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"Ullmann's Encyclopedia of Industrial Chemistry" is the benchmark reference in chemistry and chemical and life science engineering, covering inorganic and organic chemicals, advanced materials, pharmaceuticals, polymers and plastics, metals and alloys, biotechnology and biotechnological products, food chemistry, process engineering and unit operations, analytical methods, environmental protection, and much more.
The present article is part of the topic collection "Environmental Protection and Industrial Safety". It covers plant and process safety, focusing on hazardous materials and process conditions.
REALight ‐ Leichtgranulate und REA‐Gips aus feinkörnigen sulfatbelasteten Bau‐ und Abbruchabfällen
(2023)
Ziel des Projekts REALight ist die Entwicklung einer Referenzanlage zur Herstellung von Leichtgranulaten (leichte Gesteinskörnungen) aus Bau‐ und Abbruchabfällen und zur Gipsrückgewinnung. Als Rohstoffe werden bisher ungenutzte oder auf niedrigem Niveau eingesetzte Bau‐ und Abbruchabfälle und industrielle Nebenprodukte verwendet. Als Produkte werden leichte Gesteinskörnungen hergestellt. Die Sulfatabtrennung durch eine thermische Zersetzung bildet die Grundlage für die zusätzliche Gewinnung von Rauchgasentschwefelungs‐Gips (REA‐Gips). Das Projekt wird im Rahmen der Fördermaßnahme „Ressourceneffiziente Kreislaufwirtschaft – Bauen und Mineralische Stoffkreisläufe (ReMin)” gefördert. ReMin ist eine Maßnahme zur Umsetzung des BMBF‐Forschungskonzepts „Ressourceneffiziente Kreislaufwirtschaft” als Teil der BMBF Strategie „Forschung für nachhaltige Entwicklung – FONA”. Ziel der Förderung ist es, den Ausbau der Kreislaufwirtschaft voranzutreiben. Im Mittelpunkt steht dabei die Bauwirtschaft mit ihrer hohen Nachfrage nach Rohstoffen und gleichzeitig großen Mengen an anfallenden mineralischen Abfällen. Am Projekt REALight sind 12 Partner aus verschiedenen Bereichen der Baustoffherstellung und ‐anwendung, Abfallaufbereitung, Verfahrenstechnik sowie Forschung und Entwicklung beteiligt.
The development of a test to evaluate the degradation of semi-volatile fuels as diesel by microorganisms is presented. This method is based on the principles described in the CEC-L-103 Standard procedure that is exclusively meant for testing the biodegradability of non-volatile lubricants. Therefore, significant modifications involve aseptic conditions for testing specific microorganisms and conducting the test in closed vessels avoiding evaporation losses, while fuel quantification using gas chromatography-flame ionization detection (GC-FID) is retained. It is suggested that the modified procedure should enable routine application for semi-volatile hydrocarbon-based fuels. GC-FID provides additionally valuable information on the alteration of fuel component patterns during biodegradation. The procedure was successfully tested using two bacteria (Pseudomonas aeruginosa and Sphingomonas sp.) and two yeasts (Moesziomyces sp. and Candida sp.) isolated from real diesel contamination cases. All tested microorganisms caused a significant degradation of diesel fuel achieving hydrocarbon degradation percentages ranging from 23% to 35%. Specific aspects on the test modification and prospects for further modification regarding targeted investigations in the field of fuel contamination by microorganisms are briefly discussed.
Soiling of photovoltaic (PV) systems compromises their performance causing a significant power loss and demanding periodical cleaning actions. This phenomenon raises great concerns in the solar energy field, thus leading to notable research efforts over the last decades. Soiling is caused by a dual action of dust deposition and biofouling. However, surprisingly, the microbiological contribution to PV soiling is often overlooked or underestimated. In this study, a variety of qPCR-based methods have been developed to quantify the microbial load of fungi, bacteria and phototrophs on PV panels. These protocols were evaluated by comparison with culturedependent methods, and were implemented with real solar plants for two years. The results show that the developed molecular methods are highly sensitive and reliable to monitor the microbial component of the soiling. Fungal biomass was clearly dominant in all analysed PV modules, while bacteria and phototrophs showed much lower abundance. Light microscopy and qPCR results revealed that melanised microcolonial fungi and phototrophs are the main biofilm-forming microorganisms on the studied solar panels. In particular, the fungal qPCR protocol is proposed as a useful tool for monitoring of PV soiling, and investigating the microbial contribution to specific soiling cases.
Miscanthus x Giganteus (Miscanthus) energy crop was examined at laboratory scale to assess its self-heating and self-ignition risks during storage. Chipped Miscanthus (18 mm) from February and March harvests, in 2012, were assessed as well as ground Miscanthus (3 mm) from the March harvest. February and March crops had moisture contents of 41.6 and 20.2%, respectively. Self-ignition temperatures were independent of moisture although moisture did affect the time from the beginning of storage until storage temperature was reached. Ground Miscanthus had lower self-ignition temperatures than chipped Miscanthus. Isothermal respirometric tests carried out showed increase risk of self-heating in the February crop compared to the March crop due to increased microbial activity. Numerical simulations were used to determine critical enhanced start temperatures, e.g. caused by microbial decomposition, of the stored Miscanthus. Safe storage conditions have been derived from the investigations. The numerical simulations demonstrated that self-ignition was possible in Miscanthus chip piles with a height greater than 6 m if there was significant heat release from microbiological activity. Reliable assessment of self-heating and self-ignition risks in large scale Miscanthus energy crop clamps or piles are required to prevent losses due to decomposition and fire damage.
