Wissenschaftliche Artikel der BAM
Filtern
Erscheinungsjahr
Dokumenttyp
- Zeitschriftenartikel (1778)
- Beitrag zu einem Tagungsband (37)
- Forschungsbericht (1)
Sprache
- Englisch (1801)
- Deutsch (11)
- Mehrsprachig (3)
- Portugiesisch (1)
Referierte Publikation
- ja (1816) (entfernen)
Schlagworte
- Additive manufacturing (54)
- Fluorescence (54)
- SAXS (43)
- Nanoparticles (40)
- Quantum yield (36)
- MALDI-TOF MS (34)
- Concrete (32)
- Corrosion (28)
- Mechanochemistry (28)
- Polylactide (26)
Organisationseinheit der BAM
- 6 Materialchemie (399)
- 1 Analytische Chemie; Referenzmaterialien (331)
- 8 Zerstörungsfreie Prüfung (266)
- 5 Werkstofftechnik (173)
- 4 Material und Umwelt (168)
- 7 Bauwerkssicherheit (166)
- 6.3 Strukturanalytik (155)
- 9 Komponentensicherheit (152)
- 8.5 Röntgenbildgebung (103)
- 6.1 Oberflächen- und Dünnschichtanalyse (93)
Paper des Monats
- ja (71)
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.
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.
Ultrasonic testing of adhesively bonded joints using air-coupled cellular polypropylene transducers
(2014)
In air-coupled ultrasonic testing, the impedance mismatch between the transducer and the air is commonly being solved by adding matching layers to composite transducers. To avoid the difficult technological procedure regarding matching layers, some new piezoelectric materials have been proposed. Most promising are ferroelectrets, which are charged cellular polymers, having ferroelectric and consequently piezoelectric properties. In particular, the extreme softness of cellular polypropylene (cPP) leads to a high piezoelectric constant and to a good impedance match with the air, making matching layers redundant. Its elasticity modulus below 1 MPa causes an additional effect not observed with common piezoelectric materials: that is the electrostrictive effect, here defined as the thickness change due to the attractive force between the transducer electrodes. This effect exceeds the piezoelectric effect at excitation voltages over 1 kV. The extreme softness of cPP leads also to high flexibility, enabling easy focusing by bending the transducer.
We have developed air-coupled ultrasonic transducers based on cPP. This includes the electrical matching networks for the transmitter and for the receiver. The transmitter is excited with voltages up to 2.5 kV, so that the electrostrictive effect dominates, leading to sound pressure around 145dB at the transducer surface. These transducers have been applied for testing carbon-fiber-reinforced polymer plates, adhesive joints and other composite structures. Here we report about ultrasonic transmission of two types of adhesive joints. The first one is multi-layer aluminium components with some artificial disbonds, which are common in aerospace industry, and the second one is an aluminium-steel joint with polyurethane adhesive, which is used in automotive industry.
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.
The most successful additive manufacturing (AM) technologies are based on the layer-by-layer deposition of a flowable powder. Although considered as the third industrial revolution, one factor still limiting these processes to become completely autonomous is the often necessary build-up of support structures. Besides the prevention of lateral shifts of the part during the deposition of layers, the support assures quality and stability to the built process. The loose powder itself surrounding the built object, or so-called powder-bed, does not provide this sustenance in most existent technology available. Here we present a simple but effective and economical method for stabilizing the powder-bed, preventing distortions in the geometry with no need for support structures. This effect, achieved by applying an air flow through the powder-bed, is enabling an entirely autonomous generation of parts and is a major contribution to all powder-based additive manufacturing technologies. Moreover, it makes powder-based AM independent of gravitational forces, which will facilitate crafting items in space from a variety of powdery materials.
The synthesis of the polymorphic cocrystal caffeine:anthranilic acid was investigated to obtain a better understanding of the processes leading to the formation of different polymorphic forms. In the case of these cocrystal polymorphs synthesized by liquid-assisted grinding a distinct influence of the dipole moment of the solvent was found. A pre-coordination between the solvent molecules and the caffeine:anthranilic acid cocrystal could be identified in the formation of form II. In the case of form II the solvent can be regarded as a catalyst. The formation pathway of each polymorph was evaluated using synchrotron X-ray diffraction.
