuracy of 'unknown' samples when used as calibration model, compared to classical, univariate data evaluation methods.
Geophysical methods have been used in civil engineering for decades. The main field of application is - to no surprise – in geotechnical projects from site characterization to foundation quality assurance. For more than 25 years, ground penetrating radar (GPR) and seismic methods have found applications in structural engineering. Recently introduced geophysical methods have been adopted to ultrasonic investigations in various fields. They help to improve the quality of structural imaging and to detect small changes in concrete. An overview of the history and current use of geophysics in civil engineering is given. Selected examples of new concepts include advances in wave based imaging, quality assurance for foundations, detecting small changes in concrete as well as moisture and corrosion detection are discussed.
Challenging new constructions and ageing infrastructure are increasing the demand for permanent monitoring of loads and condition. Various methods and sensors are used for this purpose. But the technologies available today have difficulties in detecting slowly progressing locally confined damages. Extensive investigations or instrumentations are required so far for this purpose. In this study we present new sensors and data processing methods for ultrasonic transmission, which can be used for non-destructive long term monitoring of concrete. They can be mounted during construction or thereafter. Larger volumes can be monitored by a limited number of sensors for changes of material properties. The principles of ultrasonic transmission and influencing factors are presented. This latter include load, damages as well as environmental parameters as temperature or moisture. Various methods for data processing, e. g. coda wave interferometry are introduced. They allow the detection of very small changes in the medium. The embedded sensors are shown including mounting and operation. Application examples so far include small scale laboratory freeze-thaw experiments, localizing loads in larger concrete models, monitoring load effects on real structures as well as detecting acoustic events. Some sensors are operating already for several years. The sensors can be used as transmitter or receivers or switched between both roles. While most of the previous experiments have been active (at least one sensor serving as transmitter), new studies show that the sensors are useful as well for passive measurements, e. g. in acoustic emission or time reversal experiments. Besides application in civil engineering our setups can also be used for model studies in geosciences.
SASfit: a tool for small-angle scattering data analysis using a library of analytical expressions
(2015)
SASfit is one of the mature programs for small-angle scattering data analysis and has been available for many years. This article describes the basic data processing and analysis workflow along with recent developments in the SASfit program package (version 0.94.6). They include (i) advanced algorithms for reduction of oversampled data sets, (ii) improved confidence assessment in the optimized model parameters and (iii) a flexible plug-in system for custom user-provided models. A scattering function of a mass fractal model of branched polymers in solution is provided as an example for implementing a plug-in. The new SASfit release is available for major platforms such as Windows, Linux and MacOS. To facilitate usage, it includes comprehensive indexed documentation as well as a web-based wiki for peer collaboration and online videos demonstrating basic usage. The use of SASfit is illustrated by interpretation of the small-angle X-ray scattering curves of monomodal gold nanoparticles (NIST reference material 8011) and bimodal silica nanoparticles (EU reference material ERM-FD-102).
This paper gives a brief overview on3D imaging of magnetic domains with shearing grating neutron tomography. We investigated the three-dimensional distribution of magnetic domain walls in the bulk of a wedge-shaped FeSi single crystal. The width of the magnetic domains wasanalyzed at different locations within the crystal. Magnetic domains close to the tip of the wedge are much smaller than in the bulk. Furthermore, the three-dimensional shape of individual domains wasinvestigated. We discuss prospects and limitations of the applied measurement technique.
Melt flow and dripping of the pyrolysing polymer melt can be both a benefit and a detriment during a fire. In several small-scale fire tests addressing the ignition of a defined specimen with a small ignition source, well-adjusted melt flow and dripping are usually beneficial to pass the test. The presence of flame retardants often changes the melt viscosity crucially. The influence of certain flame retardants on the dripping behaviour of four commercial polymers, poly(butylene terephthalate) (PBT), polypropylene (PP), polypropylene modified with ethylene-propylene rubber (PP-EP) and polyamide 6 (PA 6), is analysed based on an experimental monitoring of the mass loss due to melt dripping, drop size and drop temperature as a function of the furnace temperature applied to a rod-shaped specimen. Investigating the thermal transition (DSC), thermal and thermo-oxidative decomposition, as well as the viscosity of the polymer and collected drops completes the investigation. Different mechanisms of the flame retardants are associated with their influence on the dripping behaviour in the UL 94 test. Reduction in decomposition temperature and changed viscosity play a major role. A flow limit in flame-retarded PBT, enhanced decomposition of flame-retarded PP and PP-EP and the promotion of dripping in PA 6 are the salient features discussed.
This paper reflects recent progress in the field of fluorescent polymer optical fiber sensors (F-POF) for partial discharge (PD) detection in high voltage (HV) cable accessories using optical-only PD detection by coincidence single photon counting. In experiments with artificial PD sources these sensors show the ability to detect optical emissions from picocoulomb-level PDs in a real-scale model of a translucent high voltage cable accessory. False positives (caused by detector noise) are efficiently suppressedwhile maintaining sufficient sensitivity,even when the sensor is located in an unfavorable position.
N-Hydroxysuccinimide (NHS) esters are the most important activated esters used in many different bioconjugation techniques, such as protein labelling by fluorescent dyes and enzymes, surface activation of chromatographic supports, microbeads, nanoparticles, and microarray slides, and also in the chemical synthesis of peptides. Usually, reactions with NHS esters are very reliable and of high yield, however, the compounds are sensitive to air moisture and water traces in solvents. Therefore, the quantification of NHS would be a very helpful approach to identify reagent impurities or degradation of stored NHS esters. No robust and sensitive method for the detection of NHS (or the more hydrophilic sulfo-NHS) has been reported yet. Here, a chromatographic method based on HILIC conditions and UV detection is presented, reaching a detection limit of about 1 mg L-1, which should be sensitive enough for most of the applications mentioned above. Exemplarily, the hydrolytic degradation of a biotin-NHS ester and a purity check of a fluorescent dye NHS ester are shown. An important advantage of this approach is its universality, since not the structurally variable ester compound is monitored, but the constant degradation product NHS or sulfo-NHS, which avoids the necessity to optimize the separation conditions and facilitates calibration considerably.