The H2 effusion from H2 saturated glass powders, H2 permeation through the wall of blown glass bulbs, and H2 permeation through the wall of glass capillaries were applied to evaluate the permeability of hydrogen gas in a barium-aluminoborosilicate (BABS) glass. To validate these methods, two commercial glasses (vitreous silica and borosilicate) were used as a reference. Permeation values obtained from the different experiments agreed within a factor of 3 or less. The H2 permeability of BABS glass at temperatures close to ambient was found to be at least 3 orders of magnitude below that of borosilicate and silica glasses. The powder method, which requires minimal sample preparation efforts, turned out to provide easy access to the measurement of H2 permeability of glasses down to P = 3.9 × 10- 21 mol s- 1 Pa- 1 m- 1.
This paper presents the state-of-the-art of using non-destructive testing (NDT) methods based on elastic waves for the condition assessment of structural timber. Two very promising approaches based on the propagation and reflections of elastic waves are described. While the first approach uses ultrasonic echoes for the testing of wooden building elements, the second approach uses guided waves (GW) for the testing of timber pole and pile structures. The basic principle behind both approaches is that elastic waves induced in a timber structure will propagate through its material until they encounter a change in stiffness, cross-sectional area or density, at which point they will reflect back. By measuring the wave echoes, it is possible to determine geometric properties of the tested structures such as the back wall of timber elements or the underground length of timber poles or piles. In addition, the internal state of the tested structures can be assessed since damage and defects such as rot, fungi or termite attacks will cause early reflections of the elastic waves as well as it can result in changes in wave velocity, wave attenuation and wave mode conversion. In the paper, the principles and theory of using elastic wave propagation for the assessment of wooden building elements and timber pole/pile structures are described. The state-of-the-art in testing equipment and procedures is presented and detailed examples are given on the practical application of both testing approaches. Recent encouraging developments of cutting edge research are presented along with challenges for future research.
In this article a comparative study of the behaviour of
different commercial anti-graffiti on natural stone and
brick is presented. 8 different European substrates were
selected and 4 commercial anti-graffiti of different
chemical nature were applied on these substrates. The
variations of their hydric properties and aspect (colour
and gloss) with regard to the untreated substrates were
later studied in the laboratory.
The results obtained permitted to assess the suitability of
4 of the main types of chemical formulations employed
to be used as anti-graffiti. This study concludes that the
sacrificial anti-graffiti with polymeric paraffins in its
composition presents the lowest reductions of the hydric
properties of the studied substrates, being also the
variations in colour the least perceptible.
Beurteilung des Selbstentzündungsverhaltens brennbarer Stäube mit Hilfe adiabatischer Warmlagerung
(2010)
In order to prevent incidents in the
industrial production of Teflon® from
Tetrafluoroethylene (TFE), the safety related
aspects of the self-heating process of TFE must
be taken into account. Simulations of this self
heating process were performed with COMSOL
Reaction Engineering Lab® and COMSOL®
COMSOL Multiphysics®. A complex reaction
net was employed, resulting in a model allows
for a good agreement with experimentally
achieved results.
Self-ignition of coal dust deposits poses a higher risk of fires in oxygen-enriched oxy-fuel combustion systems. In this work, we develop a numerical method, using the commercial software COMSOL Multiphysics, to investigate self-ignition behaviour of coal dust accumulations with a main emphasis on the roles of oxygen, diluent gas and dust volume. A one-step 2nd-order reaction kinetic model considering both coal density and oxygen density is used to estimate reaction rate using the kinetic parameters from previously conducted hot-oven tests. This model is validated to predict the transient temperature and concentration profiles of South African coal dusts until ignition. The computed self-ignition temperatures of dust volumes show a good agreement with experimental results. In addition, it is found that the inhibiting effect of carbon dioxide is comparatively small and oxygen consumption increases dramatically after ignition. Parameter analysis shows that the heating value and kinetic parameters have a comparatively pronounced effect on self-ignition temperature. The model provides a satisfactory explanation for the dependence of self-ignition behaviour on gas atmospheres, thus helping to further understand the fire risk of self-ignition in oxy-fuel combustion systems.
The SuSu Knolls and DESMOS hydrothermal fields are located in the back-arc extensional transform zone of the Eastern Manus Basin. In 2006, highly acidic and ΣSO4-rich vent fluids were collected at both sites and analyzed for the chemical and isotopic composition of major and trace species. Fluids exiting the seafloor have measured temperatures from 48 to 215 °C and are milky white in appearance due to precipitation of elemental S0. Vent fluid concentrations of Na, K, and Mg are depleted by as much as 30% relative to seawater, but have the same relative abundance. In contrast, the fluids are highly enriched in dissolved ΣCO2, Cl, SiO2(aq), Fe, and Al relative to seawater. Measured pH (25 °C) ranged from 0.95 to 1.87 and aqueous ΣSO4 ranged from 35 to 135 mmol/kg. The chemical and isotopic composition points to formation via subsurface mixing of seawater with a Na-, K-, Mg-, and Ca-free, volatile-rich magmatic fluid exsolved from subsurface magma bodies during a process analogous to subaerial fumarole discharge. Estimates of the magmatic end-member composition indicate a fluid phase where H2O > SO2 > CO2 ≈ Cl > F. The hydrogen and oxygen isotopic composition of H2O and carbon isotopic composition of ΣCO2 in the vent fluids strongly suggest a contribution of slab-derived H2O and CO2 to melts generated in the mantle beneath the Eastern Manus volcanic zone. Abundant magmatically-derived SO2 undergoes disproportionation during cooling in upflow zones and contributes abundant acidity, SO42-, and S0 to the venting fluids. Interaction of these highly acidic fluids with highly altered mineral assemblages in the upflow zone are responsible for extensive aqueous mobilization of SiO2(aq), Fe, and Al. Temporal variability in the speciation and abundance of aqueous S species between 1995 and 2006 at the DESMOS vent field suggests an increase in the relative abundance of SO2 in the magmatic end-member that has mixed with seawater in the subsurface. Results of this study constrain processes responsible for the formation of hot-spring fluids in magmatically active back-arc environments and the resulting chemical exchange between the lithosphere and water column.
