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Predictive Methods for Determining the Thermal Decomposition Properties of Hazardous Substances
(2019)
Due to the fast development and availability of computers, predictive approaches are increasingly used in the evaluation process of hazardous substances complementary to experiments. Their use was recommended as alternative to experimental testing by the REACH regulation to complete the lack of knowledge on properties for existing substances that must be registered before 2018 (upon quantities). Among the proposed predictive approaches, Quantitative Structure Property Relationships (QSPR) are powerful methods to predict macroscopic properties from the only molecular structure of substances. In that context, the HAZPRED project (2015-2018, founded by the SAF€RA consortium) aims to develop theoretical models (e.g. QSPR) and small-scale tests to predict complex physico-chemical properties (e.g. thermal stability, explosivity) of hazardous substances to complete the lack of knowledge on these hazardous substances quickly or to understand their decomposition behaviour better. In particular, this contribution will present the work done in this project on the physical hazards of organic peroxides and self-reactive substances: gathering of existing experimental data, new experimental campaigns, review of existing models and proposition of new estimation methods.
The use of high niobium alloyed cast iron alloys is a relatively new approach in which the niobium addition intends to improve the properties of the material by the precipitation of hard niobium carbides during solidification. Steels can be replaced by ductile cast iron in some rolling applications, such as gears and cams, in order to reduce material costs. The aim of this work is to evaluate ductile iron alloyed with 1 weight percent (wt.%) niobium for the as cast specimens and with 1.8 wt.% and 2.4 wt.% niobium for the austempered specimens under lubricated slip-rolling tests using mixed/boundary conditions in an Amsler-type machine. Austempered ductile iron (ADI) alloyed with 1 wt.% chromium, or Carbidic ADI, was tested for comparison. For the as cast conditions, the niobium addition resulted in an increase of wear resistance owing to the low contact pressure of these tests. However, for the austempered specimens, the best performance was found for unalloyed ADI. The main factor acting in the initiation and propagation of cracks in ductile iron is the presence of the graphite nodules. The coarse carbides also contributed to the initiation of cracks and spalling of the material.
Carbidic Austempered Ductile Iron (CADI) microstructures containing eutectic carbides can be produced by the addition of carbide stabilizing elements, such as chromium. Carbides formed from the addition of Cr are eutectic of M3C type. The presence of such hard phases can enhance the abrasion wear resistance of ductile iron. A new CADI can be produced by the addition of Nb. Niobium carbide particles are formed in the beginning of solidification and remain stable once they are insoluble in solid iron matrix. The dry sand abrasive wear resistance of ductile irons alloyed with 1.0, 1.8, and 2.4 wt% Nb were tested in both “as-cast” and “heat treated” conditions using standard ASTM G65. Results were compared to abrasive wear data obtained on ductile iron alloyed with 1 wt% Cr, CADI (1 wt% Cr), and the basic composition of iron without carbide stabilizing elements. In the “ascast” condition, the addition of Nb did not lead to a reduction in wear, while CADI with Nb is a promising substitute for CADI with Cr addition, because both materials showed very similar values of abrasion resistance.
Micro-ploughing and micro-cutting mechanisms were observed on the worn surfaces of ductile irons. Abrasive wear resistance of these alloys was correlated with the volume fraction of carbides.
Eu2+ is used to replace toxic Pb2+ in metal halide perovskite nanocrystals (NCs). The synthesis implies injection of cesium oleate into a solution of europium (II) bromide at an experimentally determined optimum temperature of 130 ○C and a reaction time of 60 s. Structural analysis indicates the formation of spherical CsEuBr3 nanoparticles with a mean size of 43 ± 7 nm. Using EuI2 instead of EuBr2 leads to the formation of 18-nm CsI nanoparticles, while EuCl2 does not show any reaction with cesium oleate forming 80-nm EuCl2 nanoparticles.
The obtained CsEuBr3 NCs exhibit bright blue emission at 413 nm (FWHM 30 nm) with a room temperature photoluminescence quantum yield of 39%. The emission originates from the Laporte-allowed 4f7–4f65d1 transition of Eu2+ and shows a PL decay time of 263 ns.
The long-term stability of the optical properties is observed, making inorganic lead-free CsEuBr3 NCs promising deep blue emitters for optoelectronics.
