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Subjecting a thin NiTi specimen to uniaxial tension often leads to a localized martensitic transformation: macroscopic transformation bands form and propagate through the specimen, separating it into regions of fully transformed martensite and original austenite. In the present study, the alternating current potential drop (ACPD) technique is used to analyze the change in electrical resistance of ultra-fine grained NiTi wires subjected to a broad range of thermo-mechanical load cases: (i) uniaxial tensile straining at constant temperatures (pseudoelastic deformation); (ii) cooling and heating through the transformation range at constant load (actuator load case); (iii) a combination of mechanical and thermal loading. We monitor the ACPD signals in several zones along the gauge length of specimens, and we demonstrate that a localized type of transformation is a generic feature of pseudoelastic as well as of shape memory deformation. Moreover, the ACPD signals allow to differentiate between temperature-induced martensite (formed during cooling at no or relatively small loads), stress-induced martensite, and reoriented martensite (formed under load at low temperatures).
Die Ressourcenverknappung und steigende Preise rücken nachhaltiges Wirtschaften und die Wiederverwertung von Abfällen in den Blickpunkt der Forschung. Bauabfälle sind in Deutschland – mit 72,4 Mio.t im Jahr 2004 – der größte Abfallstrom. Es wird ein Überblick über den Stand der Technik zur Aufarbeitung und Verwertung von Bauabfällen gegeben und die Anforderungen an Bauabfälle, die als Sekundärrohstoff eingesetzt werden sollen, diskutiert. Die Forschung im Baustoffrecycling bezieht sich sowohl auf neue Aufbereitungstechniken als auch auf die Charakterisierung der Recyclingmaterialien sowie auf deren Einfluss auf die Betonqualität. Die Eignung und Verwertung von Bauabfällen als Sekundärrohstoffe für Baustoffe wird anhand ihrer chemischen Zusammensetzungen mit Hilfe von ternären Diagrammen diskutiert.----------------------------------------------------------------------
An overview about quantity of construction and demolition waste (CDW) and a state of the art of the reuse is given. The technology is described, which is applied for the processing of CDW in a stationary plant. The requirements on recycled aggregates, which shall be used in road construction or in manufacturing of concrete, can be divided in such related to the material and physical properties and such related to the environmental properties. The rules give guidance on the composition with the aim of excluding the constituents with unfavourable features. The environmental standards which yet in discussion are give threshold of the leachable components in recycled aggregates. The material potential of building waste is discussed. Information on the chemical composition of recycled materials is compared with the composition of pure materials. With the aid of ternary charts such building materials are identified, in which the recycled materials can be used as recycled feedstock.
Analysis of Kikuchi band contrast reversal in electron backscatter diffraction patterns of silicon
(2010)
We analyze the contrast reversal of Kikuchi bands that can be seen in electron backscatter diffraction (EBSD) patterns under specific experimental conditions. The observed effect can be reproduced using dynamical electron diffraction calculations. Two crucial contributions are identified to be at work: First, the incident beam creates a depth distribution of incoherently backscattered electrons which depends on the incidence angle of the beam. Second, the localized inelastic scattering in the outgoing path leads to pronounced anomalous absorption effects for electrons at grazing emission angles, as these electrons have to go through the largest amount of material. We use simple model depth distributions to account for the incident beam effect, and we assume art exit angle dependent effective crystal thickness in the dynamical electron diffraction calculations. Very good agreement is obtained with experimental observations for silicon at 20 key primary beam energy.
Reinforced concrete bridge decks are exposed to several types of deterioration processes: corrosion, alkali silica reaction, carbonation, shrinkage, freeze thaw actions, and so forth. The most commonly found problem is corrosion-induced bridge deck delamination. Previous studies have shown that surveys of bridges relying on a single nondestructive evaluation (NDE) technology provide limited information about the condition of concrete bridge decks. To overcome limitations of individual technologies, a complementary approach using several NDE technologies should be used in bridge deck evaluation. The presented approach utilizes a suite of NDE technologies, namely, impact echo (IE), ultrasonic surface waves (USW), ground-penetrating radar (GPR), half-cell potential (HCP), and electrical resistivity (ER). The suite of NDE technologies was implemented in the evaluation of bridge decks on nine bridges in Iowa. The NDE was complemented by ground-truth measurements on the cores extracted from all nine bridge decks. Condition assessment with the five NDE technologies has clearly shown their advantages and limitations. For example, the GPR surveys provided assessment of concrete deterioration at relatively high speeds of data collection. In contrast, IE provided high accuracy in detection and characterization of delaminations in the deck but at a lower testing speed. HCP and ER tests provided assessment of the likelihood of corrosion, whereas the USW test provided accurate assessment of the effects of deterioration processes and defects on mechanical properties, primarily the degradation of the elastic modulus. Most important, the survey showed the advantages of use of multimodal NDE surveys in the comprehensiveness of condition assessment of concrete bridge decks.
Commercially available linear alkylbenzenesulfonates (LASs) are a mixture of various homologues and isomers, leading to 20 major species. In this work we investigated the commercial product by liquid chromatography-solid phase extraction-nuclear magnetic resonance spectroscopy-mass spectrometry (LC-SPE-NMR/MS). The commercial product was separated into 17 fractions by liquid chromatography (LC). After chromatographic separation, 5% of the flow was split to a mass spectrometer (MS) while 95% was send to post-column solid phase extraction cartridges for enrichment of the analytes (LC-SPE). After elution from the SPE-cartridges a NMR-spectrometer equipped with a cryo-probe was used for the characterisation of the different LASs species. For the first time H-1-1D and H-H-COSY spectra for 14 LASs species out of 20 major isomers are presented, whereas the 6 remaining species are detected as mixtures in 3 H-1-1D and H-H-COSY spectra. These data were used to correlate the chromatographic retention of the LASs isomers to the substitution pattern of the alkyl chain.
The paper describes past and present efforts in modeling of laser-induced plasma and overviews plasma diagnostics carried out by pump-probe techniques. Besides general information on existing plasma models, the emphasis is given to models relevant to spectrochemical analysis, i.e. models of radiating plasma. Special attention is paid to collisional-radiative (CR) and collisional-dominated (CD) plasma models where radiative processes play an important role. Also, calibration-free (CF) models are considered which may endow with the possibility for standardless spectroscopic analysis. In the diagnostic part, only methods based on the use of additional diagnostic tools (auxiliary lasers, optics, and probes) are described omitting those based on plasma own radiation. A short review is provided on image-based diagnostics (shadowgraphy, schlieren, and interferometry), absorption and fluorescence, Langmuir probe, and less frequently used cavity ringdown and Thomson scattering methods.
Pulse thermography of concrete structures is used in civil engineering for detecting voids, honeycombing and delamination. Quantitatively realistic numerical 3D simulation is difficult due to the arising boundary layer at the heated surface and unreliable information about material parameters and environmental conditions. We address both issues by a semi-analytic reformulation of the heat transport problem and by parameter identification. Numerical results are compared with measurements of a test specimen.
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.
The influence of humin preparations obtained from low-moor peat by the mechanochemical method on the changes in the microflora number and hydrocarbon composition in oil-polluted soils was studied. The intense growth of the microorganisms in number especially in the oil-polluted soil was observed upon the application of humin acids (at a concentration of 0.005 wt %) extracted from mechanically processed peat. In this case, the content of the extracted bitumoids decreased down to 40 wt %. The soil microflora stimulated by the humin preparations was shown to have highly destructive oil-oxidizing activity reflected in the indices of the hydrocarbon biodegradation. The mechanochemical activation of peat allows raising the efficiency of extracting the humic acids and can be a reason for increasing the availability of their individual components and parts of molecules, including micro- and macroelements that are used by microbial cells as sources of nutrition and energy.
In contrast to classical low temperature polymer electrolyte fuel cells (LT-PEFCs), the membrane conductivity in high temperature polymer electrolyte fuel cells (HT-PEFCs) (operating temperature ~ 160 °C) is based on proton transport within phosphorus-oxygen acids at different levels of hydration, orthophosphoric acid (H3PO4) being the simplest example. We present for the first time in-situ synchrotron X-ray radiography measurements applied to a HT-PEFC to gain insight into the local composition of the membrane electrode assembly (MEA) under dynamic operating conditions. Transmission changes during the radiographic measurements exhibit a clear influence of the formation of product water on the membrane composition.
The impact-echo method has been successfully applied to identify defects inside concrete. In addition, to detect ungrouted tendon ducts in a large concrete slab, a scanning impact-echo technique is developed. However, since resonant frequencies in the spectrum responsible for the travel paths via defects are only taken into account, the method could lead to erroneous results due to complicated spectra obtained in the tests. Consequently, Stack Imaging of spectral amplitudes Based on Impact-Echo (SIBIE) procedure has been developed to improve the data interpretation. Conventionally, SIBIE is applied to a single measurement data and a point information of defects is obtained at the area, where the impact test is performed. In this study, SIBIE is applied to scanning impact-echo data. Locations of ungrouted tendon ducts embedded in a large concrete specimen are investigated. In order to visualize the whole cross-section tested, the SIBIE analysis is modified, introducing an elliptical integration mode. It is demonstrated that ungrouted tendon ducts are successfully located by the modified SIBIE analysis, whereas results of the conventional B-scan analysis are not so good as the modified SIBIE analysis.