The interest in (micro)porous systems is greater than ever before with microporous polymers finding application in areas such as gas storage/separation and catalysis. In contrast to the vast majority of publications on microporous polymers seeking ever higher values for surface area or uptake capacity for a particular gas, this work presents a means to render a microporous system responsive to electromagnetic stimuli. The incorporation of a diarylethene (DAE) derivative in the backbone of a polymer of intrinsic microporosity (PIM) produces a microporous system that exhibits photochromism as proven by UV–vis absorption and NMR studies. In the resulting DAE-PIM, surface area is not a fixed unalterable property but can be influenced by the external and nondestructive stimulus light in a reversible manner. Furthermore, in combination with Matrimid, free-standing membranes can be produced that display light-switchable diffusivity and permeability for carbon dioxide and oxygen. In this way, material scientists are offered the potential to employ only one system that can assume several states with different properties for each.
Two novel species of the fungal genus Ochroconis, O. lascauxensis and O. anomala have been isolated from the walls of the Lascaux Cave, France. The interest in these fungi and their melanins lies in the formation of black stains on the walls and rock art which threatens the integrity of the paintings. Here we report solid-state cross polarization magic-angle spinning 13C and 15N nuclear magnetic resonance (NMR) spectroscopy and surface-enhanced Raman spectroscopy (SERS) of the melanins extracted from the mycelia of O. lascauxensis and O. anomala in order to known their chemical structure. The melanins from these two species were compared with those from other fungi. The melanins from the Ochroconis species have similar SERS and 13C and 15N NMR spectra. Their chemical structures as suggested by the data are not related to 3,4-dihydroxyphenylalanine, 5,6-dihydroxyindole or 1,8-dihydroxynaphthalene precursors and likely the building blocks from the melanins have to be based on other phenols that react with the N-terminal amino acid of proteins. The analytical pyrolysis of the acid hydrolysed melanin from O. lascauxensis supports this assumption.
We combined two completely different methods measuring the frequency-dependent electrical properties of moist porous materials in order to receive an extraordinary large frequency spectrum. In the low-frequency (LF) range, complex electrical resistivity between 1 mHz and 45 kHz was measured for three different soils and sandstone, using the spectral induced polarization (SIP) method with a four electrode cell. In the high-frequency (HF) radio to microwave range, complex dielectric permittivity was measured between 1MHz and 10 GHz for the same samples using dielectric spectroscopy by means of the coaxial transmission line technique. The combined data sets cover 13 orders of magnitude and were transferred into their equivalent expressions: the complex effective dielectric permittivity and the complex effective electrical conductivity.We applied the Kramers-Kronig relation in order to justify the validity of the data combination. A new phenomenological model that consists of both dielectric permittivity and electrical conductivity terms in a Debye- and Cole–Cole-type manner was fitted to the spectra. The combined permittivity and conductivity model accounts for the most common representations of the physical quantities with respect to the individual measuring method. A maximum number of four relaxation processes was identified in the analysed frequency range. Among these are the free water and different interfacial relaxation processes, the Maxwell-Wagner effect, the counterion relaxation in the electrical double layer and the direct-current electrical conductivity. There is evidence that free water relaxation does not affect the electrical response in the SIP range. Moreover, direct current conductivity contribution (bulk and interface) dominates the losses in the HF range. Interfacial relaxation processes with relaxations in the HF range are broadly distributed down to the LF range. The slowest observed process in the LF range has a minor contribution to the HF response.
In this paper, we present an autonomous aerial robot to reconstruct tomographic 2D slices of gas plumes in outdoor environments. Our platform, the so-called Unmanned Aerial Vehicle for Remote Gas Sensing (UAV-REGAS) combines a lightweight Tunable Diode Laser Absorption Spectroscopy (TDLAS) sensor with a 3-axis aerial stabilization gimbal for aiming on a versatile octocopter. The TDLAS sensor provides integral gas concentration measurements but no information regarding the distance traveled by the laser diode's beam or the distribution of the gas along the optical path. We complemented the set-up with a laser rangefinder and apply principles of Computed Tomography (CT) to create a model of the spatial gas distribution from these integral concentration measurements. To allow for a rudimentary ground truth evaluation of the applied gas tomography algorithm, we set up a unique outdoor test environment based on two 3D ultrasonic anemometers and a distributed array of 10 infrared gas transmitters. We present first results showing the 2D plume reconstruction capabilities of the system under realistic conditions.