In this work, sample losses of silver nanoparticles (Ag NPs) in asymmetrical flow field-flow fractionation (AF4) have been systematically investigated with the main focus on instrumental conditions like focusing and cross-flow parameters as well as sample concentration and buffer composition. Special attention was drawn to the AF4 membrane. For monitoring possible silver depositions on the membrane, imaging laser ablation coupled to inductively coupled plasma mass spectrometry (LA-ICP-MS) was used. Our results show that the sample residue on the membrane was below 0.6% of the total injected amount and therefore could be almost completely avoided at low sample concentrations and optimized conditions. By investigation of the AF4 flows using inductively coupled plasma mass spectrometry (ICP-MS), we found the recovery rate in the detector flow under optimized conditions to be nearly 90%, while the cross-flow, slot-outlet flow and purge flow showed negligible amounts of under 0.5%. The analysis of an aqueous ionic Ag standard solution resulted in recovery rates of over 6% and the ionic Ag content in the sample was found to be nearly 8%. Therefore, we were able to indicate the ionic Ag content as the most important source of sample loss in this study.
In carrier gas hot extraction the calibration of low amounts of non-metals with masses of a few micrograms with small uncertainty remains a challenge. To achieve high flexibility a high precision gas mixture pump was combined with an automated syringe drive. The gas mixing pump allows filling the syringe with different gas compositions; the automated syringe drive allows matching to modulate the signal profiles to those of real samples. The system was designed and its experimental potential explored. The resulting calibration curves were comparable to those obtained by calibration using solid materials of sufficient purity and stoichiometry. However smaller uncertainties and lower limits of quantification (i.e. 0.5 µg and 0.6 µg for O and N, respectively) were found using the gas calibration device.
Characterization of silver nanoparticles in cell culture medium containing fetal bovine serum
(2015)
Nanoparticles are being increasingly used in consumer products worldwide, and their toxicological effects are currently being intensely debated. In vitro tests play a significant role in nanoparticle risk assessment, but reliable particle characterization in the cell culture medium with added fetal bovine serum (CCM) used in these tests is not available. As a step toward filling this gap, we report on silver ion release by silver nanoparticles and on changes in the particle radii and in their protein corona when incubated in CCM. Particles of a certified reference material, p1, and particles of a commercial silver nanoparticle material, p2, were investigated. The colloidal stability of p1 is provided by the surfactants polyethylene glycol-25 glyceryl trioleate and polyethylene glycol-20 sorbitan monolaurate, whereas p2 is stabilized by polyvinylpyrrolidone. Dialyses of p1 and p2 reveal that their silver ion release rates in CCM are much larger than in water. Particle characterization was performed with asymmetrical flow field-flow fractionation, small-angle X-ray scattering, dynamic light scattering, and electron microscopy. p1 and p2 have similar hydrodynamic radii of 15 and 16 nm, respectively. The silver core radii are 9.2 and 10.2 nm. Gel electrophoresis and subsequent peptide identification reveal that albumin is the main corona component of p1 and p2 after incubation in CCM that consists of Dulbecco's modified Eagle medium with 10% fetal bovine serum added.
The color X-ray camera SLcam® is a full-field, single photon detector providing scanning-free, energy and spatially resolved X-ray imaging. Spatial resolution is achieved with the use of polycapillary optics guiding X-ray photons from small regions on a sample to distinct energy dispersive pixels on a charged-coupled device detector. Applying sub-pixel resolution, signals from individual capillary channels can be distinguished. Therefore, the SLcam® spatial resolution, which is normally limited to the pixel size of the charge-coupled device, can be improved to the size of individual polycapillary channels. In this work a new approach to a sub-pixel resolution algorithm comprising photon events also from the pixel centers is proposed. The details of the employed numerical method and several sub-pixel resolution examples are presented and discussed.
A user-friendly open-source Monte Carlo regression package (McSAS) is presented, which structures the analysis of small-angle scattering (SAS) using uncorrelated shape-similar particles (or scattering contributions). The underdetermined problem is solvable, provided that sufficient external information is available. Based on this, the user picks a scatterer contribution model (or 'shape') from a comprehensive library and defines variation intervals of its model parameters. A multitude of scattering contribution models are included, including prolate and oblate nanoparticles, core-shell objects, several polymer models, and a model for densely packed spheres. Most importantly, the form-free Monte Carlo nature of McSAS means it is not necessary to provide further restrictions on the mathematical form of the parameter distribution; without prior knowledge, McSAS is able to extract complex multimodal or odd-shaped parameter distributions from SAS data. When provided with data on an absolute scale with reasonable uncertainty estimates, the software outputs model parameter distributions in absolute volume fraction, and provides the modes of the distribution (e.g. mean, variance etc.). In addition to facilitating the evaluation of (series of) SAS curves, McSAS also helps in assessing the significance of the results through the addition of uncertainty estimates to the result. The McSAS software can be integrated as part of an automated reduction and analysis procedure in laboratory instruments or at synchrotron beamlines.
Fire and explosion hazards associated with storage and transportation of flammable materials have been a matter of great interest in the recent times. BLEVE is a scenario that occurs when a closed fuel container is subjected to heat for a longer duration. Such events are disastrous to human beings and assets both. In the past there have been numerous studies on BLEVEs and fireballs of hydrocarbon fuels, e.g. kerosene, gasoline, LPG, LNG and others. Though, the fireballs of peroxy-fuels are not looked into detail as such. This article tries to overcome this lack of knowledge. Both, experimental investigation and CFD simulations are performed to measure and predict the fireball characteristics of a peroxy-fuel. Due to thermal decomposition in the liquid phase and active oxygen content a peroxy-fuel fireball burns at a very fast rate and emit higher thermal radiation whereas exhibits smaller diameter and elevation compared to hydrocarbons. That eventually leads to consideration of larger safety distances from them which are also verified by CFD results.