Improved large mesoporous ordered molecular sieves - Stabilization and acid/base functionalization
(2010)
The preparation of nanoporous materials with enhanced stability using an improved synthesis route using reactive inorganic silica and alumina species is reported. This way improved mesoporous molecular sieves were obtained. The synthesized aluminum substituted mesoporous molecular materials (Al-MMS) contain very large pores of 50200 Å size combined with an improved pore wall thickness. Increased wall thickness and Al substitution lead to an improved chemical stability against alkaline solution. The textural, structural and acid properties are investigated by physico-chemical methods. The catalytic performance acidic materials was tested in the benzoylation reaction; amino functionalized materials were studied in the base catalyzed Michael addition.
Thin metal-filled polyterafluoroethylene films with various metal concentration were produced by co-deposition in vacuum. Metal nanocluster size increased with metal concentration. Films were heated up to 300 degrees C, their optical spectra were recorded during heating. The changes in plasmon band shape and wavelength of the nanocluster ensemble during heating are not linearly related with metal concentration and heating temperature. This is caused by different thermal behavior of the complex processes, which are taking place in each of the two materials present in the film. The metal cluster size and optical properties of the whole ensemble can be purposefully formed by varying metal nature, its concentration and annealing temperature of the film. Nano- and micro-domains with properties different from original film were generated by focused excimer laser or electron beam. Gold-filled PTFE nano-structured films were used as substrate for surface enhanced Raman scattering measurements of ultrathin film of Rhodamine 6G dye.
Synchrotron radiation-based microcomputed tomography (SR-µCT) has become a valuable tool in the
structural characterization of different types of materials, achieving volumetric details with micrometre
resolution. Biomedical research dealing with porous polymeric biomaterials is one of the research fields
which can benefit greatly from the use of SR-µCT. This study demonstrates that current experimental setups
at synchrotron beamlines achieve a sufficiently high resolution in order to visualize the positions of
individual cartilage cells cultivated on porous gelatine scaffolds made by a freeze-structuring technique.
Depending on the processing parameters, the pore morphology of the scaffolds investigated was changed
from large-pore sized but non-ordered structures to highly directional and fine pored. The cell-seeded
scaffolds were stained with a combined Au/Ag stain to enhance the absorption contrast in SR-µCT. While
only some cells showed enhanced absorption contrast, most cells did not show any difference in contrast
to the surrounding scaffold and were consequently not detectable using conventional greyscale threshold
methods. Therefore, using an image-based three-dimensional segmentation tool on the tomographic data
revealed a multitude of non-stained cells. In addition, the SR-µCT data were compared with data obtained
from scanning electron microscopy, energy dispersive X-ray spectroscopy and histology, while further
linking the initial cell density measured via a MTT assay to the pore size as determined by SR-µCT.
This review introduces multifunctional optical nanosensors based on surface-enhanced Raman scattering (SERS) and demonstrates their application in live cells. The novel nanosensors have the potential to improve our understanding of cellular processes on the molecular level. The hybrid sensor consists of gold or silver nanoparticles with an attached reporter species. The sensor can be detected and imaged based on the SERS signature of the reporter. This results in several advantages, such as high spectral specificity, multiplex capabilities, improved contrast, and photostability. SERS sensors not only highlight cellular structures, based on enhanced Raman spectra of intrinsic cellular molecules measured in the local optical fields of the gold nanoparticles, they also provide molecular structural information on their cellular
environment. Moreover, the SERS signature of the reporter can deliver information on the local pH value inside a cell at subendosomal resolution. SERS sensors are suitable for one- and two-photon excitation.
Creep damage of single-crystal nickel base superalloys: mechanisms and effect on low cycle fatigue
(2010)
The main mechanisms of creep damage of single-crystal nickel-base superalloys are the loss of the interface coherency, coarsening of the γ / γ'-microstructure, precipitation of topologically closed packed phases and growth of porosity. This degradation deteriorates the mechanical properties such as yield stress, creep lifetime and especially low-cycle fatigue life, which can be reduced nearly by a factor of 10. The degradation kinetics during creep was characterised quantitatively on the superalloy CMSX-4. A new non-destructive testing technique was applied to cover a wide test parameter range with few specimens in a relatively short time: repeated load annealing of wedge shaped specimens.
The results from several laboratory studies of the relationships between electrical polarization and physical properties of porous media have prompted interest in the potential use of low-frequency electrical spectra to qualitatively or quantitatively map variation in hydrogeologic properties in the field. Compiling several published and unpublished data sets, supported by new measurements, we have examined the low-frequency electrical spectra of a range of natural and artificial porous media to assess the generality of proposed relationships between electrical and physical properties. Our work confirms a significant positive correlation between the magnitude of electrical polarization (quantified as imaginary conductivity at a specific frequency) and the surface-area/pore-volume ratio Spor. Analyzing the parameters of ageneralized Cole-Cole resistivity relaxation model fitted to many electrical spectra, we observe two apparent controls on the electrical relaxation. For samples with abundant relatively large pore throats, we observe a distinct increase in the time constant of the model with modal pore-throat size, in accordance with classical electrical relaxation models. However, for media with pore structures dominated by small pore throats, the diffusion-length scales do not appear to be controlled by modal pore-throat size. We conclude that for such media, the microstructure of the network of small pores leads to some connectivity of diffusion paths; thus, these samples exhibit relatively large time constants. There is potential value in addition to limitations when using electrical spectra to estimate physical properties of porous media, and we see the need for more appropriate generalized theories of electrical polarization in hydrogeologic media.
A number of recent investigations have highlighted the potential value of using relaxation times derived from electrical spectra to infer key physical properties of permeable rocks. To date, most studies have assumed a grain size or pore throat as a measure of the length scale of the ionic diffusive process, although this has been challenged in recent experimental investigations. We compare the electrical spectra of three sandstones, adopting a new approach in which the temperature of the rock samples is perturbed and the relaxation time measured as a function of temperature. Our results suggest that, for the sandstones tested here, the effective diffusion coefficient should be considered as a function of the electrical tortuosity. These findings may help explain the apparent long relaxation times observed in low-permeability rocks in recent experimental studies. We also highlight the need to account for temperature in related studies of electrical spectra.
In this study, we use and extend a recently developed zonal cooperative inversion approach and apply it to the inversion of three independent geophysical field data sets. We invert crosshole P-wave, S-wave, and georadar data sets acquired in sand and gravel dominated unconsolidated sediments to detect and characterize different sedimentary units relevant for an engineering or hydrological site characterization. The zonal cooperative inversion of the three traveltime data sets results in a single subsurface model, which is a geophysical three-parameter model (P-wave, S-wave, and georadar velocity) outlining the major subsurface zonation while explaining all input data sets. Comparing our zonal model to direct push (DP) logging data (tip resistance, sleeve friction, and dielectric permittivity) shows good agreement; i.e., the zones in our geophysical model largely correspond to major DP parameter changes. Furthermore, we demonstrate how the sparse DP data can be inter- and extrapolated to the entire tomographic plane which allows for further geotechnical and hydrological interpretations. This study illustrates that the zonal cooperative inversion approach is highly flexible and an excellent tool to characterize a variety of environments in terms of multiple physical parameters.
The most efficient construction materials for boiler water walls and superheaters in steam power plants are ferritic and martensitic steels. In practical operation, tubes are exposed simultaneously to combustion gas and air/steam on their opposite surfaces. The corrosion behavior of ferritic-martensitic steels under such dual atmospheres is nondistinctive and has been investigated in a specially designed test equipment between 500°C and 620°C. The power plant conditions were simulated with a flowing and pressurized (80 bar) combustion gas on the inner side of the tube, which contains water (H2O) and carbon dioxide (CO2). On the outer side, tube material was exposed to air. Oxides that formed on the air side under dual atmosphere conditions were significantly different from the oxide scales formed when the alloy was exposed to air only. It is assumed that the anomalous corrosion behavior during the dual atmosphere exposure is due to hydrogen and carbon diffusion through the bulk alloy from the combustion gas side to the air side. Both species are produced when the material reacts with the gas phase. Because of its high diffusivity, hydrogen is thought to affect the corrosion process on the air side from the beginning of the corrosion exposure, whereas carbon reaches the opposite side after a considerably longer time period.