Recently, C K-edge Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of graphite (HOPG) surfaces have been measured for the pristine material, and for HOPG treated with either bromine or krypton plasmas (Lippitz et al., Surf. Sci., 2013, 611, L1). Changes of the NEXAFS spectra characteristic for physical (krypton) and/or chemical/physical modifications of the surface (bromine) upon plasma treatment were observed. Their molecular origin, however, remained elusive. In this work we study by density functional theory, the effects of selected point and line defects as well as chemical modifications on NEXAFS carbon K-edge spectra of single graphene layers. For Br-treated surfaces, also Br 3d X-ray Photoelectron Spectra (XPS) are simulated by a cluster approach, to identify possible chemical modifications. We observe that some of the defects related to plasma treatment lead to characteristic changes of NEXAFS spectra, similar to those in experiment. Theory provides possible microscopic origins for these changes.
Hemocompatible materials are needed for internal and extracorporeal biomedical applications, which should be realizable by reducing protein and thrombocyte adhesion to such materials. Polyethers have been demonstrated to be highly efficient in this respect on smooth surfaces. Here, we investigate the grafting of oligo- and polyglycerols to rough poly(ether imide) membranes as a polymer relevant to biomedical applications and show the reduction of protein and thrombocyte adhesion as well as thrombocyte activation. It could be demonstrated that, by performing surface grafting with oligo- and polyglycerols of relatively high polydispersity (>1.5) and several reactive groups for surface anchoring, full surface shielding can be reached, which leads to reduced protein adsorption of albumin and fibrinogen. In addition, adherent thrombocytes were not activated. This could be clearly shown by immunostaining adherent proteins and analyzing the thrombocyte covered area. The presented work provides an important strategy for the development of application relevant hemocompatible 3D structured materials.
In order to investigate molecular recognition on surfaces, an azide-functionalized monolayer was deposited on gold. The monolayer was characterized by X-ray photoelectron spectroscopy (XPS) and angle-resolved near-edge X-ray absorption fine structure (NEXAFS) experiments and the decomposition of the azide upon irradiation with X-ray beams was investigated. Subsequently, various alkyne-functionalized host and guest molecules were attached to the azide by 1,3-dipolar cycloaddition. These modified surfaces and their host–guest chemistry were analysed by XPS and angle-resolved NEXAFS. The reversibility of guest binding was shown for one example as a proof of principle.
The mechanochemical synthesis of two model compounds, a metal organic framework ([Bi(1,4-bdc)2]*(Im) (bdc = benzene dicarboxylate, Im = imidazole cation)) and a cocrystal (Carbamazepine:Indometacin 1:1) were followed ex situ by combined analytical methods. Powder X-ray diffraction (XRD) and Raman spectroscopy data were evaluated for the synthesis of the metal organic framework. XRD measurements and REM images were analysed for the synthesis of the cocrystal. The measurements revealed that both model compounds were synthesised within minutes. The metal organic framework [Bi(1,4-bdc)2]*(Im) is synthesised via an intermediate structure. The cocrystal Carbamazepine:Indometacin 1:1 is formed within few seconds and afterwards the crystallite size decreases extremely.
Two metal organic structures composed of the ligands benzene-1,4-dicarboxylate and pyridine-2,5-dicarboxylate and bismuth cations are presented: (H2Im)[Bi(1,4-bdc)2] (1) and [Bi(pydc)(NO3)2(H2O)2]*H2O (2) (bdc = benzenedicarboxylate, H2Im = imidazole cation, pydc = pyridinedicarboxylate). Both compounds were synthesised via grinding and the crystal structure of compound (2) was solved based on its powder diffraction pattern. Compound 1 crystallises isostructurally to the dimethyl ammonium containing compound (dma)[(Bi(1,4-bdc)2]. Raman spectroscopy and Extended X-ray absorption fine structure (EXAFS)
measurements provided additional information about the two mechanochemically synthesised metal organic compounds.