Synchrotron-induced X-ray fluorescence (Sy-XRF) analysis was used to study the chemical composition of precious Renaissance silverpoint drawings. Drawings by famous artists such as Albrecht Dürer (14711528) and Jan van Eyck (approximately 13951441) must be investigated non-destructively. Moreover, extremely sensitive synchrotron- or accelerator-based techniques are needed since only small quantities of silver are deposited on the paper. New criteria for attributing these works to a particular artist could be established based on the analysis of the chemical composition of the metal points used. We illustrate how analysis can give new art historical information by means of two case studies. Two particular drawings, one of Albrecht Dürer, showing a profile portrait of his closest friend, Willibald Pirckheimer (1503), and a second one attributed to Jan van Eyck, showing a Portrait of an elderly man, often named Niccolò Albergati, are the object of intense art historical controversy. Both drawings show inscriptions next to the figures. Analyses by Sy-XRF could reveal the same kind of silverpoint for the Pirckheimer portrait and its mysterious Greek inscription, contrary to the drawing by Van Eyck where at least three different metal points were applied. Two different types of silver marks were found in this portrait. Silver containing gold marks were detected in the inscriptions and over-subscriptions. This is the first evidence of the use of gold points for metal point drawings in the Middle Ages.
Spatially resolved X-ray fluorescence analysis using synchrotron radiation (SR-XRF) at the wavelength shifter beamline, BAMline, at BESSY was used to investigate Renaissance silverpoint drawings as it is extremely sensitive, non-destructive and can be carried out in air using an excitation spot in the hundred micrometer range.
This paper deals with first results of the study of silverpoint drawings of Albrecht Dürer (14711528) belonging to the sketchbook that Albrecht Dürer used during a travel to the Netherlands in 1520/21. These results are compared to a PIXE study performed on drawings from the same sketchbook.
The minor element composition of the silverpoint used for the drawings in the sketchbook was (10.6 ± 3.5) wt.% of Cu and traces of Zn. Mercury was found in the marks but does not belong to the initial composition of the silverpoint as it is attributed to an alteration phenomenon. One drawing of the sketchbook represents an exception. It consists of silver marks containing an additional minor element, Zn, in the marks and was, therefore, created with another silverpoint, probably at a different time than the other drawings.
Cell-to-cell variation and specialization in sugar metabolism in clonal bacterial populations
(2017)
While we have good understanding of bacterial metabolism at the population level, we know little about the metabolic behavior of individual cells: do single cells in clonal populations sometimes specialize on different metabolic pathways? Such metabolic specialization could be driven by stochastic gene expression and could provide individual cells with growth benefits of specialization. We measured the degree of phenotypic specialization in two parallel metabolic pathways, the assimilation of glucose and arabinose. We grew Escherichia coli in chemostats, and used isotope-labeled sugars in combination with nanometer-scale secondary ion mass spectrometry and mathematical modeling to quantify sugar assimilation at the single-cell level. We found large variation in metabolic activities between single cells, both in absolute assimilation and in the degree to which individual cells specialize in the assimilation of different sugars. Analysis of transcriptional reporters indicated that this variation was at least partially based on cell-to-cell variation in gene expression. Metabolic differences between cells in clonal populations could potentially reduce metabolic incompatibilities between different pathways, and increase the rate at which parallel reactions can be performed.
Measurements of ion distributions at a charged solid–liquid interface using X-ray standing waves (XSW) are presented. High energy synchrotron radiation (17.48 keV) is used to produce an XSW pattern inside a thin water film on a silicon wafer. The liquid phase is an aqueous solution containing Br and Rb ions. The surface charge is adjusted by titration. Measurements are performed over a pH range from 2.2–9, using the native Si oxide layer and functional (amine) groups as surface charge. The Debye length, indicating the extension of the diffuse layer, could be measured with values varying between 1–4 nm. For functionalized wafers, the pH dependent change from attraction to repulsion of an ion species could be detected, indicating the isoelectric point. In combination with the measurement of the streaming current, the surface charge of the sample could be quantified.
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.
Well-defined and facetted bimetallic gold–palladium nanoalloys have been synthesized and anchored in spherical polyelectrolyte brushes (SPB) as composite particles (AuPd@SPB). These particles are better catalysts in aqueous phase than the pure metals. The atomistic arrangement of these nanoalloys has been analysed by extended X-ray absorption fine structure (EXAFS) spectroscopy at the Au–L3 and the Pd–K absorption edge. The samples with high amounts of gold appear as almost statistically mixed random alloys. Alloy compositions with less gold show slight enrichment of Pd at the surface of the particle. In addition, signals of non-metallic palladium appear at the Pd–K edge which indicate the presence of the Pd2+ species in addition to metallic palladium. The relation of these structural features to the catalytic activity is discussed.
Four hundred and sixteen silver coins stemming from the Ottoman Empire (16th and 17th centuries) were analyzed to confirm the fineness of the coinage as well as to study the provenance of the alloy used for the coins. As most of the coins showed the typical green patina on their surfaces due to corrosion processes that have led to the depletion of copper in the near surface domains of the silver coins in comparison to their core composition, small samples had to be taken, embedded in synthetic resin, and cross sectioned to investigate the true-heart metal composition. µ-synchrotron micro X-ray fluorescence analysis and µ-proton-induced X-ray emission were applied to determine the silver contents as well as the minor and trace elements. The type of the alloy was investigated as well as if coins minted in different locations demonstrated homogeneous traits concerning the predominant impurities (Au and Bi), which could suggest a common ore. Finally, energy-dispersive microanalysis in a scanning electron microscope was applied to study the homogeneity/heterogeneity of the coins and the presence of surface enrichments and to explain differences between the µ-synchrotron micro X-ray fluorescence analysis and µ-proton-induced X-ray emission measurements concerning the main component. In general, the silver content of the analyzed specimen varies between 90 and 95%. These outcomes have not supported the historical interpretations, which predict that during the period studied, a debasement of approximately 44% of the silver content of the coins should have occurred.