The surface enhanced Raman scattering (SERS) spectrum of a reporter molecule attached to gold or silver nanostructures, which is pH-sensitive, can deliver information on the local pH in the environment of the nanostructure. Here, we demonstrate the use of a mobile SERS nanosensor made from gold nanaoaggregates and 4-mercaptobenzoic acid (pMBA) attached as a reporter for monitoring changes in local pH of the cellular compartments of living NIH/3T3 cells. We show that SERS nanosensors enable the dynamics of local pH in individual live cells to be followed at subendosomal resolution in a timeline of cellular processes. This information is of basic interest for a better understanding of a broad range of physiological and metabolic processes as well as for a number of biotechnological applications.
Surface-enhanced Raman scattering: a new optical probe in molecular biophysics and biomedicine
(2010)
Sensitive and detailed molecular structural
information plays an increasing role in molecular biophysics
and molecular medicine. Therefore, vibrational
spectroscopic techniques, such as Raman scattering, which
provide high structural information content are of growing
interest in biophysical and biomedical research. Raman
spectroscopy can be revolutionized when the inelastic
scattering process takes place in the very close vicinity of
metal nanostructures. Under these conditions, strongly
increased Raman signals can be obtained due to resonances
between optical fields and the collective oscillations of the
free electrons in the metal. This effect of surface-enhanced
Raman scattering (SERS) allows us to push vibrational
spectroscopy to new limits in detection sensitivity, lateral
resolution, and molecular structural selectivity. This opens
up exciting perspectives also in molecular biospectroscopy.
This article highlights three directions where SERS can offer interesting new capabilities. This includes SERS as a
technique for detecting and tracking a single molecule, a
SERS-based nanosensor for probing the chemical composition
and the pH value in a live cell, and the effect of socalled
surface-enhanced Raman optical activity, which
provides information on the chiral organization of molecules
on surfaces.
Surface-enhanced Raman scattering hybrid nanoprobe multiplexing and imaging in biological systems
(2010)
Surface-enhanced Raman scattering (SERS) labels and probes consisting of gold and silver nanoaggregates and attached reporter molecules can be identified by the Raman signature of the reporter molecule. At the same time, SERS hybrid probes deliver sensitive molecular structural information on their nanoenvironment. Here we demonstrate full exploitation of the multifunctional and multiplexing capabilities inherent to such nanoprobes by applying cluster methods and principal components approaches for discrimination beyond the visual inspection of individual spectra that has been practiced so far. The reported results indicate that fast, multivariate evaluation of whole sets of multiple probes is feasible. Spectra of five different reporters were shown to be separable by hierarchical clustering and by principal components analysis (PCA). In a duplex imaging approach in live cells, hierarchical cluster analysis, K-means clustering, and PCA were used for imaging the positions of different types of SERS probes along with the spectral information from cellular constituents. Parallel to cellular imaging experiments, cytotoxicity of the SERS hybrid probes containing aromatic thiols as reporters is assessed. The reported results suggest multiplexing applications of the nontoxic SERS nanoprobes in high density sensing and imaging in complex biological structures.
The processes associated with pollen germination were studied in vitro for two tree species, Salix caprea and Fraxinus excelsior under different nutrient conditions. The results provide evidence of changes in chemical composition of the pollen grains during germination. From the comparison of spectra of the pollen grain body and the growing pollen tube, it can be concluded that there are major chemical differences between these two morphological units. Comparison of germinated and ungerminated pollen grains reveals alterations in the metabolism. Composition of the germinating pollen grain and its morphological units depends on the plant species, but also on the nutrient conditions. The results suggest species-specific utilization of metabolite storage, and potential alterations of the pollen outer coat. Furthermore, discharge of molecules into the nutrient medium may depend on the nutrient conditions in the germination experiments. This has implications for further experiments on dynamic processes in pollen and related plant materials.
HBCD stereoisomer pattern in mirror carps following dietary exposure to pure Gamma-HBCD enantiomers
(2010)
We report the results of an analytical investigation
on 416 silver-copper coins stemming from the Ottoman
Empire (end of 16th and beginning of 17th centuries), using
synchrotron micro X-ray fluorescence analysis (SRXRF).
In the past, analyses had already been conducted with energy
dispersive X-ray fluorescence analysis (EDXRF), scanning
electron microscopy with energy dispersive X-ray spectrometry
(SEM/EDX) and proton induced X-ray emission spectroscopy (PIXE).With this combination of techniques it was
possible to confirm the fineness of the coinage as well as to
study the provenance of the alloy used for the coins.
For the interpretation of the data statistical analysis
(principal component analysis—PCA) has been performed.
A definite local assignment was explored and significant
clustering was obtained regarding the minor and trace elements
composing the coin alloys.
The Sarmizegetusa bracelets
(2010)
We present the authentication and analysis of these beautiful Dacian bracelets of the first century BC, originally pillaged by treasure hunters and recovered thanks to an international crime chase. They were originally fashioned from gold panned from the rivers or dug from the mines of Transylvania and hammered into the form of coiled snakes. The lack of context is the greatest loss, but a votive purpose is likely given their proximity to the great sacred centre at Sarmizegetusa Regia.
The corrosion behaviour of martensitic stainless injection-pipeline steel X46Cr13 exposed to CO2 saturated artificial saline brine with high chloride concentration similar to onshore CCS-site at Ketzin, Germany has been investigated by means of electrochemical technique and microscopic observations at short exposure times (up to 24?h) and by mass loss and metallographic observations at exposure times up to 17520?h. Pitting corrosion kinetics has been characterised and the predictions about the corrosion mechanism are made.
Die Wettbewerbsfähigkeit der Chemischen und Pharmazeutischen Industrie basiert auf der Sicherung der geforderten Produktqualität bei einer optimalen Nutzung von Anlagen, Rohstoffen und Energie [1]. Eine gute Prozessführung unter Einsatz zuverlässiger Prozessanalytik sichert hier den globalen Wettbewerbsvorteil gegenüber Niedriglohnländern, die mit weniger effizienten Verfahren produzieren. Prozessanalytik trägt zur Erhöhung der Prozess- und Anlagensicherheit bei. In Kombination mit geeigneten Informationsmanagementsystemen verbessert dieser Ansatz ständig das Wissen über den Prozess und führt damit zu einer präventiven Sicherstellung der geforderten Qualität.
Plasmaparticle interactions are explored through the introduction of single microdroplets into laser-induced plasmas. Both spectroscopic analysis and direct imaging of analyte atomic emission are used to provide insight into the various fundamental processes, namely desolvation, atomization, and atomic diffusion. By doping the 50 µm droplets with Lu, Mg or Ca, the analyte excitation temperature and the ion-to-neutral emission ratio are explored as a function of plasma residence time following breakdown. The data suggest a change in the local plasma conditions about the analyte atoms around 1520 µs following breakdown, which may be interpreted as an overall transition from localized (i.e. perturbed) plasma conditions to the global (i.e. bulk) plasma conditions. A direct assessment of the hydrogen atomic diffusion coefficient following analyte desolvation reveals a value of 1.7 m² s-1 in the first 250500 ns. This value is in good overall agreement with a theoretical analysis and with an analytical treatment of a surface source of hydrogen atoms. In contrast, calcium emission is only observed beyond about 1 µs, with a diffusion coefficient at least an order of magnitude below the hydrogen value. The temporal H and Ca emission data suggest that water vaporizes first, leaving an ever increasing Ca analyte concentration until finally, with nearly all water desorbed, the Ca fraction is vaporized. Overall, the data support the conclusion that finite time-scales of heat and mass transfer play an important role in localized plasma perturbations in the vicinity of the analyte, which has important implications for the LIBS analyte signal.
End-on inductively coupled plasma optical emission spectrometry (ICP-OES) of the relative mass distributions in ensembles of spherical SiO2 particles with small and large size variations is presented. The particles are introduced into the ICP by injection of monodisperse microdroplets generated from diluted particle suspensions. The spectroscopic signals, taking into account the peak or the integrated intensities of the Si 288.16 nm line, are compared with mass distribution measurements of corresponding SiO2 particle ensembles performed by Scanning Electron Microscopy (SEM). It is found that the relative mass distributions measured by ICP-OES are in good agreement with SEM measurements if the spectroscopic signal to noise ratio is sufficiently large indicating that intensity variations due to different particle trajectories in the ICP are less important than expected.