Temperature-memory polymers are able to generate a substantial mechanical response when heated above the temperature, at which a preceding deformation was carried out. Here we show how to design the temperature-memory effect (TME) by thermomechanical treatment. As a model polymer, phase segregated poly(ester urethane) (PEU) containing crystallizable segments of poly(1,4-butylene adipate) (PBA) was used. For programming, strain elongation was applied at temperatures within the PBA melting transition area, before temperature holding, unloading and cooling were carried out. Upon heating under stress-free or constant strain recovery conditions, precisely set temperature-memory onsets could be witnessed. Most importantly, strain fixities and recoverabilities the same as maximum recovery stresses turned out to be controllable by strain rate and temperature holding time after deformation, while transition temperatures remained largely unaffected. The tailoring of thermoresponsiveness was structurally enabled by different PBA crystallinities in the programmed state as verified by wide-angle X-ray scattering (WAXS). The reported studies intend to design TMEs in semicrystalline polyurethanes according to user-defined needs to make this technology broadly applicable.
Geosynthetics are planar polymeric products, which are used in connection with soil, rock or other soil-like materials to fulfill various functions in geoenvironmental engineering. Geosynthetics are of ever-growing importance in the construction industry. Sealing of waste storage facilities to safely prevent the emission of wastewater, landfill gas and contaminated dust as well as the diffusion of pollutants into the environment and coastal protection against storms and floods and reconstruction after natural disaster are important fields of application. We will give an overview of the various geosynthetic products. Two examples of the material problems related to geosynthetics are discussed in detail: the effect of creep on the long-term performance of geocomposite drains and the numerical simulation of the interaction of soil with geogrids. Both issues are of importance for the use of these products in landfill capping systems. The various functions, which geosynthetics may fulfill in the protection of coastal lines, are illustrated by case studies. The geosynthetic market is evaluated and economical and environmental benefits, as well as environmental side effects related to the use of geosynthetics, are discussed.
Quantifying degradation of collagen in ancient manuscripts: the case of the Dead Sea Temple Scroll
(2013)
Since their discovery in the late 1940s, the Dead Sea Scrolls, some 900 ancient Jewish texts, have never stopped attracting the attention of scholars and the broad public alike, because they were created towards the end of the Second Temple period and the 'time of Christ'. Most of the work on them has been dedicated to the information contained in the scrolls' text, leaving physical aspects of the writing materials unexamined. They are, however, crucial for both historical insight and preservation of the scrolls. Although scientific analysis requires handling, it is essential to establish the state of degradation of these valued documents. Polarized Raman Spectroscopy (PRS) is a powerful tool for obtaining information on both the composition and the level of disorder of molecular units. In this study, we developed a non-invasive and non-destructive methodology that allows a quantification of the disorder (that can be related to the degradation) of protein molecular units in collagen fibers. Not restricted to collagen, this method can be applied also to other protein-based fibrous materials such as ancient silk, wool or hair. We used PRS to quantify the degradation of the collagen fibers in a number of fragments of the Temple Scroll (11Q19a). We found that collagen fibers degrade heterogeneously, with the ones on the surface more degraded than those in the core.
Synthesis, structure determination, and formation of a theobromine: oxalic acid 2:1 cocrystal
(2015)
The structure and the formation pathway of a new theobromine : oxalic acid (2 : 1) cocrystal are presented. The cocrystal was synthesised mechanochemically and its structure was solved based on the powder X-ray data. The mechanochemical synthesis of this model compound was studied in situ using synchrotron XRD. Based on the XRD data details of the formation mechanism were obtained. The formation can be described as a self-accelerated ('liquid like') process from a highly activated species.
The objective of the report is to present the state-of-the art of non-destructive testing methods and technologies for the inspection of thick, heavily-reinforced structures, (e.g. found in nuclear power plants). Wall thicknesses can be in excess of one meter and the structures often have increased steel reinforcement density. The accessibility for any testing method may be limited due to the presence of liners and other components such as cast-in-place items. Testing methods have to provide solutions for tasks such as locating failure (inclusions, corrosion, voids, delaminations) in the structures or the assessment of the condition of the structure in general.
Solgel prepared ternary FeF3–MgF2 materials have become promising heterogeneous catalysts due to their porosity and surface Lewis/Brønsted acidity (bi-acidity). Despite the good catalytic performance, nanoscopic characterisations of this type of material are still missing and the key factors controlling the surface properties have not yet been identified, impeding both a better understanding and further development of ternary fluoride catalysts. In this study, we characterised the interaction between the bi-acidic component (FeF3) and the matrix (MgF2) on the nano-scale. For the first time, the formation pathway of FeF3–MgF2 was profiled and the template effect of MgF2 during the synthesis process was discovered. Based on these new insights two novel materials, FeF3–CaF2 and FeF3–SrF2, were established, revealing that with decreasing the atomic numbers (from Sr to Mg), the ternary fluorides exhibited increasing surface acidity and surface area but decreasing pore size. These systematic changes gave rise to a panel of catalysts with tuneable surface and bulk properties either by changing the matrix alkaline earth metal fluoride or by adjusting their ratios to Fe or both. The template effect of the alkaline earth metal fluoride matrix was identified as the most probable key factor determining the surface properties and further influencing the catalytic performance in ternary fluoride based catalysts, and paves the way to targeted design of next-generation catalysts with tunable properties.
The Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre (JRC), a Directorate General of the European Commission, operates the International Measurement Evaluation Program (IMEP). IMEP organises inter-laboratory comparisons in support of European Union policies. This paper presents the results of two proficiency tests (PTs): IMEP-116 and IMEP-39, organised for the determination of total Cd, Pb, As, Hg and inorganic As (iAs) in mushrooms. Participation in IMEP-116 was restricted to National Reference Laboratories (NRLs) officially appointed by national authorities in European Union member states. IMEP-39 was open to all other laboratories wishing to participate. Thirty-seven participants from 25 countries reported results in IMEP-116, and 62 laboratories from 36 countries reported for the IMEP-39 study. Both PTs were organised in support to Regulation (EC) No. 1881/2006, which sets the maximum levels for certain contaminants in food. The test item used in both PTs was a blend of mushrooms of the variety shiitake (Lentinula edodes). Five laboratories, with demonstrated measurement capability in the field, provided results to establish the assigned values (Xref). The standard uncertainties associated to the assigned values (uref) were calculated by combining the uncertainty of the characterisation (uchar) with a contribution for homogeneity (ubb) and for stability (ust), whilst uchar was calculated following ISO 13528. Laboratory results were rated with z- and zeta (ζ)-scores in accordance with ISO 13528. The standard deviation for proficiency assessment, σp, ranged from 10% to 20% depending on the analyte. The percentage of satisfactory z-scores ranged from 81% (iAs) to 97% (total Cd) in IMEP-116 and from 64% (iAs) to 84% (total Hg) in IMEP-39.
In- and quasielastic neutron scattering is employed to investigate both the vibrational density of states and the molecular dynamics of two homologous discotic liquid crystals (DLC) with different length of the alkyl side chain based on a triphenylene derivate. For both compounds characteristic low frequency excess contributions to the vibrational density of states are found. Therefore it is concluded that these liquid crystals show a glass-like behaviour. Elastic scans further show that in these materials a rich molecular dynamics takes place.
Polyglycerol (PG) coated polypropylene (PP) films were synthesized in a two-step approach that involved plasma bromination and subsequently grafting hyperbranched polyglycerols with very few amino functionalities. The influence of different molecular weights and density of reactive linkers were investigated for the grafted PGs. Longer bromination times and higher amounts of linkers on the surface afforded long-term stability. The protein adsorption and bacteria attachment of the PP-PG films were studied. Their extremely low amine content proved to be beneficial for preventing bacteria attachment.
In order to assess the anisotropy-related uncertainties of relatively determined photoluminescence quantum yields (ΦPL) of molecular emitters and luminescent nanomaterials, we compared ΦPL values measured without and with polarizers using magic angle conditions and studied systematically the dependence of the detected emission intensity on the polarizer settings for samples of varying anisotropy. This includes a dispersion of a spherical quantum dot (QD) with an ideally isotropic emission, a solution of a common small organic dye in a fluid solvent as well as dispersions of elongated quantum dot rods (QDR) with an anisotropic luminescence and a small organic dye in a rigid polymeric matrix, as ideally anisotropic emitter. Our results show that for instruments lacking polarizers, anisotropy-related measurement uncertainties of relative photoluminescence quantum yields can amount to more than 40%, with the size of these systematic errors depending on the difference in emission anisotropy between the sample and the standard.
Ergopeptides, like ergocornine and a-ergocryptine, exist in an S- and in an R-configuration. Kinetic experiments imply that certain configurations are preferred depending on the solvent. The experimental methods are explained in this article. Furthermore, computational methods are used to understand this configurational preference. Standard quantum chemical methods can predict the favored configurations by using minimum energy calculations on the potential energy landscape. However, the explicit role of the solvent is not revealed by this type of methods. In order to better understand its influence, classical mechanical molecular simulations are applied. It appears from our research that 'folding' the ergopeptide molecules into an intermediate state (between the S- and the R-configuration) is mechanically hindered for the preferred configurations.
Slicing - a new method for non destructive 3D elemental sensitive characterization of materials
(2014)
Recent advances in synchrotron sources and detector technology have led to substantial improvements in spatial resolution and detection limits for X-ray fluorescence analysis (XRF). However, the non-destructive three-dimensional elemental sensitive characterization of samples remains a challenge. We demonstrate the use of the so-called 'Color X-ray Camera' (CXC) for 3D measurements for the first time. The excitation of the sample is realized with a thin sheet-beam. The stepwise movement of the sample allows getting the elemental distribution for each layer with one measurement. These layers can be combined to a full 3D dataset for each element afterwards. Since the information is collected layer by layer, there is no need to apply reconstruction techniques, which quite often are the reason for artifacts in the results achieved by computed tomography (CT). The field of applications is wide, as the 3D elemental distribution of a material contains clues to processes inside the samples from a variety of origins. The technique is of special interest and well suited for biological specimens, because their light matrix minimizes restricting absorption effects. Measurement examples of a hornet and the teeth of a Sorex araneus are shown.
In this work an air-based sensor network for the localization of persons at extensive areas is presented. The developed network consists of a localization device which the person is wearing (BodyGuard-System), a mobile relay station in the air, and a base station. All three parts communicate with the same radio chip. The BodyGuard-System is an inertial navigation system which was developed for localization in difficult environments with high accuracy and low measurement uncertainty. To increase the range of the system, a multi-hop network was built up. The measured data of the BodyGuard-System and the mobile relay station is visualized on a PC in the base station. This multi-hop network is necessary for example for fire department missions.
The adsorption of porphyrin derivatives on a Au(111) surface was studied by scanning tunneling microscopy and spectroscopy at low temperatures in combination with density functional theory calculations. Different molecular appearances were found and could be assigned to the presence of single gold adatoms bonded by a coordination bond underneath the molecular monolayer, causing a characteristic change of the electronic structure of the molecules. Moreover, this interpretation could be confirmed by manipulation experiments of individual molecules on and off a single gold atom. This study provides a detailed understanding of the role of metal adatoms in surface–molecule bonding and anchoring and of the appearance of single molecules, and it should prove relevant for the imaging of related molecule–metal systems.