Singlet oxygen can severely damage biological tissue, which is exploited in photodynamic therapy (PDT). In PDT, the effective range is limited by the distribution of the photosensitizer (PS) and the illuminated area. However, no distinction is made between healthy and pathological tissue, which can cause undesired damage. This encouraged us to exploit the more acidic pH of cancerous tissue and design pH-controllable singlet oxygen-generating boron-dipyrromethene (BODIPY) dyes. A pH sensitivity of the dyes is achieved by the introduction of an electronically decoupled, photoinduced electron transfer (PET)-capable subunit in meso-position of the BODIPY core. To favor triplet-state formation as required for singlet Oxygen generation, iodine substituents were introduced at the chromophore core. The resulting pH-controlled singlet oxygen-generating dyes with pKa values in the physiological range were subsequently assessed regarding their potential as pH-controlled PS for PDT.
Using HeLa cells, we could successfully demonstrate markedly different pH-dependent cytotoxicities upon illumination.
Due to the penetration of harmful chlorides into concrete, e.g. from de-icing salt, damage processes such as chloride-related pitting corrosion can occur if critical values are exceeded. In this study, multiphase materials such as chloride-contaminated concrete are examined in detail. A direct comparison is made by analyzing the spectroscopic information of simultaneously measured atomic and molecular emissions with laser-induced breakdown spectroscopy (LIBS). In addition, the influence on the calibration is examined on the basis of the combined spectral information of both reaction paths of the penetrated chlorides. The calibration models of univariate and multivariate methods were validated using reference samples with wet chemical analysis. The results are applied to a concrete sample of a parking deck, which was also analyzed by potentiometric wet chemistry. In order to account for the heterogeneity of concrete, spatially (200 μm) and spectroscopically (0.1 nm) resolved LIBS measurements were performed using a fully automated laboratory system. Simultaneous measurements with three spectrometers allow the analysis of the emission processes of several elements such as Cl, Ca, O, Si and Mg as well as the newly formed molecules CaO and CaCl. The evaluation of the molecular emission in combination with atomic lines extends the analytical performance, since different concrete phases such as aggregates and cement matrix can be better represented. The measurements were carried out in ambient air and with helium purge gas. The limit of detection (LOD) achieved for a combined evaluation of atomic and molecular emission was determined to be 0.028 wt%.
Formale Pflichterfüllung
(2019)
Probleme mit der Einhaltung formaler Anforderungen bei der Beantragung von Baumusterzulassungen können für Verärgerung sorgen – nicht nur beim Antragsteller, sondern auch bei der Zulassungsbehörde. Warum die Formalitäten aber so wichtig sind, welche Spielräume die Behörden tatsächlich haben und wie Sorgfalt und Gründlichkeit zu mehr Planungssicherheit innerhalb eines komplexen Systems führen, möchte dieser Beitrag anhand einiger Beispiele zeigen.
Due to the stochastic nature of crack nucleation by Vickers indentation, a statistical analysis of propagation rates of 185 radial cracks was performed. Crack growth was observed directly using a video camera with high Image acquisition rate. It is found that propagation rates are controlled by the environmental reactions at the crack-tip shortly after their initiation (< 1 s). Calibration of the stress intensity KI showed that the residual stress factor χ and the exponent n of the equation KI==χPc−n (with P==load and c==crack length) are broadly distributed among the 185 analyzed cracks, ranging from 10−16 to 104 and from 0.1 to 5, respectively. For the most frequent crack, the equation KI==0.052Pc−1.47 holds. The results show that correlations of indentation-induced crack length to stress intensity necessitate the use of statistical significant data that are calibrated by the environmental reactions at the crack-tip.
Hydrogen gas diffusivity of fourteen glasses of the Na2O-Al2O3-SiO2 system are studied along the joins quartzalbite-jadeite-nepheline (Qz-Ab-Jd-Np, fully polymerized) and albite-sodium disilicate (Ab-Ds, depolymerized).
Density measurements show that ionic porosity decreases from 54.4% (Qz) to 51.5% (Np) and from 52.4% (Ab) to 50.2% (Ds). Hydrogen diffusivity D follows similar trends but at another scale. D at 523 K decreases from 4×10−12 to 3×10−14m2 s−1 (Qz-Np) and from 4×10−13 to 3×10−15m2 s−1 (Ab-Ds). Charge compensating Na+ acting as a filling agent in fully polymerized network structures leads to up to one order of Magnitude higher diffusivities as depolymerized glass structures of the same SiO2 content where Na+ takes the role of a
modifier ion. Temperature dependence of the diffusivity indicates that both the activation energy involved with the moving H2 molecule as well as the accessible volume in the structure contribute to this compositional trend.