An international intercomparison involving eight national metrology institutes (NMIs) was conducted to establish their current measurement capabilities for determining five selected congeners from the brominated flame retardant classes polybrominated diphenyl ethers and polybrominated biphenyls. A candidate reference material consisting of polypropylene fortified with technical mixtures of penta-, octa- and decabromo diphenyl ether and decabromo biphenyl, which was thoroughly assessed for material homogeneity and stability, was used as study material. The analytical procedures applied by the participants differed with regard to sample pre-treatment, extraction, clean-up, employed calibrants and type of calibration procedure as well as regarding analytical methods used for separation, identification and quantification of the flame retardant congeners (gas chromatography coupled to an electron capture detector (GC-ECD), gas chromatography-mass spectrometry in the electron ionisation mode (GC-EI-MS), gas chromatography-mass spectrometry in the electron capture negative ionisation mode (GC-ECNI-MS), and liquid chromatography-inductive coupled plasma-mass spectrometry (LC-ICP-MS)). The laboratory means agreed well with relative standard deviations of the mean of means of 1.9%, 4.8%, 5.5% and 5.4% for brominated diphenyl ether (BDE) 47, 183 and 209 and for the brominated biphenyl (BB) congener 209, respectively. For BDE 206, a relative standard deviation of 28.5% was obtained. For all five congeners, within-laboratory relative standard deviations of six measurements obtained under intermediate precision conditions were between 1% and 10%, and reported expanded measurements uncertainties typically ranged from 4% to 10% (8% to 14% for BDE 206). Furthermore, the results are in good agreement with those obtained in the characterization exercise for determining certified values for the flame retardant congeners in the same material. The results demonstrate the state-of-the-art measurement capabilities of NMIs for quantifying representative BDE congeners and BB 209 in a polymer. The outcome of this intercomparison (pilot study) in conjunction with possible improvements for employing exclusively calibrants with thoroughly assessed purity suggests that a key comparison aiming at underpinning calibration and measurement capability (CMC) claims of NMIs can be conducted.
Slags from the production of high-alloyed steel contain both chemically bound chromium (mainly as Cr2O3) in the mineral fraction and elemental chromium in the metallic remainders. Thermochemical post treatment of the slag in an electric arc furnace under reducing conditions enables the nearly complete recovery of the total amount of chromium in form of a metallic alloy. The best results were achieved by resistance melting (submerged electrodes) with addition of a reducing agent into the melt. The efficiencies of the reducing agents carbon, aluminium, silicon (as ferrosilicon) and silicon carbide were investigated and compared. As aluminium is the strongest reducing agent, it is less selective and reduces much more SiO2 than Cr2O3. While SiC shows only low reactivity because of its high thermal resistance, carbon and silicon had the highest reducing potentials: More than 97% of the chemically bound chromium can be recovered by application of these reducing agents. Due to the high temperature required for the reduction of the chromium compounds, the reduction of SiO2 as an undesired side reaction cannot be avoided. However, compared with mechanical procedures that are limited to the recovery of the metallic remainders, the total chromium recovery can be significantly increased by the described reductive melting procedure.
Thermal barrier coatings (TBCs) are used to increase the operating temperature of land-, sea-, or air-based turbines. As failure of the coating may result in serious damage of the turbine, reliable estimation of the lifetime is essential. Most experiments to assess the lifetime or to determine parameters for simulations of the behavior of TBCs are done by burner-rig-tests, where the operating conditions are simulated by cyclic heating of the surface and cooling of the backside of a coated sample.
In this work a possibility is presented to do comparable experiments by heating the surface with laser irradiation instead of a burner. For this purpose a Nd:YAG-laser with a maximum output power of 1?kW and a wavelength of 1064?nm is used. The laser spot can be moved by integrated optics across the sample surface to achieve homogeneous heating of the coating. Cooling of the backside is done by air. The temperature of the sample surface is determined by an infrared-camera which also enables the possibility to detect failures in the coating via thermography. Additionally, acoustic sensors attached to the sample holder are used to detect failures in the sample. The investigated ceramic material (yttria stabilized zirconia) has a very low absorption coefficient at the used laser wavelength. Therefore, a pre-treatment of the samples was needed to increase the absorption coefficient to be able to heat up the samples.
In this paper, the experimental setup and first experimental results are presented.
Quantification of energy dispersive SRXRF for the certification of reference materials at BAMline
(2010)
The certification of reference materials (CRMs) is one of the main tasks of the BAM Federal Institute for Materials Research and Testing. In this context CRMs for analytical chemistry play the dominant role. Traditionally, energy dispersive X-ray fluorescence (EDXRF) has been excluded from the final certification scheme. It has lacked the proof to be reliable enough due to peak overlapping and risks of incorrect background subtraction leading to unacceptable uncertainty and bias of the results. The development described aims at enabling ED-SRXRF to really contribute to certification by the aid of synchrotron radiation. This has been partly shown for macrocontents and has been successfully demonstrated for trace elements and thin layers. The method is based on a combination of measurements of pure elements or stoichiometric compounds as comparator materials and Monte Carlo simulations. Measurements have been performed at the BAMline, the hard X-ray beam line of the BAM at the synchrotron BESSY II in Berlin.
A market survey has been performed of commercially available hydrogen safety sensors, resulting in a total sample size of 53 sensors from 21 manufacturers. The technical specifications, as provided by the manufacturer, have been collated and are displayed herein as a function of sensor working principle. These specifications comprise measuring range, response and recovery times, ambient temperature, pressure and relative humidity, power consumption and lifetime. These are then compared against known performance targets for both automotive and stationary applications in order to establish in how far current technology satisfies current requirements of sensor end users. Gaps in the performance of hydrogen sensing technologies are thus identified and areas recommended for future research and development.
Corrosion of steel reinforcement in concrete exposed to chloride containing environments is a serious problem in civil engineering practice. Electrochemical methods, e.g., potential mapping, provide information whether the steel reinforcement is still passive or depassivation has been initiated. By applying such techniques no information on the type of corrosion, its extent and distribution of corrosion products is available. Particular the corrosion progress is a significant problem. Especially in the case of macrocell corrosion in reinforced concrete structures, the development at the anode cannot be separated into corrosion damage resulting from macrocell corrosion or self-corrosion. Until now also in laboratory tests it is impossible to collect such information without destroying specimens after electrochemical testing was performed. To overcome this problem it was tried to study the steel surface within the mortar specimens by X-ray tomography (CT). Within the scope of these investigations it could be shown, that X-ray tomography is suitable to make corrosion pits and their development visible which are embedded in a mortar with a cover thickness of about 35 mm. In this publication the time-dependent corrosion damage of reinforced steel is documented by X-ray tomography.
Complex special inspection of an old masonry arch bridge according to the Guideline on Inspection and Condition Assessment of Railway Bridges and numerical analysis of the structure are presented. The guideline summarises recommendations for the step-by-step investigation of railway bridges applying enhanced methods developed during the EU-funded project Sustainable Bridges. For the investigation of the arch barrel, the ballast parameters and the inner structure of the backfill behind the arch barrel a number of various advanced non-destructive and minor-destructive testing methods were applied. Deformation of the structure during load tests was measured using three independent measuring systems: laser vibrometer, LVDT and microwave radar. Results of calculations performed with 2D and 3D models based on FEM are compared with the field load tests. Sensitivity of the ultimate load of the structure to investigated parameters is studied in FE model. Some general conclusions according to methods of testing and modelling of masonry arch bridges are presented and discussed.
Single-pulse tests of the catastrophic optical damage (COD) are performed for three batches of diode lasers with different gain-regions. The tests involve in situ inspection of front, rear, and side of the devices by a thermocamera. Devices with an Al-containing gain-region show COD at the front facet, as expected for strong facet heating via surface recombination and reabsorption of laser light. In contrast, Al-free devices with low surface recombination rates tend to fail at the rear facet, pointing to a different heating scenario. The high carrier density at the rear facet favors heating and COD via Auger recombination processes.
Water transport in an operating PEM fuel cell was investigated with synchrotron X-ray radiography with a spatial resolution of 3 µm and a temporal resolution of 5 s. This method allows for the detection of water accumulations with less than 10 µm diameter. We demonstrate that synchrotron X-ray imaging can dramatically expand the possibilities of imaging with high spatial and time resolution, especially as a complement to neutron radiography. Water transport processes from the first appearance of small water accumulations in the gas diffusion layer to their transport into the channel system were analysed in situ. Correlations between local effects such as water formation and operating conditions of the whole system, e.g. power variations, were found. A recently described eruptive water transport mechanism is analysed in detail.