The current furfural production yield is low due to the use of non-selective homogeneous catalysts and expensive separation. In this work, partially hydroxylated MgF2 catalysts, synthesized using different water contents, were screened during xylose dehydration in watertoluene at 160 °C. The different Lewis/Brønsted ratios on the MgF2 catalysts showed that under-coordinated Mg can isomerize xylose to xylulose, whilst the surface OH-groups were responsible for the dehydration reactions. The presence of glucose as a co-carbohydrate reduced the furfural selectivity from 86 to 81%, whilst it also led to high 5-hydroxymethylfurfural selectivity. The tests catalyzed by MgF2 in combination with simultaneous N2-stripping showed that a furfural selectivity of 87% could be achieved using low xylose loadings. Moreover, the catalysts regenerated by H2O2 showed high activity during the dehydration tests in watertoluene at 160 °C.
Recent advances in vacuum sciences and applications are reviewed. Novel optical interferometer cavity devices enable pressure measurements with ppm accuracy. The innovative dynamic vacuum standard allows for pressure measurements with temporal resolution of 2 ms. Vacuum issues in the construction of huge ultra-high vacuum devices worldwide are reviewed. Recent advances in surface science and thin films include new phenomena observed in electron transport near solid surfaces as well as novel results on the properties of carbon nanomaterials. Precise techniques for surface and thin-film characterization have been applied in the conservation technology of cultural heritage objects and recent advances in the characterization of biointerfaces are presented. The combination of various vacuum and atmospheric-pressure techniques enables an insight into the complex phenomena of protein and other biomolecule conformations on solid surfaces. Studying these phenomena at solid–liquid interfaces is regarded as the main issue in the development of alternative techniques for drug delivery, tissue engineering and thus the development of innovative techniques for curing cancer and cardiovascular diseases. A review on recent advances in plasma medicine is presented as well as novel hypotheses on cell apoptosis upon treatment with gaseous plasma. Finally, recent advances in plasma nanoscience are illustrated with several examples and a roadmap for future activities is presented.
The vibrational density of states of a series of homologous triphenylene-based discotic liquid crystals HATn (n = 5, 6, 8, 10, 12) depending on the length of the aliphatic side chain is investigated by means of inelastic neutron scattering. All studied materials have a plastic crystalline phase at low temperatures, followed by a hexagonally ordered liquid crystalline phase at higher temperatures and a quasi isotropic phase at the highest temperatures. The X-ray scattering pattern for the plastic crystalline phase of all materials shows a sharp Bragg reflection corresponding to the intercolumnar distance in the lower q-range and a peak at circa 17 nm-1 related to intracolumnar distances between the cores perpendicular to the columns as well as a broad amorphous halo related to the disordered structure of the methylene groups in the side chains in the higher q-range. The intercolumnar distance increases linearly with increasing chain length for the hexagonal columnar ordered liquid crystalline phase. A similar behaviour is assumed for the plastic crystalline phase. Besides n = 8 all materials under study exhibit a Boson peak. With increasing chain length, the frequency of the Boson peak decreases and its intensity increases. This can be explained by a self-organized confinement model. The peaks for n = 10, 12 are much narrower than for n = 5, 6 which might imply the transformation from a rigid system to a softer one with increasing chain length. Moreover the results can also be discussed in the framework of a transition from an uncorrelated to a correlated disorder with increasing n where n = 8 might be speculatively considered as a transitional state.
A mechanical structure supported by nonlinear springs subjected to an external load is considered. If all mechanical parameters of the system were known, the displacement of the system subjected to this load could be easily calculated. If not all of the parameters are known, but the load and the displacement are measured at one location, an inverse problem exists. In the presented problem the nonlinear springs are unknown and have to be determined. At first glance a problem needs to be solved, which is underdetermined due to the number of unknown variables. However, evolutionary computing can be applied to solve this inverse, nonlinear and multimodal problem. Sometimes a prior knowledge exists on certain system properties, which is difficult to implement into analytical or numerical solver. This knowledge can play a decisive role in identifying the system properties and it can be easily included as boundary condition when applying evolutionary algorithm. This article examines how and under what conditions the spring resistances can be identified. The procedure is exemplified at a mechanical system of a pile foundation.