The conventional hybridoma screening and subcloning process is generally considered to be one of the most critical steps in hapten-specific antibody production. It is time-consuming, monoclonality is not guaranteed, and the number of clones that can be screened is limited. Our approach employs a novel hapten-specific labeling technique of hybridoma cells. This allows for fluorescence-activated cell sorting (FACS) and single-cell deposition and thereby eliminates the above-mentioned problems. A two-step staining approach is used to detect antigen specificity and antibody expression: in order to detect antigen specificity, hybridoma cells are incubated with a hapten−horseradish peroxidase conjugate (hapten−HRP), which is subsequently incubated with a fluorophore-labeled polyclonal anti-peroxidase antibody (anti-HRP−Alexa Fluor 488). To characterize the expression of membrane-bound immunoglobulin G (IgG), a fluorophore-labeled anti-mouse IgG antibody (anti-IgG−Alexa Fluor 647) is used. Hundreds of labeled hybridoma cells producing monoclonal antibodies (mAbs) specific for a hapten were rapidly isolated and deposited from a fusion mixture as single-cell clones via FACS. Enzyme-linked immunosorbent assay (ELISA) measurements of the supernatants of the sorted hybridoma clones revealed that all hapten-specific hybridoma clones secrete antibodies against the target. There are significant improvements using this high-throughput technique for the generation of mAbs including increased yield of antibody-producing hybridoma clones, ensured monoclonality of sorted cells, and reduced development times.
Surface self-assembly of spherical nanoparticles of sizes below 10 nm into hierarchical heterostructures is under arising development despite the inherent difficulties of obtaining complex ordering patterns on a larger scale. Due to template-mediated interactions between oil-dispersible superparamagnetic nanoparticles (MNPs) and polyethylenimine-stabilized gold nanoparticles (Au(PEI)NPs) at the water–oil interface of microemulsions, complex nanostructured films can be formed. Characterization of the reverse microemulsion phase by UV–vis absorption revealed the formation of heteroclusters from Winsor type II phases (WPII) using Aerosol-OT (AOT) as the surfactant. SAXS measurements verify the mechanism of initial nanoparticle clustering in defined dimensions. XPS suggested an influence of AOT at the MNP surface. Further, cryo-SEM and TEM visualization demonstrated the elongation of the reverse microemulsions into cylindrical, wormlike structures, which subsequently build up larger nanoparticle superstructure arrangements. Such WPII phases are thus proven to be a new form of soft template, mediating the self-assembly of different nanoparticles in hierarchical network-like filaments over a substrate during solvent evaporation.
The application of compact NMR instruments to hot flowing samples or exothermically reacting mixtures is limited by the temperature sensitivity of permanent magnets. Typically, such temperature effects directly influence the achievable magnetic field homogeneity and hence measurement quality. The internal-temperature control loop of the magnet and instruments is not designed for such temperature compensation. Passive insulation is restricted by the small dimensions within the magnet borehole. Here, we present a design approach for active heat shielding with the aim of variable temperature control of NMR samples for benchtop NMR instruments using a compressed airstream which is variable in flow and temperature. Based on the system identification and surface temperature measurements through thermography, a model predictive control was set up to minimise any disturbance effect on the permanent magnet from the probe or sample temperature. This methodology will facilitate the application of variable-temperature shielding and, therefore, extend the application of compact NMR instruments to flowing sample temperatures that differ from the magnet temperature.
EXAFS analysis of pure elements, binary and ternary equiatomic refractory alloys within the Nb-Zr-Ti-Hf- Ta system is performed at the Nb and Zr K-edges to analyze the evolution of the chemical local environ- ment and the lattice distortion. A good mixing of the elements is found at the atomic scale. For some compounds, a distribution of distances between the central atom and its neighbors suggests a distortion of the structure. Finally, analysis of the Debye-Waller parameters shows some correlation with the lat- tice distortion parameter δ², and allows to quantify experimentally the static disorder in medium entropy alloys.
Fire-gilding is a historic technique for the application of golden layers on a number of different base materials utilizing a gold amalgam. This technique leaves a significant amount of Hg in the golden layer, giving archeometrists a reliable indicator to identify firegildings.
Recent findings on presumably fire-gilded objects have shown in several cases significantly lower Hg content than previously studied objects. This prompted a synchrotron-based X-ray fluorescence investigation into the Hg distribution along the material–gilding interface, as well as a series of measurements regarding the Hg content development in fire-gilded samples during artificial aging. This work presents findings on laboratory-prepared fire-gildings, indicating an Hg enrichment at the interface of firegilded silver samples. Notably, such an enrichment is missing in fire-gilded copper samples. Further, it is confirmed that fire-gilded layers typically do not undercut an Hg bulk content of 5%. In this light, it seems improbable that ancient samples that contain <5% Hg are fire-gilded. The results presented in this study might lead to a non-destructive method to identify the Hg enrichment at the interface. This might be obtained by a combination of different non-destructive measurements and might also work unambiguously in samples in which the gold top layer is altered.