Die Entwicklung zerstörungsfreier Prüfverfahren im Bauwesen (ZfPBau-Verfahren) hat in den letzten Jahren zu einer rasanten Leistungssteigerung geführt. Etliche Verfahren haben das Potenzial, in der Zukunft vom 'Stand der Wissenschaft' zum 'Stand der Technik' zu werden. Damit dies geschieht, muss möglichen Kunden vermittelt werden, welche Prüfaufgabe mit welchem Verfahren bearbeitet werden kann und wie zuverlässig die Ergebnisse sind. Um die Leistungsfähigkeit von ZfPBau-Verfahren nachzuweisen, ist eine genaue Kenntnis des wirklichen Bestands und der tatsächlichen Schäden erforderlich, um diese mit den Messergebnissen zu vergleichen und deren Güte zu bewerten. Mit dem Abriss der Spandauer- Damm-Brücke in Berlin ergab sich die Gelegenheit, zunächst eine großflächige Zustandsermittlung der Fahrbahnplatte bezüglich des Grads vorhandener Korrosionsschäden und des Verpresszustands von Spanngliedern vorzunehmen. Durch den vorgefundenen Zustand der Quervorspannung mit nachweislich vorhandenen Brüchen der Spanndrähte konnte an diesem Abrissbauwerk die Leistungsfähigkeit des Remanenzmagnetismusverfahrens zur Ortung von Spanndrahtbrüchen erstmals großflächig nachgewiesen werden, wobei auch der Vergleich der Untersuchungen mit und ohne Fahrbahnbelag durchgeführt wurde. Da der Anteil an vorhandenen Verpressfehlern nach großflächiger Auswertung sich als sehr gering herausstellte und an den ausgelösten Brückenteilen keine Verpressfehler vorhanden waren, wird in diesem Beitrag die Leistungsfähigkeit der Kombination von Radar und Ultraschall mit bildgebender Darstellung gezeigt. Damit wird es künftig möglich sein, Informationen zur Rekonstruktion nicht vorhandener Bestandspläne zu gewinnen.
An immunoassay was developed for ochratoxin A (OTA) detection in wine and two completely different detection methods were compared: ICP-MS and photometry. For labelling, we applied secondary antibodies conjugated with gold nanoparticles for ICP-MS and with horseradish peroxidase for photometric detection, respectively. Detection limits of the assay were determined as 0.003 µg L-1 for both detection methods. OTA in wine was determined below the EU limit value of 2 µg kg-1. The measurement range was between 0.01 and 1 µg L-1 for ICP-MS and photometric detection. Assay precision detected by ICP-MS and photometry were similar showing that precision of the detection method has only a minor effect on total assay precision. By using BSA as a buffer additive to minimize nonspecific binding, we could also confirm that OTA strongly binds to BSA. In a comparison study of several additives, casein was found to be preferable.
Chromophore-based fluorescence standards for the characterization of photo-luminescence measuring systems and the determination of relevant fluorometric quantities are classified according to their scope and area of application. General and type-specific requirements for suitable standards are derived for each class of standards. Metrological requirements linked to the realization of comparable measurements are addressed and recommendations on selecting, using, and developing fluorescence standards are given.
The wood protection industry has refined their products from chrome-, copper-, and arsenate-based wood preservatives toward solely copper-based preservatives in combination with organic biocides. One of these is Cu-HDO, containing the chelation product of copper and N-cyclohexyldiazenium dioxide (HDO). In this study, the fate of isotope-labeled (13C) and nonlabeled (12C) Cu-HDO incorporated in wood sawdust mixed with soil was investigated. HDO concentration was monitored by high-pressure liquid chromatography. The total carbon and the δ13C content of respired CO2, as well as of the soil-wood-sawdust mixture, were determined with an elemental analyzer-isotopic ratio mass spectrometer. The concentration of HDO decreased significantly after 105 days of incubation, and after 24 days the 13CO2 concentration respired from soil increased steadily to a maximum after 64 days of incubation. Phospholipid fatty acid-stable isotope probing (PFA-SIP) analysis revealed that the dominant PFAs C19:0d8,9, C18:0, C18:1ω7, C18:2ω6,9, C17:1d7,8, C16:0, and C16:1ω7 were highly enriched in their δ13C content. Moreover, RNA-SIP identified members of the phylum Acidobacteria and the genera Phenylobacterium and Comamonas that were assimilating carbon from HDO exclusively. Cu-HDO as part of a wood preservative effectively decreased fungal wood decay and overall microbial respiration from soil. In turn, a defined bacterial community was stimulated that was able to metabolize HDO completely.
Bei Konformitätsentscheidungen müssen in der Regel mehrere Spezifikationen bzgl. unterschiedlicher Eigenschaften gleichzeitig eingehalten werden, was zu erhöhten Risiken führen kann. In dem Beitrag werden Verfahren zur Bestimmung der Entscheidungssicherheit bzw. der Irrtumswahrscheinlichkeit bei multivariaten Konformitätsprüfungen dargestellt. Auf die Berücksichtigung von möglichen Korrelationen zwischen den bewerteten Größen des Untersuchungsobjektes wird eingegangen. Grundlage des Verfahrens bildet die Bayes'sche Statistik.
Although metallic nanoparticles play an important role in the area of nanotechnology, a coherent mechanistic explanation for the evolution of the particles during their chemical synthesis has not yet been provided in many cases. To gain a profound understanding of the growth mechanism of colloidal nanoparticles, new approaches using Small Angle X-Ray Scattering (SAXS) combined with X-ray absorption near-edge structure (XANES) are presented. This combination allows for insights into two prominent syntheses routes of gold nanoparticles (GNP): The 'slow' reaction using sodium citrate (30-90 min) as a reducing agent and the 'fast' reaction employing NaBH4 (within few seconds). In the first case data derived with the coupled XANES and SAXS suggests a four-step particle formation mechanism. For the second system a time resolution in the order of 100-200 ms was achieved by coupling a common laboratory SAXS instrument with a microstructured mixer, which allows data acquisition in a continuous-flow mode. The results indicate a coalescence driven growth process. Based on the capabilities to deduce the size, number and polydispersity of the particles, the results of both methods enable the development of mechanistic schemes explaining the different phases of particle formation and growth, thus providing a basis for improved control over the synthesis processes.
Force–displacement curves have been acquired with a commercial atomic force microscope on thin films of poly(n-butyl methacrylate) on glass substrates in order to examine the so-called 'mechanical double layer' topic, i.e. the influence of the substrate on the mechanical properties of the film in dependence of the film thickness. The hyperbolic fit, a novel semi-empirical equation introduced in previous articles, has been further corroborated. The interpretation of this equation has been deepened, yielding a quantitative and demonstrative characterization of the mechanical properties of double layers. Provided that the Young's moduli of bulk polymer and substrate are measured from the deformation curves, this mathematical model permits to fit the deformationforce curves on the double layers and to determine the thickness of the polymer films in wide range (0200 nm).
A large number of azodicarboxylates and their derivatives are produced and used in the chemical industries. The versatile applications of these azodicarboxylates in research institutes and in the chemical industries for chemical synthesis arouse additional hazards. The intent of this paper is to obtain first knowledge about the structure–response relationship regarding the explosive properties and the thermal hazards of different versatile used azodicarboxylates. The substances are examined with the differential scanning calorimetry (DSC). Furthermore, different laboratory test methods, based on the UN Recommendations on the Transport of Dangerous Goods, are applied to determine the explosive properties of the mentioned substances. On the basis of the obtained results, the known influence of the nitrogen content within the molecule regarding their thermal behaviour could be confirmed. The measured heat of decomposition appeared to be proportional to the nitrogen content within the group of the aliphatic and the aromatic azodicarboxylates. To emphasize this dependency, further investigations should be done. The long term objective of this research is to develop structure–response relationships of the explosive properties and the thermal hazards originating from azodicarboxylates.
Solid residues of bisphenol A polycarbonate (containing 0.45 wt% poly(tetrafluoroethylene))/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) after thermal treatment were investigated by solid-state and liquid-state NMR, focusing on the role and interaction of SiR with the other components of the polymer blend.
In PC/SiR/BDP, part of the SiR reacts to an amorphous silicate network rather than being completely released in the gas phase. The silicate network consists of Q4 and Q3 groups formed via intermediate D and T groups. The D groups are formed by a reaction of SiR with bisphenol-A units as well as phenyl groups of PC and BDP. In addition a small amount of silicon diphosphate was observed after thermal treatment at temperatures higher than 810 K. The same decomposition products (without SiP2O7) occur in the solid residues of PC/SiR/BDP/ZnB samples. The formation of intermediate D and T groups occurs earlier, at slightly lower temperatures. Any formation of a borosilicate network was excluded. The results also apply for the fire residues of PC/SiR/BDP and PC/SiR/BDP/ZnB and are thus valuable for understanding the impact of SiR on pyrolysis and flame retardancy mechanisms in the condensed phase during the burning of PC/SiR/BDP blends. SiR was found to influence the pyrolysis and the char formed. Beyond the replacement of highly combustible mechanical modifiers, SiR harbours the potential to enhance flame retardancy.
Structural changes in the condensed phase of bisphenol A polycarbonate (containing 0.45 wt% poly (tetrafluoroethylene))/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) during thermal treatment in nitrogen atmosphere and in fire residues were investigated by solid-state NMR. H-1, B-11, C-13 and P-31 NMR experiments using direct excitation with a single pulse and H-1-P-31 cross-polarization (CP) were carried out including 31P(1 H) and C-13{P-31}double-resonance techniques (REDOR: Rotational Echo Double Resonance) on a series of heat-treated samples (580 K-850 K). Because many amorphous phases occur in the solid residues, and solid-state NMR spectroscopy addresses the most important sites carbon, phosphorus and boron, this paper is the key analytical approach for understanding the pyrolysis and flame retarding phenomenon in the condensed phase of PC/SiR/BDP and PC/SiR/BDP/ZnB.