We present a systematic study on the effect of surface ligands on the luminescence properties and colloidal stability of β-NaYF4:Yb3+,Er3+ upconversion nanoparticles (UCNPs), comparing nine different surface coatings to render these UCNPs water-dispersible and bioconjugatable. A prerequisite for this study was a large-scale synthetic method that yields ~2 g per batch of monodisperse oleate-capped UCNPs providing identical core particles. These ~23 nm sized UCNPs display an upconversion quantum yield of ~0.35% when dispersed in cyclohexane and excited with a power density of 150 W cm-2, underlining their high quality. A comparison of the colloidal stability and luminescence properties of these UCNPs, subsequently surface modified with ligand exchange or encapsulation protocols, revealed that the ratio of the green (545 nm) and red (658 nm) emission bands determined at a constant excitation power density clearly depends on the surface chemistry. Modifications relying on the deposition of additional (amphiphilic) layer coatings, where the initial oleate coating is retained, show reduced non-radiative quenching by water as compared to UCNPs that are rendered water-dispersible via ligand exchange. Moreover, we could demonstrate that the brightness of the upconversion luminescence of the UCNPs is strongly affected by the type of surface modification, i.e., ligand exchange or encapsulation, yet hardly by the chemical nature of the ligand.
Quantitative determination of acidic surface sites is highly important for the characterization of solid acids because the activity of a catalyst is often related to the concentration of these sites. A recently developed method using 15N Nuclear Magnetic Resonance spectroscopy (NMR) for the quantification of acidic Lewis and Brønsted sites has been tested for a series of nanoscopic aluminum hydroxide fluorides. Comparison with other methods for the quantitative determination of acidic sites shows that this 15N NMR quantification method is a promising technique for the comprehensive investigation of acidic sites. Three different acidic sites, one Brønsted and two Lewis sites, can be distinguished by their 15N chemical shifts of pyridine and simultaneously quantified under conditions corresponding to catalytic reaction conditions. Determination of the individual concentrations of acidic sites allows further insight into the catalytic process. It was found that the concentration of Brønsted sites correlates with catalyzed conversion of citronellal to isopulegol in the investigated series of catalysts. Additionally, investigations indicate that one of the Lewis sites become blocked during the reaction of citronellal.
The digital photography has almost completely substituted the film photography. The film replacement is also fast progressing in medical X-ray radiography. This process is slower in NDT and especially in Europe. Reasons for the hesitating change to digital radiography (RT-D) in NDT are the necessary time for adoption of standards and the conservative request for film RT by auditors and NDT managers for applications in large plants and at construction areas. The fast serial inspection for small castings is already almost completely dominated by RT-D due to the cost effective short exposure and interpretation times. Standards were developed in parallel at CEN, ISO, ASTM and ASME. Unfortunately, the standard practices are different and the requirements on image quality and useable hardware are different too. The first standard series on Computed Radiography were developed and published by CEN and ASTM in 2005. Harmonized classification and qualification standards are available but the published practices are different. ASTM has developed the first standards for application of Digital Detector Arrays (DDA) in 2010. The first digital RT ISO standard practice is ISO 17636-2 (2013), which describes the practice for application of DDAs and Imaging Plates for weld inspection. At the first time this standard provides requirements for the selection of suitable hardware. Minimum image quality requirements are specified in analogy to film radiography and 3 Compensation Principles are defined to enable the application of a wider range of digital detectors. A comparison of the different international digital RT standards is given and first experiences with ISO 17636-2 are discussed. New standards on RT wall thickness and corrosion measurements (EN 16407, film and digital) have been developed recently.
A comparative study on the performance of digital detector systems for high energy applications
(2014)
For cast components reaching or exceeding total material thicknesses of 150mm, high energy sources such as linear accelerators or Betatrons are required in order to obtain reasonable exposure times. In this study, the performance of digital detector systems, involving imaging plates (IP) and digital detector arrays (DDA), was evaluated with respect to the testing class B requirements as formulated in the standard EN ISO 17636-2. As a reference, traditional radiographic film and a Cobalt-60 source was used. With film exposures, testing class B was achieved with Co-60 and Betatron (7.5 MV) at longer exposure times. The preliminary results show that the testing class B was not obtained with the examined digital detector arrays (DDA) and the high resolution imaging plates (IP) , even at 40, 60 and 80 minutes exposure time with a 7.5 MV Betatron. Class A was achieved using high resolution imaging plates with optimized metal filters between object and IPs and a high resolution DDA with intermediate Cu filters. Class A was also achieved applying a DDA with lower basic spatial resolution than required by Table B.13 of EN ISO 17636-2, but using the compensation principle as described in this standard. The next generation of digital detector arrays might potentially be able to obtain class B performance with the expected spatial resolution and sensitivity improvements.
The progress in X-ray detector electronics (sensitivity and speed) allows meanwhile fast single photon detection by a matrix detector. Combined photon counting and energy discrimination is implemented in the electronic circuit of each detector pixel. The company XCounter developed detectors based on CdTe single crystals, which can be tiled to larger areas and have a pixel size of 100ìm. The largest area available in beginning of 2014 is 50x75 mm². These detectors have very promising properties, which make them very suitable for NDT applications:
1. A CdTe attenuation layer of 750 µm thickness allows efficient X-ray detection up to ca. 300 keV. In counting mode only photon noise is important; no other detector noise sources need to be considered. There is no Offset signal without radiation.