Corrosion fatigue specimen with different surfaces (technical surfaces after machining and polished surfaces) of high alloyed martensitic stainless steel X46Cr13 (1.4043) and duplex stai nless steel X2CrNiMoN22 3 2 (1.4462) were compared at load amplitudes from 175 MPa to 325 MPa in the geothermal brine of the N orthern German Basin at 98 °C. Surface corrosion layers and pits reveal carbonate corrosion products on the surface such as FeCO 3 and FeOOH as the main precipitation phases with no dependence on the original surface roughness . At high stress amplitudes above 275 MPa technical surfaces (P50% at σa 300 MPa=5 × 10 5 ) resulted in more cycles to failure than polished (P50% at σa 300 MPa=1.5 × 10 5 ). The greater slope coefficient for technical surfaces k = 19.006 compared to polished surfaces k =8.78 demonstrate s earlier failure at given stress amplitude σa .
CCQM key comparison K-153 Measurement of Specific Adsorption A [mol/kg] of N-2 and Kr on nonporous SiO2 at LN temperature (to enable a traceable determination of the Specific Surface Area (BET) following ISO 9277) has been performed by the Surface Analysis Working Group (SAWG) of the Consultative Committee for Amount of Substance (CCQM). The objective of this key comparison is to compare the equivalency of the National Metrology Institutes (NMIs) and Designated Institutes (DIs) for the measurement of specific adsorption, BET specific surface area) of nonporous substances (sorbents, ceramics, catalytic agents, etc) used in advanced technology.
In this key comparison, a commercial nonporous silicon dioxide was supplied as a sample. Eight NMIs participated in this key comparison, but only five NMI's have reported in time. All participants used a gas adsorption method, here nitrogen and (or) krypton adsorption at 77.3 K, for analysis according to the international standards ISO 15901-2 and 9277.
In this key comparison, the degrees of equivalence uncertainties for specific adsorption nitrogen and krypton, BET specific surface area were established.
Biofouling constitutes a major challenge in the application of biosensors and biomedical implants, as well as for (food) packaging and marine equipment. In this work, an antifouling surface coating based on the combination of mussel-inspired dendritic polyglycerol (MI-dPG) and an amine-functionalized block copolymer of linear polyglycerol (lPG−b−OA11, OA = oligo-amine) was developed. The coating was compared to a MI-dPG surface which was postfunctionalized with commercially available amine-terminated Polyethylene glycol (HO−PEG−NH2) of similar molecular weight. In the current work, These coatings were compared in their chemical stability, protein fouling characteristics, and cell fouling characteristics. The lPG−b−OA11-functionalized coating showed high chemical stability in both phosphate buffered saline (PBS) and sodium dodecyl sulfate (SDS) solutions and reduced the adhesion of fibrinogen from human plasma with 99% and the adhesion of human serum albumin with 96%, in comparison to the bare titanium dioxide substrate. Furthermore, the Proliferation of human umbilical vein endothelial cells (HUVECs) was reduced with 85% when the lPG−b−OA11 system was compared to bare titanium dioxide. Additionally, a reduction of 94% was observed when the lPG−b−OA11 system was compared to tissue culture polystyrene.
Roaldite – Fe4N – has been identified in the São Julião de Moreira iron meteorite using electron backscatter diffraction (EBSD) and simultaneously acquired energy-dispersive x-ray spectroscopy (EDS). Mean-periodic-number images derived from raw EBSD patterns confirm this phase by an even higher spatial resolution compared to EDS.
Roaldite appears in the form of systematically and repetitively aligned plates. Despite the locally heavy plastic deformation, it is shown that the origin of the oriented precipitation of roaldite is linked to the orientation of the kamacite matrix. Roaldite can be considered to be precipitated from kamacite using an inverse Kurdjumov-Sachs (K-S) or Nishiyama-Wassermann (N-W) orientation relationship. A more accurate discrimination is impossible due to the accumulated shock deformation, which blurs the local reference orientation of kamacite. The habit plane of roaldite is found to be {112}R, which is most likely parallel to {120}K of kamacite. Some of the roaldite plates contain two orientation variants which repeatedly alternate. Their misorientation angle is about 12°.