For the system PC/SiR/BDP it is shown that (i) at temperatures around 750-770 K (main decomposition step) carbonaceous charring of PC occurs and arylphosphate structures are still present, reacted in part with the decomposing PC; (ii) for higher temperatures from 770 K the phosphorus remaining in the solid phase increasingly converts to amorphous phosphonates and inorganic orthophosphates with a minor amount of crystalline orthophosphates; and (iii) H-1-P-31{H-1} CP REDOR and H-1-C-13{P-31} CP REDOR NMR experiments suggest that the phosphates and phosphonates are bound via oxygen to aromatic carbons, indicating the interaction with the carbonaceous char.
When ZnB is added to the system PC/SiR/BDP, (i) ZnB leads to a slightly enhanced PC decomposition for temperatures below 750 K; (ii) alpha-Zn-3(PO4)(2) and borophosphate (BPO4) are formed in small amounts at high temperatures suggesting a reaction between BDP and ZnB during thermal decomposition; and (iii) most of the borate remains in the solid residues, forming an amorphous pure borate network, with the BO3/BO4 ratio increasing with higher temperatures.
The NMR data of thermal and fire residues are highly correlated, underlining the importance of this work for understanding the pyrolysis and flame retardancy mechanisms in the condensed phase during the burning of the PC/SiR blends. (C) 2010 Elsevier Ltd. All rights reserved.
We present our results on the comparison of two methods for the SADT determination. Both methods, UN test H.1 and UN test H.4 are recommended by the international transport regulations from the UN. But during the last years the applicability of the UN test H.4 has been questioned for solid substances. Therefore, three organic peroxides and one self-reactive substance have been investigated in 5 kg and 20 kg packages as well as in the UN test H.4 in a 500 mL Dewar vessel. The SADT values determined with the different methods match. The UN test H.4 seems to be well suited for solid organic peroxides and self-reactive substances of at least 20 kg or 60 L.
The effect of a nanometer confinement on the vibrational
and molecular dynamics of a liquid crystals E7 was studied by dielectric
spectroscopy (DS) and neutron scattering (NS). E7 undergoes a
glass transition phenomenon besides the nematic to isotropic phase
transition. As confining host a molecular sieve of the MCM-41 type
is used having cylindrical pores with a radius of 1.25 nm. The results
obtained by both methods are compared in detail.
The degradation mechanisms of state-of-the-art Nb-Ti/Cu superconductors are described, based on in-situ synchrotron X-ray diffraction measurements during heat treatment. A quantitative description of the Nb-Ti/Cu degradation in terms of critical current density, Cu stabiliser resistivity and mechanical composite strength is presented. In an applied magnetic field a significant critical current degradation is already observed after a 5-minute 400 °C heat treatment, due to variations of –Ti precipitate size and distribution within the Nb-Ti alloy filaments. A strong degradation of the strand mechanical properties is observed after several minutes heating above 550 °C, which is also the temperature at which the formation of Cu-Ti intermetallic phases is detected. Several minutes heating at 250 °C are sufficient to increase the RRR of the strongly cold work strands inside a Rutherford type cable from about 80 to about 240. Heating for several minutes at 400 °C does not cause a significant conductor degradation in self-field and, thus, leaves enough temperature margin for the electrical interconnection of Nb-Ti/Cu conductors with common low temperature solders.
Der Einsatz aktiver (Pumpprobennahme,
Schöpfprobennahme) und passiver (Diffusionsprobennahme)
Probennahmetechniken zur Gehaltsbestimmung von
LHKW sowie Ethen und Methan in Grundwasser wird aus
ordnungsbehördlicher Sicht hinsichtlich der Vergleichbarkeit
von Analysendaten untersucht. Am Beispiel einer Kontamination
mit Trichlorethen sowie 1,2-Dichlorethen und
Vinylchlorid kann deutlich gemacht werden, dass die Einsatzmöglichkeit
der passiven Probennahme durch unzureichende
Strömungsverhältnisse im Aquifer sowie biologische
Aktivität im Pegelrohr begrenzt ist. Der aktiven Probennahme
ist bei ungeklärten oder unzureichenden Strömungsverhältnissen
im Grundwasserleiter daher der Vorzug
zu geben. Das gaschromatographische Verfahren für Vinylchlorid
mittels Dampfraumtechnik wird um die Quantifizierung
von Methan und Ethen erweitert. Dabei werden für
die Bewertung von Altlasten relevante Bestimmungsgrenzen
von 0,1 µg/l (Vinylchlorid, Ethen) sowie 5 µg/l (Methan)
erreicht.
Aus der Validierung der Analysenmethode und den
Ergebnissen verschiedener Probennahmen werden Toleranzbereiche
für die Ergebnisse eines Grundwassermonitorings
abgeschätzt. Diese Streubreiten von Monitoring-
Ergebnissen sollten von Ingenieurbüros und zuständigen
Ordnungsbehörden bei der Bewertung der komplexen Abbauprozesse
eines LHKW-Grundwasserschadens beachtet
werden.
Immobilization of silanized DNA on glass: influence of the silane tether on the DNA hybridization
(2010)
Two trifunctional (trimethoxy and triethoxy) and one difunctional (methyldimethoxy) 3-mercaptopropyl-alkoxysilanes were covalently tethered to thiolated DNA oligonucleotides in solution. After deposition as microarrays onto glass, the immobilized DNA probes were tested for hybridization ability by a florescence-based method. The results demonstrate a large enhancement in the fluorescence signal when the functionality of the silane tether is reduced from three to two. An XPS analyses revealed that this is not due to a higher DNA surface density. FTIR spectra of the spin-coated silanes showed that the trifunctional silanes form branched and cyclic siloxane moieties, whereas the difunctional silane generates predominantly short straight siloxane chains. Therefore, the propensity of trifunctional silanes to form more complex networks leads to conformations of the bound DNA which are less favorable for the specific interaction with the complementary strand. The data implicate that further significant improvements in the DNA hybridization ability are possible by adroit choice of the silane system.
The influence of weathering on the fire retardancy of polymers is investigated by means of a cone calorimeter test, before and after artificial weathering. The surface degradation was monitored using different techniques (ATR–FTIR, microscopy, colour measurement). Different kinds of polymeric materials were chosen, all as they are used in practice: polycarbonate (PC) blends, polyamide (PA) and polypropylene (PP) flame-retarded with arylphosphate, melamine cyanurate (MC) and intumescent formulation based on ammonium polyphosphate (APP), respectively.
All samples show material degradation at the surface due to weathering. No significant weathering influence occurs on the flame retardancy when it is a bulk property, as was observed for aryl phosphates in PC blends and MC in PA. When the fire retardancy is dominated by a surface mechanism, dependence on the duration of weathering is detected: for intumescent formulations based on ammonium APP in PP, a worsening in the formation of the intumescent network was observed.
Magnetic domains have been the subject of much scientific investigation since their theoretical existence was first postulated by P.-E. Weiss over a century ago. Up to now, the three-dimensional (3D) domain structure of bulk magnets has never been observed owing to the lack of appropriate experimental methods. Domain analysis in bulk matter thus remains one of the most challenging tasks in research on magnetic materials. All current domain observation methods are limited to studying surface domains or thin magnetic films. As the properties of magnetic materials are strongly affected by their domain structure, the development of a technique capable of investigating the shape, size and distribution of individual domains in three dimensions is of great importance. Here, we show that the novel technique of Talbot-Lau neutron tomography with inverted geometry enables direct imaging of the 3D network of magnetic domains within the bulk of FeSi crystals.
Applications of infrared thermography in civil engineering are not limited to the identification of heat losses in building envelopes. Active infrared thermography methods enable structural investigations of building elements with one-sided access up to a depth of about 10 cm. Masonry and especially historical masonry has a very heterogeneous structure containing several different materials (brick, stone, mortar, plaster, wood, metal, etc.) with various thermal properties. As many classes of damage originate from defects that are close to the surface, active thermography is in general very well suited to assessing different test problems in cultural heritage buildings. In this paper, the physical background, equipment, environmental influences and material properties are discussed. Several application results are presented. It is shown how active thermography can be integrated into a holistic approach for the assessment of historical structures.
This work compares thin layers (films) and monoliths prepared from alumina sols with respect to their microstructure, thermal evolution, porosity and specific surface area. After heat treatment at similar temperatures, films and monoliths showed the same qualitative changes in porosity and specific surface area. However, some marked quantitative differences were detected. Film fragments had a lower open porosity, a lower specific surface area and a narrower pore size distribution. Furthermore, the thermal evolution showed a markedly different burnout of organic components between films and monoliths. The observed differences between films and monolith can be explained by the ageing history of the sols during sample preparation.