The impact of phosphorus-containing flame retardants (FR) on rigid polyisocyanurate (PIR) foams is studied by systematic variation of the chemical structure of the FR, including non-NCO-reactive and NCO-reactive dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO)- and 9,10 dihydro-9-oxa-10 phosphaphenanthrene-10-oxide (DOPO)-containing compounds, among them a number of compounds not reported so far. These PIR foams are compared with PIR foams without FR and with standard FRs with respect to foam properties, thermal decomposition, and fire behavior. Although BPPO and DOPO differ by just one oxygen atom, the impact on the FR properties is very significant: when the FR is a filler or a dangling (dead) end in the PIR polymer network, DOPO is more effective than BPPO. When the FR is a subunit of a diol and it is fully incorporated in the PIR network, BPPO delivers superior results.
Polymers of intrinsic microporosity (PIMs) are promising candidates for the active layer in gas separation membranes due to their high permeability and reasonable permselectivity. These appealing properties originate from a microporous structure as a result of inefficient segment packing in the condensed state due to a combination of a ladder-like rigid backbone and sites of contortion. However, this class of polymers suffers from a significant decrease in the permeability with time due to physical aging, whereby typically, the permselectivity increases. The initial microporous structures approach a denser state via local rearrangements, leading to the reduction of the permeability. Hence, a detailed characterization of the molecular mobility in such materials can provide valuable information on physical aging. In this work, the dielectric behavior of PIM-1 films and their behavior upon heating (aging) were revisited by isothermal frequency scans during different heating/cooling cycles over a broad temperature range between 133 and 523 K (−140 to 250 °C). In addition, the obtained results were compared with data of samples that were annealed at ambient temperatures over different time scales. Multiple dielectric processes were observed: several relaxation processes due to local fluctuations and a Maxwell−Wagner−Sillars polarization effect related to the microporosity. The temperature dependence of the rates of all processes follows the Arrhenius law where the estimated activation energy depends on the nature of the process. The influence of the thermal history (aging) on the processes is discussed in detail.
Im deutschen Eisenbahnnetz sind ca. 80 Millionen Spannbetonschwellen verbaut. Analog zu anderen Bauwerken werden Wpannbetonschwellen regelmäßig visuell inspiziert. Die Rissbildung ist bei diesen Inspektionen ein Kriterium für die Schädigung einer Spannbetonschwelle. Durch Rissbildung kann es passieren, dass Betonschwellen ihre Nutzungsdauer nicht erreichen.
A series of new flame retardants (FR) based on dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO) incorporating acrylates and benzoquinone were developed previously. In this study, we examine the fire behavior of the new flame retardants in polyisocyanurate (PIR) foams. The foam characteristics, thermal decomposition, and fire behavior are investigated. The fire properties of the foams containing BPPO-based derivatives were found to depend on the chemical structure of the substituents. We also compare our results to state-of-the-art non-halogenated FR such as triphenylphosphate and chemically similar phosphinate, i.e. 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide (DOPO), based derivatives to discuss the role of the phosphorus oxidation state.
In this paper, we present and validate the concept of an autonomous aerial robot to reconstruct tomographic 2D slices of gas plumes in outdoor environments. Our platform, the so-called Unmanned Aerial Vehicle for Remote Gas Sensing (UAV-REGAS), combines a lightweight Tunable Diode Laser Absorption Spectroscopy (TDLAS) gas sensor with a 3-axis aerial stabilization gimbal for aiming at a versatile octocopter. While the TDLAS sensor provides integral gas concentration measurements, it does not measure the distance traveled by the laser diode’s beam nor the distribution of gas along the optical path. Thus, we complement the set-up with a laser rangefinder and apply principles of Computed Tomography (CT) to create a model of the spatial gas distribution from a set of integral concentration measurements. To allow for a fundamental ground truth evaluation of the applied gas tomography algorithm, we set up a unique outdoor test environment based on two 3D ultrasonic anemometers and a distributed array of 10 infrared gas transmitters. We present results showing its performance characteristics and 2D plume reconstruction capabilities under realistic conditions. The proposed system can be deployed in scenarios that cannot be addressed by currently available robots and thus constitutes a significant step forward for the field of Mobile Robot Olfaction (MRO).
Smouldering fires and explosions arising from self-ignition of coal dust deposits represent a serious hazard for human being, environment and industry. It is essential for plant operators to know the conditions (temperature, duration and quantity) at which storage will be safe. In this work, self-ignition behaviour of three bituminous coal dusts in large scales are theoretically studied, based on the experimental data via a standardized hot-basket apparatus. A comprehensive 2-D transient model is developed, using a 2nd-order reaction kinetics considering both coal and oxygen consumptions, to investigate self-ignition parameters of coal dust accumulations. The numerical model shows a less conservative prediction compared with the steady-state methods. The computational self-ignition temperature and ignition delay time show a satisfaction agreement with lab-scale experimental results. In addition, the influences of ambient temperature and moisture content are analysed. The result shows that the moisture content delays the ignition and a small variation of the ambient temperature nearby the critical condition will lead to a large difference of the ignition delay time.
Besides conventional scanning X-ray fluorescence imaging at synchrotron sources, full-field X-ray fluorescence (FF-XRF) imaging techniques that do not implicitly require spatial scanning of the sample have become available. FF-XRF has become achievable thanks to the development of a new type of energy dispersive CCD-based 2D detector, also referred to as a 'color X-ray camera (CXC)' or 'SLcam'. We report on different imaging schemes for biological samples using FF-XRF imaging: (a) 2D 'zoom' imaging with pinhole optics using the 'camera obscura' principle; (b) 2D 'fixed magnification' imaging using magnifying polycapillary optics; and (c) 3D-FF-XRF imaging using an X-ray sheet beam or computed tomography (CT). The different FF-XRF imaging modes are illustrated using the crustacean Daphnia magna, a model organism for investigating the effects of metals on organism/ecosystem health, and foraminifera, a class of amoeboid protist. Detailed analytical characterization of the set-up is performed through analyzing various reference materials in order to determine limits of detection (LODs) and sensitivities. Experiments were performed using the BAMline at the BESSY synchrotron (Berlin, Germany) and using the P06 Hard X-ray Microprobe at the PETRAIII synchrotron (Hamburg, Germany).