The presence of any aflatoxin contamination in exported figs needs to be monitored and measured through reliable and traceable methods, which require pure and matrix certified reference materials. On the other hand, certified reference materials (CRM) for determination of aflatoxins in dried fig are not yet available. Moreover, there is a lack of CRMs to be used in routine testing laboratories for method validation and quality control. The routine testing laboratories, participating in commercial proficiency testing (PT) programs, use the results available from consensus values to evaluate the performance of the participating laboratories, rather than metrologically traceable assigned values. This study initially proposed as a key comparison and presented at the EURAMET TC-MC SCOA meeting in Malta in 2015 and subsequently at the CCQM OAWG meeting in April 2015, proposes a CRM candidate for determination of levels of aflatoxins B1, B2, G1, G2 and their total in dried. Evidence of successful participation in formal, relevant international comparisons are needed to document measurement capability claims (CMCs) made by national metrology institutes (NMIs) and designated institutes (DIs).
In total nine NMI/DI participated in the Track C Key Comparison CCQM-K138 Determination of aflatoxins (AFB1, AFB2, AFG1, AFG2 and Total AFs) in Dried Fig. Participants were requested to evaluate the mass fractions expressed in ng/g units, of aflatoxins B1, B2, G1, G2 and total aflatoxin in a dried food matrix, dried fig. The CCQM-K138 results for the determination of aflatoxins (AFB1, AFB2, AFG1, AFG2 and total AFs) are ranging from 5.17 to 7.27 ng/g with an %RSD of 10.47 for AFB1, ranging from 0.60 to 0.871 ng/g with an %RSD of 11.69 for AFB2, ranging from 1.98 to 2.6 ng/g with an %RSD of 10.36 for AFG1, ranging from 0.06 to 0.32 ng/g with an %RSD of 35.6 for AFG2, and ranging from 8.29 to 10.31 ng/g with an %RSD of 7.69 for Total AFs. All participants based their analyses on LC-MS/MS, HPLC-FLD, HR-LC/MS, and IDMS. Brief descriptions of the analytical methods used by the participants, including sample preparation, analytical technique, calibrants, and quantification approach are summarized in Appendix F. Linear Pool was used to assign the Key Comparison Reference Values (KCRVs) for B1, B2, G1, G2 and total aflatoxins. Due to the traceability requirements for the calibrants not being met, results of KEBS, INTI, VNIIM and BAM were excluded from KCRV determination.
Successful participation in CCQM-K138 demonstrates the following measurement capabilities in determining mass fraction of organic compounds, with molecular mass of 100 g/mol to 500 g/mol, having high polarity (pKow > -2), in mass fraction range from 0.05 ng/g to 500 ng/g in dried food matrices.
Приведено аналитическое решение задачи теплопроводности после прекращения действия подвижного источника теплоты для различных комбинаций источника и свариваемого тела. Показано, что после выключения источника возможно дополнительное плавление основного металла за счет перегретого жидкого металла сварочной ванны. Например, при лазерной сварке со сквозным проплавлением стальной пластины толщиной 2 мм длина кратера шва может быт на 19% больше установившейся длины сварочной ванны. Установлено, что центр кратера, в котором заканчивается затвердевание жидкого металла, смещен в сторону хвостовой части кратера относительно оси теплового источника в момент прекращения его действия. Скорость и направление кристаллизации металла сварочной ванны и кратера различны.
Es geht auch einfacher
(2019)
Mit laserbasiertem Verfahren Zustand von Betonbauwerken erfassen: Die Laserinduzierte Breakdown Spektroskopie (LIBS) stellt eine Alternative zur nasschemischen Analyse dar, um den Zustand von Betonbauwerken zu erfassen. Bei diesem Verfahren laufen der Analysevorgang und die Auswertung automatisiert ab. Ein Prototyp für die mobile Anwendung auf der Baustelle steht zur Verfügung. So kann auf Knopfdruck ein schriftlicher Bericht erstellt werden, der einen genauen Wert für die Eindringtiefe eines relevanten Elements wie Chlorid ausgibt.
Mechanochemistry has become a valuable method for the synthesis of new materials and molecules, with a particular strength for screening and preparing multicomponent crystals. In this work, two novel cocrystals of pyrazinamide (PZA) with pimelic acid (PA) were prepared mechanochemically. Their formation was monitored in real time by in situ synchrotron powder X-ray diffraction. Control over the polymorphic form was obtained through the selective choice of liquid additive via liquid assisted grinding. Slurry experiments and dispersion-corrected density functional theory calculations suggest that Form I is the thermodynamically stable form under ambient conditions. Upon aging, Form II converts to Form I. The stability of Form II upon aging was found to depend strongly on the milling duration, intensity, and material of the milling vessels. Longer or higher energy milling drastically increased the lifetime of the Form II product. For the first time, this work also demonstrates that the choice of milling jar can have a decisive effect on the aging stability of a bulk polymorphic powder. In contrast to material prepared in steel milling vessels, the preparation of Form II in Perspex (PMMA) vessels increased its lifetime 3-fold. These findings offer a new dimension to garnering control over mechanochemical cocrystallization and demonstrate the critical importance of the careful and timely ex situ screening of ball mill grinding reactions. This will be of importance for potential industrial applications of mechanochemical cocrystallization where understanding polymorph longevity is crucial for the development of a robust preparative protocol.