2. Each of the detector pixels has two energy thresholds. These can be used for dual energy imaging for materials separation. Also the suppression of scattered radiation by energy thresholding will improve the image contrast sensitivity. First experiments will be presented which demonstrate the advantages of this new detector technology over the conventional charge integrating detectors.
A challenge is the development of a modified detector calibration procedure, which becomes critical at longer exposure times.
The objects of this investigation were sculptures taken from a ca. three hundred years old baroque epitaph of a church in Tonning, a town in Northern Germany. Around 1900 it was found in a disastrous state heavily damaged by wood-worm. At that time, the whole artwork was treated with the tar extract carbolineum as a remedy. Nowadays, this substance has been identified as carcinogenic, and its presence can be perceived by its stench and visually at certain spots on the surface where it has penetrated the covering paint.
A gold-painted sculpture of a massive wooden skull was interrogated with X-rays and fast neutrons to investigate the internal distribution of the carbolineum. The X-ray tomography, with its excellent spatial resolution revealed galleries left over from the worm infestation in the outer areas and cracks in the central region. The golden color coating appeared as a thick and dense layer. In comparison the tomography with fast neutrons, though being of lower resolution and yet unresolved artefacts revealed sections of slightly different densities in the bulk of the wood. These differences we attribute to the differences in the distribution of the impregnant in the wood, visible due to its higher hydrogen content making it less transparent for neutrons.
Using ultrafast X-ray diffraction, we study the coherent picosecond lattice dynamics of photoexcited thin films in the two limiting cases, where the photoinduced stress profile decays on a length scale larger and smaller than the film thickness. We solve a unifying analytical model of the strain propagation for acoustic impedance-matched opaque films on a semi-infinite transparent substrate, showing that the lattice dynamics essentially depend on two parameters: One for the spatial profile and one for the amplitude of the strain. We illustrate the results by comparison with high-quality ultrafast X-ray diffraction data of SrRuO3 films on SrTiO3 substrates.
Innovative X-ray backscatter technique for security applications: Detection of dangerous materials
(2014)
Radiological inspections, in general, are NDT&E methods to detect the bulk of explosives without invasion into the object of analysis. In contrast to personal luggage, cargo or structural components constitute a complexity that may significantly hamper the detection of a threat by conventional transmission radiography. A novel approach of interrogating a large object to a certain depth only with a single sided access will be presented. It consists of an X-ray backscatter camera with a special twisted slit collimator for imaging backscattered objects. The new X-ray backscatter camera is not only imaging the objects due to their densities but also by taking into account the influences of surrounding objects. Additionally, it does not only image illuminated features but also depicts shadows from absorbing materials. This is a unique characteristic of the developed X-ray backscatter camera. Experimental mock-ups are conducted imitating container with threats among a complex packing as they may be encountered in reality. At the end, the significant advantages of the presented X-ray backscatter camera in the context of aviation and port security will be discussed.
In this contribution, we present a dual high-energy X-ray imaging technique for cargo container inspection using the 'spectral high-energy X-ray attenuation method'. This method is based on attenuation of continuous highenergy spectra. The developed experimental technique consists of a betatron as high-energy (up to 7.5 MeV) X-ray source and a matrix detector with high spatial resolution (400 ìm) for digital X-ray imaging. In order to evaluate the material discrimination capability using dual high-energy X-ray imaging, a test specimen is proposed, comprising step wedges of different low and high atomic number (Z) materials. The selected X-ray spectra for the dual-energy experiments correspond to 3 MV and 7.5 MV acceleration potential of the betatron. We evaluated the ratio between low- and high-energy X-ray attenuation coefficients quantitatively based on simulated poly-energetic high-energy X-ray source spectra and the detector sensitivity using the 'analytical Radiographic Testing inspection simulation tool' (aRTist) developed at BAM. The simulated effective attenuation coefficients are compared with corresponding experimental results in order to establish a method for identification of low- and high-Z materials in the container. Finally, important applications of the proposed technique in the context of aviation security are discussed.
Critical parts in aircraft manufacturing such as stringers are very commonly used in modern aircraft structures to resist the compressive loads caused by the aerodynamic effects. They are generally made-up of thin aluminium (Al) metal sheets and are one of the key components in the aircraft wings. Any defects in the stringer leads to weakening of the stiffness of the whole wing structure and consequently, failures may occur. Hence, the structural integrity of the stringers should be evaluated using reliable non-destructive testing (NDT) methods. Due to the complex shaped structure of the stringer, the one-sided access NDT method such as X-ray backscatter technique is more preferable for the non-destructive imaging. In this paper, we present a new X-ray backscatter technique to image the internal sections of the stringer with only a single-sided access. The whole object was inspected by changing the viewing direction of the X-ray backscatter camera. For the first time, the X-ray backscatter measurements were conducted using high-energy (> 0.5MeV) X-rays and proved the applicability of the present technique to inspect thick carbon-fiber laminated components. In order to improve the inspection time and image quality of the backscatter image, we used high-resolution (180ìm) digital detector arrays (DDAs). At the end, important applications of the presented X-ray backscatter technique to the aerospace industry are discussed.
Genetic transformation of Knufia petricola A95 - a model organism for biofilm-material interactions
(2014)
We established a protoplast-based system to transfer DNA to Knufia petricola strain A95, a melanised rock-inhabiting microcolonial fungus that is also a component of a model sub-aerial biofilm (SAB) system. To test whether the desiccation resistant, highly melanised cell walls would hinder protoplast formation, we treated a melanin-minus mutant of A95 as well as the type-strain with a variety of cell-degrading enzymes. Of the different enzymes tested, lysing enzymes from Trichoderma harzianum were most effective in producing protoplasts. This mixture was equally effective on the melanin-minus mutant and the type-strain. Protoplasts produced using lysing enzymes were mixed with polyethyleneglycol (PEG) and plasmid pCB1004 which contains the hygromycin B (HmB) phosphotransferase (hph) gene under the control of the Aspergillus nidulans trpC. Integration and expression of hph into the A95 genome conferred hygromycin resistance upon the transformants. Two weeks after plating out on selective agar containing HmB, the protoplasts developed cell-walls and formed colonies. Transformation frequencies were in the range 36 to 87 transformants per 10 µg of vector DNA and 106 protoplasts. Stability of transformation was confirmed by sub-culturing the putative transformants on selective agar containing HmB as well as by PCR-detection of the hph gene in the colonies. The hph gene was stably integrated as shown by five subsequent passages with and without selection pressure.