Improved wetting of bare and pre-coated steels by aqueous alumina sols for optimum coating success
(2010)
Alumina coatings are a promising candidate for
the protection of metals prone to high temperature corrosion.
If applied via sol–gel process, especially by using so
called aqueous modified Yoldas-sols, the deposition is
hardened by differences in surface free energy of substrate
and sol. In this paper the apparent surface properties of
samples to be coated and sols were examined by contact
angle measurements, IR-spectroscopy and tensiometry.
The results imply, after consideration of possible uncertainties,
the use of surface tension reducing 2-butanol
already present during hydrolysis of the sols to obtain an
easy and successful coating process.
The precursor [FeIII(L)Cl] (LH2 = N,N'-bis(2'-hydroxy-3'-X-benzyliden)-1,6-diamino-3-N-hexane) is a high-spin (S = 5/2) complex (with X = -CH3, -O-CH3). This precursor is combined with the bridging unit [SnIV(CN)4] to yield star-shaped pentanuclear clusters, [(L-X-FeIII)4Sn(CN)4]Cl4 57Fe-Mössbauer, 119mSn-Mössbauer, and ESR spectroscopy are used to study our samples. For X = -CH3 the 57Fe-Mössbauer data show a multiple spin transition between iron(III) in the high-spin and low-spin state. Changing the functional group from X = -CH3 to X = -O-CH3 turns the switchability off.
Commonly, to determine osteoclastic resorption of biomaterials only the resorbed area is measured. The depth of the resorption pit, however, may also be important for the performance of a material. To generate such data we used two calcium phosphate ceramics (Ca10 and Ca2). The solubility of the materials was determined according to DIN EN ISO 10993-14. They were scanned three-dimensionally using infinite focus microscopy and subsequently cultivated for 4 weeks in simulated body fluid without (control) or with human osteoclasts. After this cultivation period osteoclasts number was determined and surface changes were evaluated two- and three-dimensionally. Ca10 and Ca2 showed solubilities of 11.0 ± 0.5 and 23.0 ± 2.2 mg g-1, respectively. Both materials induced a significant increase in osteoclast number. While Ca10 did not show osteoclastic resorption, Ca2 showed an increased pit area and pit volume due to osteoclastic action. This was caused by an increased average pit depth and an increased number of pits, while the average area of single pits did not change significantly. The deduced volumetric osteoclastic resorption rate (vORR) of Ca2 (0.010.02 µm3 µm-2 day-1) was lower than the remodelling speed observed in vivo (0.08 µm3 µm-2 day-1), which is in line with the observation that implanted resorbable materials remain in the body longer than originally expected. Determination of volumetric indices of osteoclastic resorption might be valuable in obtaining additional information about cellular resorption of bone substitute materials. This may help facilitate the development of novel materials for bone substitution.
A series of cyclic thermo-mechanical measurements was conducted on segregated poly(ester urethane) to study substantial changes in triple-shape properties as a result of hydrolytic aging (80 °C). Prior to the analysis of aging effects, a concept of triple-shape testing was elaborated, starting with the implementation of two distinct programming units. The first one included a deformation at 60 °C to εm1 = 100% (temporary shape B) and its fixing through soft segment crystallization by cooling to -20 °C under constant strain. The second one consisted of a deformation at -20 °C to εm2 = 200% (temporary shape A) and its stabilization through soft segment vitrification as achieved by cooling to -60 °C under fixed strain constraint. Then, gradual heating of the polymer from below to above its thermal transition temperatures gave two independent shape recovery responses in the reverse order of shape fixing: A → B through passing the glass transition by heating from -60 to 23 °C and B → C (back to the permanent shape), when heating the material from 23 to 60 °C and thus above its soft segment melting temperature. In a progressive approach, the storage of loading history through the sequential fixing of two temporary shapes was proven by the development of shape recovery stresses under constrained environment. With the implementation of the two testing methods several aging-related effects could be detected. Good shape fixing abilities ≥90% for both shapes were found and contrasted by significant changes in shape recoverabilities and stress storage capacities. Further insights derived from differential scanning calorimetry (DSC) measurements, indicating an aging-related growth in soft segment crystallinity, and dynamic mechanical analysis (DMA), suggesting a plasticizer effect of water onto the polymer matrix and that aging favoured an increase in cross-linking density.
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.
The acid catalyzed solgel type synthesis of polyorganosiloxane core-shell nanoparticles with removable PDMS core in aqueous dispersion leads to the inherent formation of a bimodal size distribution with smaller spheres having approximately 26 nm radii and larger nanoparticles with 60 nm in radius. The origin of the self-organized bimodality is investigated and finally attributed to a combination of stabilization of the growing particles due to i) a miniemulsion-type stabilization by the ultrahydrophobe PDMS and ii) by surface co-stabilization by the employed surfactant. The significant influence of temperature, pH, stirrer speed and amount of the surfactant on the particle sizes allows for the design and fine-tuning of different nanoparticles sizes and distributions.
The enzymatic incorporation as well as the spectroscopic properties and photochemical stability of a series of fluorescent labels differing in dye class, charge, and rigidity were studied to identify new tools for signal enhancement in situ on microarrays without secondary labeling. These fluorophores were chosen to spectrally match or resemble the golden standard Cy3. With the rhodamine DY-555, that is three times more emissive than Cy3, we found a bright and stable chromophore, the spectroscopic properties of which are minimally influenced by dye microenvironment.
Triacetone triperoxide (TATP), an improvised explosive, is a potential security threat because of its cost-efficient synthesis and the difficulty in detecting it. A highly selective antibody could provide the necessary specificity to the detection process. To obtain antibodies, a hapten made from acetone, hydrogen peroxide, and 7-oxooctanoic acid has been designed, synthesized, and confirmed by NMR that displays the utmost similarity to the analyte. The single-crystal X-ray structures of the solvated species TATP·methanol (1:1) and the TATP derivate were determined. In both compounds, the molecules exhibit D3 symmetry and adopt a twisted boat-chair conformation. The hapten was coupled to bovine serum albumin, and mice were immunized. An immune response against TATP was elicited, and selective antibodies were detected in the mouse serum, which should be very useful for the development of a TATP biosensor system. An ELISA with a limit of detection for TATP of 65 µg L-1 is shown.
The complexation of a cylindrical polyelectrolyte–brush-surfactant complex (PMMPSS–C12) and an oppositely charged generation-5 PAMAM dendrimer (G5-PAMAM) in methanol (MeOH) leads to kinetically controlled formation of interpolyelectrolyte complexes. In contrast, the complexation of the same starting materials in solvents with higher dielectric constant such as dimethylformamide (DMF) or N-methylformamide (NMF) results in the formation of topologically controlled complexes of cylindrical morphology. The composition of the complexes is analyzed by static and dynamic light scattering (SLS, DLS) in solution and atomic force microscopy (AFM) after spin-casting the complexes onto mica. The analyzed complexes seem to consist of one PMMPSS–C12 molecule and, with increasing G5-PAMAM content, of an increasing number of G5-PAMAM dendrimers.
Nanosilver is increasingly used in optics, medicine and analytical chemistry. We recently reported on the synthesis and properties of novel peptide-coated chiral nanosilver [1] using a small hexapeptide based on the amino acids CKK. In a continuation of our previous work, we use the peptides to catalyse TEOS hydrolysis in order to form a dense silica layer shell around a single nanoparticle, preventing chemical etching, allowing their inclusion in other inorganics, and making them biocompatible. Because of mild reaction conditions, the peptide integrity is ensured, as the chiral information which is contained in the nanoparticle. Moreover, these novel core-shell structures remain well-dispersed and are biocompatible. The possibility of further processing (creation of metamaterials etc.) is also in the focus of our interest.
Transfer admittance spectra of technically induced surface wave fields are analyzed in theory and experiments. Theoretical admittance spectra of layered soils are obtained by integration in wavenumber domain and compared with experimental admittances due to hammer or vibrator excitation. The admittance spectra are strongly influenced by the layering and damping of the soil. Deep stiff-soil layers yield a low-frequency cutoff, whereas a strong damping yields a high-frequency cutoff. A sharp cutoff in a narrow frequency band, which is measured at some sites, can be explained by a damping that increases with frequency, such as viscous material or scattering damping.
The attenuation of the amplitudes with distance of technically induced surface wave fields is analyzed in theory and experiments. Experimental results of technically induced ground vibration are presented and collected from literature, which show a power-low attenuation A ~ r–q of amplitudes A with distance r and exponents q > 0.5 higher than for elastic surface waves. Additional attenuation effects are analyzed theoretically. The most important effect is due to the material or scattering damping. Each frequency component is attenuated exponentially as A ~ exp(–kr), but for a broadband excitation, the sum of the exponential laws yields a power law with a higher exponent. Some more effects are discussed, for example the dispersion of the Rayleigh wave due to the layering of the soil, which yields a stronger attenuation A ~ r–q–dq, including an additional exponent of dq = 0.5 in case of an impulsive loading.