The present work deals with the development of a strategy for the prevention of end crater defects in high-power laser welding of thick-walled circumferential welds. A series of experiments were performed to understand the influence of the welding Parameters on the formation of end crater defects such as pores, cracks, root excess weld metal and shrinkage cavities in the overlap area. An abrupt switch-off of the laser power while closing the circumferential weld leads to a formation of a hole which passes through the whole welded material thickness. A laser power ramp-down causes solidification cracks which are initiated on the transition from full-penetration mode to partial penetration. Defocusing the laser beam led to promising results in terms of avoiding end crater defects. Cracks and pores in the overlap area could be effectively avoided by using defocusing techniques.
A strategy for avoiding of end crater imperfections was tested on flat specimens of steel grade S355J2 with a wall thickness of between 8 mm and 10 mm and then transferred on the 10 mm thick pipe sections made of high-strength pipeline steel API5L-X100Q.
For the vast majority of ellipsometric measurements, the application of planar substrates is mandatory and requires a proper sample alignment prior to the measurement. Here, the authors present a generalized approach of how to extract the isotropic ellipsometric sample parameters from an imaging Mueller-matrix measurement even if the sample is significantly misaligned. They validate the method by layer-thickness calculations based on imaging Mueller-matrix measurements of flat crystalline silicon samples that were misaligned on purpose. Furthermore, they also exploit this method’s capabilities to perform spatially resolved layer-thickness measurements of a single-layer indium-tin-oxide coating on a fused-silica microlens without the need of realignment or repositioning of the sample during the measurement.
Microorganisms perform multiple metabolic functions that shape the global cycling of elements, health and disease of their host organisms, and biotechnological processes. The rates, at which different metabolic activities are performed by individual cells, can vary between genetically identical cells within clonal populations. While the molecular mechanisms that result in such metabolic heterogeneity have attracted considerable interest, the environmental conditions that shape heterogeneity and its consequences have received attention only in recent years. Here, we review the environmental drivers that lead to metabolic heterogeneity with a focus on nutrient limitation, temporal fluctuations and spatial structure, and the functional consequences of such heterogeneity. We highlight studies using single-cell methods that allow direct investigation of metabolic heterogeneity and discuss the relevance of metabolic heterogeneity in complex microbial communities.
In various kinds of radiography, deficient transmission imaging may occur due to backlighting inside the detector itself arising from light or radiation scattering. The related intensity mismatches barely disturb the high resolution contrast, but its long range nature results in reduced attenuation levels which are often disregarded. Based on X-ray observations and an empirical formalism, a procedure is developed for a first order correction of detector backlighting. A backlighting factor is modeled as a function of the relative detector coverage by the sample projection. Different cases of sample transmission are regarded at different backlight factors and detector coverage. The additional intensity of backlighting may strongly affect the values of materials’ attenuation up to a few 10%. The presented scenario provides a comfortable procedure for corrections of X-ray or neutron transmission imaging data.
Spherical mesoporous bioactive glasses in the silicon dioxide (SiO2)-phosphorus pentoxide (P2O5)–calcium oxide (CaO) system with a high specific surface area of up to 300m2/g and a medium pore radius of 4 nm were synthesized by using a simple one-pot surfactant-assisted sol–gel synthesis method followed by calcination at 500–700°C. The authors were able to control the particle properties by varying synthesis parameters to achieve microscale powders with spherical morphology and a particle size of around 5–10 mm by employing one structure-directing agent. Due to a high Calcium oxide content of 33·6mol% and a phosphorus pentoxide content of 4·0mol%, the powder showed very good bioactivity up to 7 d of immersion in simulated Body fluid. The resulting microspheres are promising materials for a variety of life science applications, as further processing – for example, granulation – is unnecessary. Microspheres can be applied as materials for powder-based additive manufacturing or in stable suspensions for drug release, in bone cements or fillers.