Thermally reduced graphite oxide (TRGO), containing only four single carbon layers on average, was combined with ammonium polyphosphate (APP) and magnesium hydroxide (MH), respectively, in polypropylene (PP). The nanoparticle's influence on different flame-retarding systems and possible synergisms in pyrolysis, reaction to small flame, fire behavior and mechanical properties were determined. TRGO has a positive effect on the yield stress, which is decreased by both flame-retardants and acts as a synergist with regard to Young's modulus. The applicability and effects of TRGO as an adjuvant in combination with conventional flame-retardants depends strongly on the particular flame-retardancy mechanism. In the intumescent system, even small concentrations of TRGO change the viscosity of the pyrolysing melt crucially. In case of oxygen index (OI) and UL 94 test, the addition of increasing amounts of TRGO to PP/APP had a negative impact on the oxygen index and the UL 94 classification. Nevertheless, systems with only low amounts (≤1 wt%) of TRGO achieved V-0 classification in the UL 94 test and high oxygen indices (>31 vol%). TRGO strengthens the residue structure of MH and therefore functions as a strong synergist in terms of OI and UL 94 classification (from HB to V-0).
In this article, the high potential of the fluorolytic sol–gel process to synthesize nanoscopic rare earth-doped calcium fluoride sols is shown. Through a fluorolytic sol–gel process we manage to achieve spherical monodisperse ~5 nm sized nanoparticles using a simple and reproducible one-pot-wet chemical route at room temperature. The as-synthesized clear sols exhibit an intense red and green luminescence under UV excitation at room temperature. A spectroscopic study of the sols revealed the characteristic transitions 5D0 → 7FJ of Eu3+ and 5D4 → 7FJ of Tb3+, with 5D0 → 7F2 (611 nm) of Eu3+ and 5D4 → 7F4 (581 nm) of Tb3+ as the most prominent transitions. This facile synthetic strategy is also valuable for developing other luminescent nanoparticles.
A flexible, sustainable, one-step thermal decomposition route for the synthesis of hierarchical, heteroatom doped carbon foams is presented. Task-specific semi-organic crystals combine functions for three different purposes: the carbon and heteroatom source, a foaming agent (CO2) and an in situ generable template (NaCl). Insights to the decomposition pathway were gained through FTIR/MS coupled TGA and an ultrafast out-of-furnace heating procedure and the products were analysed with (HR)SEM/TEM, EELS, FTIR, and N2 sorption. The resulting macroporous carbon foams are excellent supports for metallic nanoparticles due to their hierarchical structure, high surface area and tuneable heteroatom contents. This was demonstrated for catalytically active copper or the magnetic CoNi alloy for water purification.
Structural properties of iron-phosphate glasses: spectroscopic studies and ab initio simulations
(2014)
Vitrification is the most effective method for the immobilization of hazardous waste by incorporating toxic elements into a glass structure. Iron phosphate glasses are presently being considered as matrices for the storage of radioactive waste, even of those which cannot be vitrified using conventional borosilicate waste glass. In this study, a structural model of 60P2O5–40Fe2O3 glass is proposed. The model is based on the crystal structure of FePO4 which is composed of [FeO4][PO4] tetrahedral rings. The rings are optimized using the DFT method and the obtained theoretical FTIR and Raman spectra are being compared with their experimental counterparts. Moreover, the proposed model is in very good agreement with X-ray absorption fine structure spectroscopy (XANES/EXAFS) and Mössbauer spectroscopy measurements. According to the calculations the Fe3+ is in tetrahedral and five-fold coordination. The maximal predicted load of waste constituents into the glass without rebuilding of the structure is 30 mol%. Below this content, waste constituents balance the charge of [FeO4]- tetrahedra which leads to their strong bonding to the glass resulting in an increase of the chemical durability, transformation and melting temperatures and density.
Rigid rod-type metallo-supramolecular coordination polyelectrolytes with Fe(II) centres (Fe-MEPEs) are produced via the self-assembly of the ditopic ligand 1,4-bis(2,2':6',2''-terpyridine-4'-yl)benzene (tpy-ph-tpy) and Fe(II) acetate. Fe-MEPEs exhibit remarkable electrochromic properties; they change colour from blue to transparent when an electric potential is applied. This electrochemical process is generally reversible. The blue colour in the ground state is a result of a metal-to-ligand charge transfer at the Fe(II) centre ion in a quasi-octahedral geometry. When annealed at temperatures above 100 °C, the blue colour turns into green and the formerly reversible electrochromic properties are lost, even after cooling down to room temperature. The thermally induced changes in the Fe(II) coordination sphere are investigated in situ during annealing of a solid Fe-MEPE using X-ray absorption fine structure (XAFS) spectroscopy. The study reveals that the thermally induced transition is not accompanied by a redox process at the Fe(II) centre. From the detailed analysis of the XAFS spectra, the changes are attributed to structural changes in the coordination sphere of the Fe(II) site. In the low temperature state, the Fe(II) ion rests in a quasi-octahedral coordination environment surrounded by six nitrogen atoms of the pyridine rings. The axial Fe–N bond length is 1.94 Å, while the equatorial bond length amounts to 1.98 Å. In the high temperature state, the FeN6-site exhibits a distortion with the axial Fe–N bonds being shortened to 1.88 Å and the equatorial Fe–N bonds being elongated to 2.01 Å.