The observation of morphological details down to the nanometer range of the outer surface of micro-, submicro- and nanoparticles in a high-resolution scanning electron microscope (SEM) was extended with in-depth observation by enabling the transmission mode in the SEM, i.e. TSEM. The micro- and nanocapsules characterized in this study were fabricated as depots for protective agents to be embedded in innovative self-healing coatings. By combining the two imaging modes (upper and in-depth observation) complementing each other a better characterisation by a more comprehensive interpretation of the 'consistency' of the challenging specimens, e.g. including details 'hidden' beyond the surface or the real specimen shape at all, has been attained. Furthermore, the preparation of the quasi electron transparent samples onto thin supporting foils enables also elemental imaging by energy dispersive X-ray spectroscopy (EDX) with high spatial resolution. Valuable information on the elemental distribution in individual micro-, submicro- and even nanocapsules completes the '3D' high resolution morphological characterization at the same multimodal SEM/TSEM/EDX system.
In welding experiments conducted on heavy wall pipes, the penetration mode (full or partial penetration) occurred to be a significant factor influencing appearance of solidification cracks. To explain the observed phenomena and support further optimization of manufacturing processes, a computational model was developed, which used a sophisticated strategy to model the material. High stresses emerged in the models in regions which showed cracking during experiments. In partial penetration welding, they were caused by the prevention of weld shrinkage due to the cold and strong material below the joint. Another identified factor having an influence on high stress localization is bulging of the weld.
On the role of fluoro-substituted nucleosides in DNA radiosensitization for tumor radiation therapy
(2014)
Gemcitabine (2',2'-difluorocytidine) is a well-known radiosensitizer routinely applied in concomitant chemoradiotherapy. During irradiation of biological media with high-energy radiation secondary low-energy (<10 eV) electrons are produced that can directly induce chemical bond breakage in DNA by dissociative electron attachment (DEA). Here, we investigate and compare DEA to the three molecules 2'-deoxycytidine, 2'-deoxy-5-fluorocytidine, and gemcitabine. Fluorination at specific molecular sites, i.e., nucleobase or sugar moiety, is found to control electron attachment and subsequent dissociation pathways. The presence of two fluorine atoms at the sugar ring results in more efficient electron attachment to the sugar moiety and subsequent bond cleavage. For the formation of the dehydrogenated nucleobase anion, we obtain an enhancement factor of 2.8 upon fluorination of the sugar, whereas the enhancement factor is 5.5 when the nucleobase is fluorinated. The observed fragmentation reactions suggest enhanced DNA strand breakage induced by secondary electrons when gemcitabine is incorporated into DNA.
A method for the determination of very volatile organic compounds (VVOC) in air was developed and successfully tested for methanol and ethanol. Carbotrap300® (a multi-bed tube using Carbopack C®, Carbopack B® and Carbosive SIII®) was selected as sorption material for thermal desorption and tested for its suitability for emission test chamber measurements. The adsorption behaviour and the chromatographic results are influenced negatively by spiking aqueous solutions on the adsorption medium for calibration purposes. The latter effect can be reduced by blowing dry air across the adsorbent to remove the adsorbed water. Detection and quantification limits were determined for a GC-FID system and compared to GC-MS. The applicability of the method was tested with a methanol eliminating silane modified polymeric adhesive (SMP-adhesive for parquet) in an emission test chamber
Algal blooms are a frequent phenomenon in nearly all kinds of fresh water. Global warming and eutrophication by waste water, air pollution and fertilizers seem to lead to an increased frequency of occurrence. Many cyanobacteria produce hazardous and quite persistent toxins, which can contaminate the respective water bodies. This may limit the use of the raw water for many purposes. The purification of the contaminated water might be quite costly, which makes a continuous and large scale treatment economically unfeasible in many cases. Due to the obvious risks of algal toxins, an online or mobile detection method would be highly desirable. Several biosensor systems have been presented in the literature for this purpose. In this review, their mode of operation, performance and general suitability for the intended purpose will be described and critically discussed. Finally, an outlook on current developments and future prospects will be given.