The resource-saving utilisation of recovered
waste wood is a matter of growing concern. In several
European countries, this utilisation is governed by regulations
and is dependent on the contents of certain trace
elements and organic compounds. Thus, for decisionmaking
with respect to waste wood management (recycling
or combustion), reliable analytical data are needed and, due
to their great economic and environmental impact, must be
assured by appropriate quality control. To support the
improvement in quality assurance in waste wood analysis,
for the first time, a wood reference material was certified
for its mass fractions of arsenic, cadmium, chromium,
copper, lead, mercury, and pentachlorophenol (PCP).
These analytes were selected because they represent typical
constituents of wood preservatives most widely used in the
past. Material preparation and testing of homogeneity and
stability were carried out by BAM Federal Institute for
Materials Research and Testing. The certification measurements
were performed involving selected laboratories
with documented expertise in the field of waste wood
analysis. The certified values and their corresponding
uncertainties were assigned in full compliance with the
requirements of ISO Guide 35. The certified mass fractions
and their expanded uncertainties (k/i> = 2) are as follows:
(3.1 ± 0.5) mg/kg for As, (3.02 ± 0.24) mg/kg for Cd,
(36.4 ± 2.6) mg/kg for Cr, (22.9 ± 1.7) mg/kg for Cu,
(0.60 ± 0.14) mg/kg for Hg, (39 ± 4) mg/kg for Pb, and
(7.9 ± 0.6) mg/kg for PCP. The certified material is
available as European Reference Material ERM®-CD100.
We present the latest advances in distributed strain measurement in perfluorinated polymer optical fibres (POFs) using backscatter techniques. Compared to previously introduced poly(methyl methacrylate) POFs, the measurement length can be extended to more than 500 m at improved spatial resolution of a few centimetres. It is shown that strain in a perfluorinated POF can be measured up to 100%. In parallel to these investigations, the incoherent optical frequency domain reflectometry (OFDR) technique is introduced to detect strained fibre sections and to measure distributed length change along the fibre with sub-millimetre resolution by applying a cross-correlation algorithm to the backscatter signal. The overall superior performance of the OFDR technique compared to the optical time domain reflectometry in terms of accuracy, dynamic range, spatial resolution and measurement speed is presented. The proposed sensor system is a promising technique for use in structural health monitoring applications where the precise detection of high strain is required.
Polymer-based nanocomposites were prepared by solution blending of polyhedral oligomeric silsesquioxane with phenethyl substituents (PhenethylPOSS) into poly(bisphenol A carbonate) (PBAC). First investigations focused on structure, morphology and dynamics, addressed mainly by dielectric relaxation spectroscopy are substantially extended in this study by the investigation of the CO2 gas transport behavior of these materials, i.e., permeation experiments using the time-lag technique as well as gravimetric gas sorption measurements. The nanocomposite materials were prepared with nanofiller contents ranging from 0 to about 40 wt % by solution blending and films of about 50-100 µm thickness were cast from this solution and used for the investigation of gas transport properties after drying and annealing. From the time-lag measurements the permeability and an effective diffusion coefficient for CO2 is obtained in dependence of POSS concentration and temperature. As main results, both, the permeability and the diffusivity, increase whereas the solubility decreases with increasing POSS concentration. These findings are discussed in the framework of a microphase separated morphology of the nanocomposite systems for POSS concentrations greater than a value cPOSScrit of ca. 7 wt % consisting of a polycarbonate-rich matrix and POSS-rich domains which are surrounded by an interfacial layer. The experimental solubility data suggest that the POSS-rich domains are more or less impermeable for CO2. On the basis of this assumption a quantitative model is provided to correct the solubility data for the phase separated morphology. Moreover the importance of the interfacial layer between the POSS particles or its domains for the properties of nanocomposites especially for the gas transport behavior is addressed by analyzing the sorption isotherms. Also, for the first time results from gas transport measurements and dielectric spectroscopy were quantitatively related to each other by taking the activation energies of CO2 diffusion and of the dielectric β-relaxation into consideration. The obtained clear correlation indicates that the CO2 gas transport is due to localized molecular fluctuations. As a further result, the diffusion coefficient obtained from time-lag and gas sorption measurements is in good agreement with respect to both their absolute values and in their concentration dependence.
High-performance liquid chromatography tandem mass spectrometry (HPLC–MS/MS) was applied to sterospecifically quantify the content of α-, β-, and γ-hexabromocyclododecane (HBCD) in six fish species from the Norwegian Etnefjorden. A combination of a β-PM cyclodextrin and an achiral column enabled the paired chromatographic separation of the stereoisomers in the order (-)-α-, (+)-α-, (-)-β-, (+)-β-, (+)-γ- and, (-)-γ-HBCD. The limits of detection were in the range of 6–21 pg g-1 depending on the stereoisomer and the concentrations of α-, β-, and γ-HBCD in fillets ranged from <5.4 ng g-1 to 11.1 µg g-1 lipid weight. α-HBCD enantiomers were throughout dominating, and in most cases the accumulation of the respective first eluted enantiomers ((-)-α-, (-)-β- and (+)-γ-HBCD) was observed. Deviations from the racemic EF-value were considered to be significant if it was outside of the expanded uncertainty range for each of the racemic HBCD-ratios. The composition of HBCD isomers varied between the investigated fish species and the relative high values for the γ-HBCD concentrations for the bottom-dwellers flounder and thorny skate seems to echo the HBCD pattern of ocean sediments.
Synthetic pressed metal powder standards doped with standard solutions were used for the calibration of both commercially available high resolution GD-MS instruments Element GD and VG 9000 for zinc matrix. Different quantification procedures (IBR, Standard RSF, matrix matched RSF from the calibration with CRMs and use of doped synthetic standards) are compared using zinc matrix as an example, whereas the calibration with doped pellets turned out to be the best quantification technique for high-purity materials. The applicability of the Standard RSF concept is scrutinised. In this context, RSF values for several Matrices (Co, Cu, Fe, In and Zn) are reported additionally.
Excitation force spectra are necessary for a realistic prediction of railway-induced ground vibration. The excitation forces cause the ground vibration and they are themselves a result of irregularities passed by the train. The methods of the related analyses - the wavenumber integration for the wave propagation in homogeneous or layered soils, the combined finite-element boundary-element method for the vehicle-track-soil interaction - have already been presented and are the base for the advanced topic of this contribution. This contribution determines excitation force spectra of railway traffic by two completely different methods. The forward analysis starts with vehicle, track and soil irregularities, which are taken from literature and axle-box measurements, calculates the vehicle-track interaction and gets theoretical force spectra as the result. The second method is a backward analysis from the measured ground vibration of railway traffic. A calculated or measured transfer function of the soil is used to determine the excitation force spectrum of the train. A number of measurements of different soils and different trains with different speeds are analysed in that way. Forward and backward analysis yield the same approximate force spectra with values around 1 kN for each axle and third of octave.
X-ray scattering may contribute significantly to the spectral background of X-ray fluorescence (XRF) spectra. Based on metrological measurements carried out with a scanning electron microscope (SEM) having attached a well characterised X-ray source (polychromatic X-ray tube) and a calibrated energy dispersive X-ray spectrometer (EDS) the accuracy of a physical model for X-ray scattering is systematically evaluated for representative samples. The knowledge of the X-ray spectrometer efficiency, but also of the spectrometer response functions makes it possible to define a physical spectral background of XRF spectra. Background subtraction relying on purely mathematical procedures is state-of-the-art. The results produced by the analytical model are at least as reliable as those obtained by Monte-Carlo simulations, even without considering the very challenging contribution of multiple scattering. Special attention has been paid to Compton broadening. Relevant applications of the implementation of the analytical model presented in this paper are the prediction of the limits of detection for particular cases or the determination of the transmission of X-ray polycapillary lenses.
Building stones are porous media and they can deteriorate through moisture ingress and secondary damage such as crystallization of soluble salts. Not only is this due to the increasing number of flood events in the past years but also structural damages of houses from activity such as leakage or rising moisture (groundwater) are the main causes. The potential benefit of several nondestructive testing methods to assess water damage in building stone has been studied in a field-scale experiment. Three testing walls made of fired clay brick, sandstone, and spongilite were flooded and their drying behavior monitored using infrared thermography, complex resistivity, ground penetrating radar, and ultrasonics. The results were compared to the average moisture content determined by gravimetric weighing of the specimens. Qualitatively, the results of the different nondestructive testing methods matched well. But in terms of quantitative data, some scatter was observed and the results should be viewed with care. Collecting time-consuming calibration data would help to overcome this problem, but especially when dealing with historic building structures, this is not always possible in practice.