Today's civil engineering NDT needs are for quantitative, fast to apply and easy to interpret methods. They are required on site both for evaluation of existing structures/infrastructure and for quality control in new construction. With this purpose, BAM has carried out in-situ feasibility studies, using radar, impact-echo and ultrasonic-echo methods. Two examples are given of their combined application on different railway slab–track constructions, using high frequency radar, scanning impact-echo and ultrasonic array methods. The aim was to evaluate limitations and advantages, comparability and complementarity of these methods. The on-site measurements demonstrated the possibility to investigate, with good accuracy via NDT, the bonding conditions between sleepers and slab, to locate voids and measure layer thickness. The acoustic and electromagnetic methods used, were found to be complementary.
On the damage behavior of dielectric films when illuminated with multiple femtosecond laser pulses
(2005)
The physical effects reducing the damage threshold of dielectric films when exposed to multiple femtosecond pulses are investigated.
The measured temperature increase of a Ta2O5 film scales exponentially with the pulse fluence. A polarized luminescence signal is observed that
depends quadratically on the pulse fluence and is attributed to twophoton excitation of self-trapped excitons that form after band-to-band
excitation. The damage fluence decreases with increasing pulse number, but is independent of the repetition rate from 1 Hz to 1 kHz at a constant
pulse number. The repetition rate dependence of the breakdown threshold is also measured for TiO2 , HfO2,
Al2O3, and SiO2 films. A theoretical model is presented that explains these findings.
Here, we present an investigation of the triple-shape properties of star-shaped polyhedral oligomeric silsesquioxane-poly(ε-caprolactone) polyurethanes (SPOSS-PUs), which have three-dimensional network structures. In a typical 'triple-shape functionalization process', mostly consisting of two tensile deformations at different temperatures, chain immobilization of the polymer network component poly(ε-caprolactone) (PCL) was successfully realized first through crystallization and then through vitrification. Subsequently, large parts of the respective strains were released under stress-free recovery conditions. The two-fold fixed ('programmed') specimens responded to heating with two independent length contractions (switching steps); the first shape change was associated with PCL devitrification and the second one with the melting of hitherto crystalline PCL. It was revealed that the triple-shape properties of SPOSS-PU networks considerably depend on PCL network chain length. When applying exactly the same 'triple-shape creation procedure', larger strain releases were detected in the first transition for polymers with a higher PCL network chain length, whereas the second transition was more accentuated for SPOSS-PU networks with a shorter PCL chain length. In the course of thermo-mechanical cycling, the formation of a neck during the second tensile deformation was repeatedly detected for SPOSS-PUs with higher PCL network chain length; in the subsequent recovery process the specimens even exhibited the highest total strain recoverability. Finally, gradual strain release could be achieved at temperatures below the PCL melting transition through the selection of up to four temperature holding steps, at which every time stable shapes were formed.
Characterization of reflector types by phase-sensitive ultrasonic data processing and imaging
(2008)
Ultrasonic and radar imaging techniques are limited in resolution by the wavelength in the material, yet information beyond those limits is hidden in complex frequency dependent reflection coefficients. The analysis of the phase of complex reflection coefficients together with the properties of imaging algorithms can help to characterize and to classify indications of defects in concrete buildings. This paper describes a method to extract phase information from measurements and SAFT reconstructed images. The influencing factors like material properties, transducer characteristics, and imaging algorithms based on Born or Physical Optics approximations are elaborated. Simulated and experimental results are briefly discussed.
This paper presents the progress of successful location of grouting faults in tendon ducts with ultrasonic imaging. The examples were obtained in the research group FOR 384 funded by DFG (German Research Foundation). The co-operation of experimental research and modeling allowed imaging and identification of grouted and ungrouted areas of tendon ducts (including strands) in a large test specimen (40 m²). In addition to the criteria for indicating grouting faults in post-tensioned ducts known until now the phase evaluation of reflected ultrasonic pulses is described. Experiments and modeling of wave propagation are presented for reflections at metal plates in concrete (thickness range 0.5 mm to 40 mm) and for tendon ducts including strands.
The main part of the progress was achieved by automated measurements using dry contact transducers, 3D-SAFT reconstruction including phase evaluation and modeling considering wave propagation for typical elastic parameters and exact experimental site conditions. The results for shear waves as well as for pressure waves are compared in the frequency range from 50 kHz to 120 kHz.
To better study the impact of nanoparticles on both in vitro and in vivo models, tissue distribution and cellular doses need to be described more closely. Here silver nanoparticles were visualized in alveolar macrophages by means of synchrotron radiation micro X-ray fluorescence spectroscopy (SR-μXRF) with high spatial resolution of 3 × 3 μm2. For the spatial allocation of silver signals to cells and tissue structures, additional elemental labeling was carried out by staining with eosin, which binds to protein and can be detected as bromine signal with SR-μXRF. The method was compatible with immunostaining of macrophage antigens. We found that the silver distribution obtained with SR-μXRF was largely congruent with distribution maps from a subsequent laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of the same tissue sites. The study shows a predominant, though not exclusive uptake of silver into alveolar macrophages in the rat lung, which can be modeled by a similar uptake in cultured alveolar macrophages. Advantages and limitations of the different strategies for measuring nanoparticle uptake at the single cell level are discussed.