Luminescence techniques are among the most widely used detection methods in the life and material sciences. At the core of these methods is an ever-increasing variety of fluorescent reporters (i.e., simple dyes, fluorescent labels, probes, sensors and switches) from different fluorophore classes ranging from small organic dyes and metal ion complexes, quantum dots and upconversion nanocrystals to differently sized fluorophore-doped or fluorophore-labeled polymeric particles. A key parameter for fluorophore comparison is the fluorescence quantum yield (Φf), which is the direct measure for the efficiency of the conversion of absorbed light into emitted light. In this protocol, we describe procedures for relative and absolute determinations of Φf values of fluorophores in transparent solution using optical methods, and we address typical sources of uncertainty and fluorophore class-specific challenges. For relative determinations of Φf, the sample is analyzed using a conventional fluorescence spectrometer. For absolute determinations of Φf, a calibrated stand-alone integrating sphere setup is used. To reduce standard-related uncertainties for relative measurements, we introduce a series of eight candidate quantum yield standards for the wavelength region of ~350950 nm, which we have assessed with commercial and custom-designed instrumentation. With these protocols and standards, uncertainties of 5–10% can be achieved within 2 h.
Odour measurements become increasingly important in view of the assessment of indoor air quality and the emissions of building products. Hence they need to be implemented into evaluation schemes such as the AgBB scheme. While there are already standards like DIN ISO 16000-28 and VDI 4302 Part 1 specifying the procedure of odour measurements using a comparison scale, no final validation of the method has been carried out so far. Therefore, a round robin test was conducted in 2012 with 12 participating laboratories that mainly consisted of the following two parts: 1) testing of the available comparison scales with respect to their operational performance and 2) execution of an odour assessment of an acrylic sealant using emission test chambers. Part one included the measurement of the air flow rates and the provided concentrations of the reference substance (acetone). Part two was conducted to test the performance of the laboratories and the applicability of DIN ISO 16000-28 and supplementary VDI 4302 Part 1 by assessing the perceived intensity and the hedonic tone of the air samples. Moreover, samples for VOC analysis were taken from the air in the emission test chamber on the 7th day of testing to allow for quality control. Resulting from this round robin test main deficits were detected and suggestions for the improvement of the odour measurement procedure were made.
A major requirement for the validation of methods assessing the risk associated with engineered nanoparticles (ENPs) is the use of reference materials (RMs). In the present contribution we review available RMs, ongoing projects and characterisation trends in the field. The conclusion is that actual approaches to RMs mostly deal with metrological considerations about single properties of the ENPs, typically their primary size, which can hardly be representative of nanoparticles characteristics in real testing media and therefore, not valid for reliable and comparable toxicological studies. As an alternative, we discussed the convenience and feasibility of establishing multi-parametric RMs for a series of ENPs, focusing on silica nanoparticles (SNPs). As a future perspective, the need to develop RMs based on hybrid nanoparticles is also discussed.
Indirect UV-absorption spectrometry was shown to be a valuable tool for chemical characterization of functionalized carbon nanotubes (CNTs). It complements data from X-ray photoelectron spectroscopy (XPS) or FTIR analysis since it helps to clarify the type and concentration of functional groups. The principles of indirect application of UV-spectrometry and its mathematical interpretation are discussed. Their facile application, together with their adequate sensitivity and high flexibility, make UV-absorption-based approaches a valuable alternative to fluorescence spectrometry. Here, the approach was applied to the chemical analysis of oxidizing substances on CNTs. For this, pristine CNTs of low but finite oxygen content as well as brominated CNTs were analyzed by reaction in suspension with UV-active thiol reagents and a styrene derivative. It was shown that carefully selected reagents allow differentiation and quantification of bromine and generally oxidizing entities like oxygen. For brominated CNTs, it was shown that physisorbed bromine may dominate the overall bromine content.
GMR sensors are widely used in many industrial segments such as information technology, automotive, automation and production, and safety applications. Each area requires an adaption of the sensor arrangement in terms of size adaption and alignment with respect to the field source involved. This paper deals with an analysis of geometric sensor parameters and the arrangement of GMR sensors providing a design roadmap for non-destructive testing (NDT) applications. For this purpose we use an analytical model simulating the magnetic flux leakage (MFL) distribution of surface breaking defects and investigate the flux leakage signal as a function of various sensor parameters. Our calculations show both the influence of sensor length and height and that when detecting the magnetic flux leakage of µm sized defects a gradiometer base line of 250 µm leads to a signal strength loss of less than 10% in comparison with a magnetometer response. To validate the simulation results we finally performed measurements with a GMR magnetometer sensor on a test plate with artificial µm-range cracks. The differences between simulation and measurement are below 6%. We report on the routes for a GMR gradiometer design as a basis for the fabrication of NDT-adapted sensor arrays. The results are also helpful for the use of GMR in other application when it comes to measure positions, lengths, angles or electrical currents.