-Background-
Laboratory leaching tests on treated wood were performed during a European robustness study in the framework of the validation of a tank leaching test procedure that has been proposed for construction products in order to determine the potential release of dangerous substances which can be transferred to soil and groundwater. The release of substances has to be determined also for materials treated with biocidal products according to the requirements of the European Biocidal Products Regulation. A similar leaching test procedure was already harmonised for treated wood for this purpose. Both test procedures were applied in parallel to wood treated with the same preservative to investigate whether the results of these tests can replace each other. Additional experiments were performed to further investigate unexpected effects of L/A ratio on leaching of copper and duration of storage of treated test specimens.
-Results-
Both procedures generate similar results concerning cumulative emissions of tebuconazole, copper, dissolved organic carbon and total nitrogen. The emission rates with time are in comparable ranges for both leaching protocols. Emissions of copper increased with decreasing L/A ratios. Strong correlation of copper concentrations and dissolved organic carbon as well as total nitrogen concentrations in eluates indicates that this observation is caused by co-elution of copper with organic substances. Duration of storage of treated test specimens affected emissions for the investigated wood preservative.
-Conclusions-
Based on these findings, results from both test procedures can be used to describe leaching characteristics and avoid double testing of treated wood to fulfil the requirements of the European regulations for either biocides or construction products. Leaching of substances from treated wood is a complex process that depends on its chemical composition and ageing processes.
The combination of complementary characterization techniques such as SEM (Scanning Electron Microscopy), T-SEM (Scanning Electron Microscopy in Transmission Mode), EDX (Energy Dispersive X-ray Spectroscopy) and SAM (Scanning Auger Microscopy) has been proven to be a powerful and relatively quick characterization strategy for comprehensive morphological and chemical characterization of individual silica and titania nanoparticles. The selected real life test materials, silica and titania, are listed in the OECD guidance manual as representative examples because they are often used as commercial nanomaterials. Imaging by high resolution SEM and in the transmission mode by T-SEM allows almost simultaneous surface and in-depth inspection of the same particle using the same instrument. EDX and SAM enable the chemical characterization of bulk and surface of individual nanoparticles. The core–shell properties of silica based materials are addressed as well. Titania nominally coated by silane purchased from an industrial source has been found to be inhomogeneous in terms of chemical composition.
The tribological and mechanical properties of niobium carbides (NbC) bonded with cobalt of Fe3Al
(2014)
The tribological and mechanical properties of niobium carbide bonded with 8 vol.-% (NbC-8Co), 12 vol.-% of cobalt (NbC-12Co) or 12 vol.-% of Fe3Al (NbC-12Fe3Al) are presented. Rotating discs made of metal-bonded niobium carbide were mated against alumina (99.7%) under unlubricated (dry) unidirectional sliding tests (0.1 m/s to 12.0 m/s; 22 °C and 400 C) as well as in oscillation tests (f=20 Hz, Δx=0.2 mm, 2/50/98% rel. humidity, n=105/106 cycles). Microstructure and phase compositions were determined as well. The tribological data obtained were benchmarked with different ceramics, cermets, hard metals and thermally sprayed coatings, where NbC bonded with 8% and 12% Co presented above 7 m/s the lowest wear rates so far in such a benchmark. Binderless NbC (HP-NbC1) and the metal-bonded NbCs exhibited low wear rates under dry sliding associated with P·V high load carrying capacities. NbC-based hard metal bonded with 12 vol.-% of Fe3Al resulted in a higher hardness level than for 12 vol.-% cobalt. The tribological profile established revealed a strong position of NbC-bearing materials under tribological considerations and for closed tribosystems against established reference tribo-couples.
Two design approaches for multifunctional information carriers are introduced. In the first one, quick response (QR) code carriers, which were composed of poly(ester urethane) (PEU) and microencapsulated thermochromic pigments (T-PIGs), differing in color and color switching temperature (CST), were prepared. The obtained material systems exhibited machine-readable QR codes at 23 °C and a two-stage decolorization when heated, culminating in unreadable QR codes at temperatures above the highest CST of the employed T-PIGs. In the second scenario, information carriers were sealed with a dark, thermochromic PEU layer. As a result, the QR codes were hidden at 23 °C and became readable upon heating due to color fading. Beyond the characterization of the employed components, preparation methods, functionality analyses and durability investigations are reported. When heated after thermo-mechanical programming, pronounced shape memory properties could be verified. The thermo-responsiveness of such multifunctional material systems may qualify them for usage in anti-counterfeiting applications.
The objective of this study was to investigate the influence of externally applied magnetic fields on the weld quality in laser beam welding. The optimization of the process parameters was performed using the results of computer simulations. Welding tests were performed with up to 20 kW laser beam power. It was shown that the AC magnet with 3 kW power supply allows for a prevention of the gravity drop-out for full penetration welding of 20 mm thick stainless steel plates. For partial penetration welding it was shown that an0.5 T DC magnetic field is enough for a suppression of convective flows in the weld pool. Partial penetration welding tests with 4 kW beam power showed that the application of AC magnetic fields can reduce weld porosity by a factor of 10 compared to the reference joints. The weld surface roughness was improved by 50%.
DNA origami nanostructures allow for the arrangement of different functionalities such as proteins, specific DNA structures, nanoparticles, and various chemical modifications with unprecedented precision. The arranged functional entities can be visualized by atomic force microscopy (AFM) which enables the study of molecular processes at a single-molecular level. Examples comprise the investigation of chemical reactions, electron-induced bond breaking, enzymatic binding and cleavage events, and conformational transitions in DNA. In this paper, we provide an overview of the advances achieved in the field of single-molecule investigations by applying atomic force microscopy to functionalized DNA origami substrates.