The increasing demand for energy efficient separation processes fosters the development of new high performance polymers as selective separation layers for membranes. PIM-1 is the archetypal representative of the class of polymers of intrinsic microporosity (PIM) which are considered most promising in this sector, especially for gas separations. Since their introduction, PIMs stimulated a vast amount of research in this field and meanwhile evolved to the state of the art in membrane technology for gas separation. The major obstacle for extending the practical membrane application is their strong tendency to physical aging. For the first time, investigations by broadband dielectric spectroscopy (BDS) addressing molecular dynamics and conductivity in PIM 1 are presented. As chain packing during film formation from the casting solution and physical aging are key factors determining the separation performance of PIMs as membrane materials, characterization of the molecular mobility in such materials as revealed by BDS will provide valuable information for further development and optimization.
For the assessmentand for monitoring of timber structures there are numerous promising methods that enable the quantitative description of the current condition of construction elements or parts of a structure. This concerns material properties like modulus of elasticity, moisture content and density as well as structural properties like dynamic characteristics, localization of inhomogeneities, cracks, and biological attack. During the work in COST Action FP 1101, since 2012 the capability of experimental methods are discussed and compared. This covers electrical and electromagnetic wave methods (resistivity, microwave, Radar, X-Ray), elastic waves (ultrasound, pile testing) and mechanical testing (static and dynamic). Describing and collecting the use of the experimental methods for monitoring purposes was the objective of working group 3 "Monitoring of Timber Structures" of the COST Action. Monitoring capabilities will extend the use of timber structures to further applications in civil engineering. So far, no standard exists but collections of application examples and review papers representing the state of the art. From there needs for further developments regarding monitoring and NDT methods for timber structures can be identified and these are described in this paper.
Polymers with intrinsic microporosity (PIMs) are of great interest in the field of gas separation membranes. Already the first synthesized PIM-1 shows extraordinary permeability and selectivity. Unfortunately, PIM-1 is susceptible to physical aging and thus gradually loses its outstanding properties. In this study a polyhedral oligomeric silsesquioxane with phenethyl substituents (PhenethylPOSS) was used as a nanofiller (0–40 wt%) in the PIM-1 matrix to potentially improve the gas transport properties and prevent physical aging. The molecular mobility of the solution-cast nanocomposite films was analyzed by Broadband Dielectric Spectroscopy (BDS). Furthermore, gas permeability was determined with the time lag method (0–20 bar upstream pressure) at 35 °C for N2, O2, CH4 and CO2.
This paper introduces a novel robotic platform for aerial remote gas sensing. Spectroscopic measurement methods for remote sensing of selected gases lend themselves for use on mini-copters, which offer a number of advantages for inspection and surveillance. No direct contact with the target gas is needed and thus the influence of the aerial platform on the measured gas plume can be kept to a minimum. This allows to overcome one of the major issues with gas-sensitive mini-copters. On the other hand, remote gas sensors, most prominently Tunable Diode Laser Absorption Spectroscopy (TDLAS) sensors have been too bulky given the payload and energy restrictions of mini-copters. Here, we introduce and present the Unmanned Aerial Vehicle for Remote Gas Sensing (UAV-REGAS), which combines a novel lightweight TDLAS sensor with a 3-axis aerial stabilization gimbal for aiming on a versatile hexacopter. The proposed system can be deployed in scenarios that cannot be addressed by currently available robots and thus constitutes a significant step forward for the field of Mobile Robot Olfaction (MRO). It enables tomographic reconstruction of gas plumes and a localization of gas sources. We also present first results showing the gas sensing and aiming capabilities under realistic conditions.
Absorption effects and the impact of specimen shape on TXRF analysis has been discussed intensively. Model calculations indicated that ring shaped specimens should give better results in terms of higher counts per mass signals than filled rectangle or circle shaped specimens. One major reason for the difference in signal is shading effects. Full field micro-XRF with a color X-ray camera (CXC) was used to investigate shading, which occurs when working with small angles of excitation as in TXRF. The device allows monitoring the illuminated parts of the sample and the shaded parts at the same time. It is expected that sample material hit first by the primary beam shade material behind it. Using the CXC shading could be directly visualized for the high concentration specimens.
In order to compare the experimental results with calculation of the shading effect the generation of controlled specimens is crucial. This was achieved by 'drop on demand' technology. It allows generating uniform, microscopic deposits of elements. The experimentally measured shadings match well with those expected from calculation.
A novel method that optimizes the screening for antibody-secreting hapten-specific hybridoma cells by using flow cytometry is described. Cell clones specific for five different haptens were analyzed. We selectively double stained and analyzed fixed hybridoma cells with fluorophore-labeled haptens to demonstrate the target-selectivity, and with a fluorophore-labeled anti-mouse IgG antibody to characterize the level of surface expression of membrane-bound IgGs. ELISA measurements with the supernatants of the individual hybridoma clones revealed that antibodies from those cells, which showed the highest fluorescence intensities in the flow cytometric analysis, also displayed the highest affinities for the target antigens. The fluorescence intensity of antibody-producing cells corresponded well with the produced antibodies' affinities toward their respective antigens. Immunohistochemical staining verified the successful double labeling of the cells. Our method makes it possible to perform a high-throughput screening for hybridoma cells, which have both an adequate IgG production rate and a high target affinity.