A unifying review of bioassay-guided fractionation, effect-directed analysis and related techniques
(2012)
The success of modern methods in analytical chemistry sometimes obscures the problem that the ever increasing amount of analytical data does not necessarily give more insight of practical relevance. As alternative approaches, toxicity- and bioactivity-based assays can deliver valuable information about biological effects of complex materials in humans, other species or even ecosystems. However, the observed effects often cannot be clearly assigned to specific chemical compounds. In these cases, the establishment of an unambiguous cause-effect relationship is not possible. Effect-directed analysis tries to interconnect instrumental analytical techniques with a biological/biochemical entity, which identifies or isolates substances of biological relevance. Successful application has been demonstrated in many fields, either as proof-of-principle studies or even for complex samples. This review discusses the different approaches, advantages and limitations and finally shows some practical examples. The broad emergence of effect-directed analytical concepts might lead to a true paradigm shift in analytical chemistry, away from ever growing lists of chemical compounds. The connection of biological effects with the identification and quantification of molecular entities leads to relevant answers to many real life questions.
Several construction and building materials, including wood, glue and coatings, are possible sources of very volatile organic compounds (VVOCs) and volatile organic compounds (VOCs) like formic and acetic acid. Due to very high air tightness and very low air exchange rates in new buildings concentrations of these harmful substances can increase considerably. To minimize the risk, emissions from building products should be identified and quantified. With the common standard method, this means Tenax® sampling followed by thermal desorption and GC-MS analysis, these acids could not be detected sufficiently. The aim oft this study is the comparison of two different methods for the determination of acetic and formic acid. The sampling of method one, which is usually used for identification and quantification of VOCs, is done in accordance with ISO 16000-6 and ISO 16017-1 on Carbotrap® 202 multi-bed thermal desorption tube by subsequent identification and quantification with GC-MS. Method two is based on sampling on 2,4-dinitrophenylhydrazine (DNPH) cartridges, derivatisation, elution, identification and quantification of the derivatives with LC-MS/MS (liquid chromatography mass spectrometry/mass spectrometry).
Triacetone triperoxide (TATP) is a primary explosive, which was used in various terrorist attacks in the past. For the development of biosensors, immunochemical µ-TAS, electronic noses, immunological test kits, or test strips, the availability of antibodies of high quality is crucial. Recently, we presented the successful immunization of mice, based on the design, synthesis, and conjugation of a novel TATP derivative. Here, the long-term immunization of rabbits is shown, which resulted in antibodies of extreme selectivity and more than 1,000 times better affinity in relation to the antibodies from mice. Detection limits below 10 ng L-1 (water) were achieved. The working range covers more than four decades, calculated from a precision profile. The cross-reactivity tests revealed an extraordinary selectivity of the antibodies—not a single compound could be identified as a relevant cross-reactant. The presented immunoreagent might be a major step for the development of highly sensitive and selective TATP detectors particularly for security applications.
Ground penetrating radar (GPR) was used to characterize the frequency-dependent dielectric relaxation phenomena in ordinary Portland cement (OPC) hydration in concrete changing from fresh to hardened state. The study was experimented by measuring the changes of GPR A-scan waveforms over a period of 90 days, and processed the waveforms with short-time Fourier transform (STFT) in joint time-frequency analysis (JTFA) domain rather than a conventional time or frequency domain alone. The signals of the direct wave traveled at the concrete surface and the reflected wave from an embedded steel bar were transformed with STFT, in which the changes of peak frequency over ages were tracked. The peak frequencies were found to increase with ages and the patterns were found to match closely with primarily the well-known OPC hydration process and secondarily, the evaporation effect. The close match is contributed to the simultaneous effects converting free to bound water over time, on both conventional OPC hydration and dielectric relaxation mechanisms.
Digital radiography in the inspection of welded pipes to be installed under deep water offshore gas and oil pipelines, like a presalt in Brazil, in the paper has been investigated. The aim is to use digital radiography for nondestructive testing of welds as it is already in use in the medical, aerospace, security, automotive, and petrochemical sectors. Among the current options, the DDA (Digital Detector Array) is considered as one of the best solutions to replace industrial films, as well as to increase the sensitivity to reduce the inspection cycle time. This paper shows the results of this new technique, comparing it to radiography with industrial films systems. In this paper, 20 test specimens of longitudinal welded pipe joints, specially prepared with artificial defects like cracks, lack of fusion, lack of penetration, and porosities and slag inclusions with varying dimensions and in 06 different base metal wall thicknesses, were tested and a comparison of the techniques was made. These experiments verified the purposed rules for parameter definitions and selections to control the required digital radiographic image quality as described in the draft international standard ISO/DIS 10893-7. This draft is first standard establishing the parameters for digital radiography on weld seam of welded steel pipes for pressure purposes to be used on gas and oil pipelines.
Phosphorus-based flame retardancy mechanisms - Old hat or a starting point for future development?
(2010)
Different kinds of additive and reactive flame retardants containing phosphorus are increasingly successful as halogen-free alternatives for various polymeric materials and applications. Phosphorus can act in the condensed phase by enhancing charring, yielding intumescence, or through inorganic glass formation; and in the gas phase through flame inhibition. Occurrence and efficiency depend, not only on the flame retardant itself, but also on its interaction with pyrolysing polymeric material and additives. Flame retardancy is sensitive to modification of the flame retardant, the use of synergists/adjuvants, and changes to the polymeric material. A detailed understanding facilitates the launch of tailored and targeted development.
The class Dothideomycetes (along with Eurotiomycetes) includes numerous rock-inhabiting fungi (RIF), a group of ascomycetes that tolerates surprisingly well harsh conditions prevailing on rock surfaces. Despite their convergent morphology and physiology, RIF are phylogenetically highly diverse in Dothideomycetes. However, the positions of main groups of RIF in this class remain unclear due to the lack of a strong phylogenetic framework. Moreover, connections between rock-dwelling habit and other lifestyles found in Dothideomycetes such as plant pathogens, saprobes and lichen-forming fungi are still unexplored. Based on multigene phylogenetic analyses, we report that RIF belong to Capnodiales (particularly to the family Teratosphaeriaceae s.l.), Dothideales, Pleosporales, and Myriangiales, as well as some uncharacterised groups with affinities to Dothideomycetes. Moreover, one lineage consisting exclusively of RIF proved to be closely related to Arthoniomycetes, the sister class of Dothideomycetes. The broad phylogenetic amplitude of RIF in Dothideomycetes suggests that total species richness in this class remains underestimated. Composition of some RIF-rich lineages suggests that rock surfaces are reservoirs for plant-associated fungi or saprobes, although other data also agree with rocks as a primary substrate for ancient fungal lineages. According to the current sampling, long distance dispersal seems to be common for RIF. Dothideomycetes lineages comprising lichens also include RIF, suggesting a possible link between rock-dwelling habit and lichenisation.
Die Analytik von Phthalaten (DMP bis DEHP) in der Luft ist mit thermischer Desorption unter Verwendung von Quarzwolle als Adsorbens erfolgreich realisierbar. Dies wurde durch eine Methodenvalidierung bestätigt. Es wurden sowohl Messungen im Innenraum als auch in Emissionskammern vorgenommen. In den Emissionskammermessungen wurden mögliche Senkeneffekte der Kammeroberfläche (Glas) untersucht. Unter Zuhilfenahme der idealen Abklingkurve wird bestätigt, dass diese Oberfläche eine Senke darstellt.
Cold cracking resistance is a relevant evaluation criterion for welded joints and affected by residual stresses which result from the welding procedure. Compressive residual stresses can thereby have a positive influence on preventing cracking. A unique possibility of generating compressive residual stresses already during the welding procedure is offered by the so-called Low Transformation Temperature (LTT) filler wires. Compared to conventional wires, these materials show decreased phase transformation temperatures which can work against the cooling-specific contraction. In consequence, distinct compressive residual stresses can be observed within the weld and adjacent areas. The strength of these fillers makes them potentially applicable to high-strength steel welding. Investigations were carried out to determine the phase transformation behaviour of different LTT-filler materials. Transformation temperatures were identified using Single Sensor Differential Thermal Analysis (SS-DTA). Additionally Synchrotron radiation was used to measure the transformation kinetics of all involved crystalline phases during heating and cooling of a simulated weld thermal cycle.
For the safety and cost efficiency of welded high-strength steel structures, precise knowledge of the level and distribution of welding- and cooling-specific stresses and residual stresses is essential, since they exert a decisive influence on strength, crack resistance, and finally on the bearable service load. This paper presents innovative filler materials, of which the phase transformation temperature was deliberately adjusted via the chemical composition. The transformation behaviour of these martensitic Low Transformation Temperature (LTT-) filler materials shows direct effects on the local residual stresses in the weld and the HAZ. These effects can purposefully be exploited to counteract the thermally induced shrinkage of the material and to produce significant compressive residual stresses in the weld. Comparative welding experiments were carried out on 690 MPa high-strength base materials using various LTT-filler materials. High energy synchrotron radiation was used for residual stress measurement. Particularly the use of high energy synchrotron radiation makes it possible to detect the residual stress condition fast without destruction of material. Thereby, residual stress depth gradients can be determined simultaneously without removing material. In steel, gradients of up to 150 µm can be resolved in such a way. Furthermore, the application of high energy radiation permits determination of residual stresses of any available residual austenite contents. Results show significant dependence of transformation temperatures on the resulting residual stress level and distribution.
Aflatoxins, a group of structurally related mycotoxins, are well known for their
toxic and carcinogenic effects in humans and animals. Aflatoxin derivatives and protein
conjugates are needed for diverse analytical applications. This work describes a reliable
and fast synthesis of novel aflatoxin derivatives, purification by preparative HPLC and
characterisation by ESI-MS and one- and two-dimensional NMR. Novel aflatoxin bovine
serum albumin conjugates were prepared and characterised by UV absorption and
MALDI-MS. These aflatoxin protein conjugates are potentially interesting as immunogens
for the generation of aflatoxin selective antibodies with novel specificities.
To date silica nanoparticles (SNPs) play an important role in modern technology and nanomedicine. SNPs are present in various materials (tyres, electrical and thermal insulation material, photovoltaic facilities). They are also used in products that are directly exposed to humans such as cosmetics or toothpaste. For that reason it is of great concern to evaluate the possible hazards of these engineered particles for human health. Attention should primarily be focussed on SNP effects on biological barriers. Accidentally released SNP could, for example, encounter the alveolar-capillary barrier by inhalation. In this study we examined the inflammatory and cytotoxic responses of monodisperse amorphous silica nanoparticles (aSNPs) of 30 nm in size on an in vitro coculture model mimicking the alveolar-capillary barrier and compared these to conventional monocultures.
Methods
Thus, the epithelial cell line, H441, and the endothelial cell line, ISO-HAS-1, were used in monoculture and in coculture on opposite sides of a filter membrane. Cytotoxicity was evaluated by the MTS assay, detection of membrane integrity (LDH release), and TER (Transepithelial Electrical Resistance) measurement. Additionally, parameters of inflammation (sICAM-1, IL-6 and IL-8 release) and apoptosis markers were investigated.
Results
Regarding toxic effects (viability, membrane integrity, TER) the coculture model was less sensitive to apical aSNP exposure than the conventional monocultures of the appropriate cells. On the other hand, the in vitro coculture model responded with the release of inflammatory markers in a much more sensitive fashion than the conventional monoculture. At concentrations that were 10-100fold less than the toxic concentrations the apically exposed coculture showed a release of IL-6 and IL-8 to the basolateral side. This may mimic the early inflammatory events that take place in the pulmonary alveoli after aSNP inhalation. Furthermore, a number of apoptosis markers belonging to the intrinsic pathway were upregulated in the coculture following aSNP treatment. Analysis of the individual markers indicated that the cells suffered from DNA damage, hypoxia and ER-stress.
Conclusion
We present evidence that our in vitro coculture model of the alveolar-capillary barrier is clearly advantageous compared to conventional monocultures in evaluating the extent of damage caused by hazardous material encountering the principle biological barrier in the lower respiratory tract.