Acoustically levitated droplets have been suggested as compartmentalized, yet wall-less microreactors for high-throughput reaction optimization purposes. The absence of walls is envisioned to simplify up-scaling of the optimized reaction conditions found in the microliter volumes. A consequent pursuance of high-throughput chemistry calls for a fast, robust and sensitive analysis suited for online interrogation. For reaction optimization, targeted Analysis with relatively low sensitivity suffices, while a fast, robust and automated sampling is paramount. To follow this approach, in this contribution, a direct coupling of levitated droplets to a homebuilt ion mobility spectrometer (IMS) is presented. The sampling, Transfer to the gas phase, as well as the ionization are all performed by a single exposure of the sampling volume to the resonant output of a mid-IR laser. Once formed, the nascent spatially and temporally evolving analyte ion cloud needs to be guided out of the acoustically confined trap into the inlet of the ion mobility spectrometer. Since the IMS is operated at ambient pressure, no fluid dynamic along a pressure Gradient can be employed. Instead, the transfer is achieved by the electrostatic potential gradient inside a dual ring electrode ion optics, guiding the analyte ion cloud into the first stage of the IMS linear drift tube accelerator. The design of the appropriate atmospheric pressure ion optics is based on the original vacuum ion optics design of Wiley and McLaren. The obtained experimental results nicely coincide with ion trajectory calculations based on a collisional model.
The efficient and sensitive detection of pathogenic microorganisms in aqueous environments, such as water used in medical applications, drinking water, and cooling water of industrial plants, requires simple and fast methods suitable for multiplexed detection such as flow cytometry (FCM) with optically encoded carrier beads. For this purpose, we combine fluorescent Cd-free Ag−In−S ternary quantum dots (t-QDs) with fluorescence Lifetimes (LTs) of several hundred nanoseconds and superparamagnetic Fe3O4 nanoparticles (SPIONs) with mesoporous CaCO3 microbeads to a magneto-fluorescent bead platform that can be surface-functionalized with bioligands, such as antibodies. This inorganic bead platform enables immuno-magnetic separation, target enrichment, and target quantification with optical readout. The beads can be detected with steady-state and time-resolved fluorescence microscopy and flow cytometry (FCM). Moreover, they are suited for readout by time gated emission. In the following, the preparation of these magneto-fluorescent CaCO3 beads, their spectroscopic and analytic characterization, and their conjugation with bacteria-specific antibodies are presented as well as proof-of-concept measurements with Legionella pneumophila including cell cultivation and plating experiments for bacteria quantification. Additionally, the possibility to discriminate between the long-lived emission of the LT-encoded capture and carrier CaCO3 beads and the short-lived Emission of the dye-stained bacteria with time-resolved fluorescence techniques and single wavelength excitation is demonstrated.
Hydroliquefaction is a possible pathway to produce liquid transportation fuels from solid feedstocks like coal or biomass. Though much effort has been put into the investigation of maximizing the oil yield using expensive catalysts and pasting oils in batch setups, little is known about how to commercialize the process. This work aims at the demonstration of lignin hydroliquefaction under conditions interesting for commercial operation. The results from hydroliquefaction experiments of two different lignin types using a cheap iron-based catalyst and anthracene oil as the pasting oil in a semibatch system are presented here. Oil yields of above 50% are reached without observing coke formation. Extensive analyses of the feedstocks and product oils were performed. The process supplies high-quality oil, while differences in the decomposition path of both lignin types are observed. An high heating value of 39 400 J/g and H/C and O/C ratios of up to 1.6 and 0.1, respectively, are detected for the produced bio-oils.
An effective method for evaluating the fatigue strength of thick unidirectional composite laminates of wing spar caps has been presented here. A typical width-tapered bending specimen has been developed for a four-point loading set up. Static and fatigue loading was performed at a load ratio R = -1. The complex stress state has been investigated numerically by finite element analysis. Finally, the concept is proven experimentally on specimens made of pultruded fibre rods.
The fatigue behavior of the continuously tapered width by water Jet cutting has been compared to discrete tapering via rod-drop. The new method enables a screening of material fatigue behavior caused by normal and shear loading.
Der 60 °C-Betonversuch ist eine in Deutschland und international verbreitete Methode um die Empfindlichkeit von Gesteinskörnungen und Betonen hinsichtlich einer Alkali-Kieselsäure Reaktion (AKR) zu prüfen. Dieser Beitrag stellt eine neuentwickelte automatisierte Variante der Prüfmethode in einem Minireaktor vor. Dabei werden die Dehnungen von Betonprismen nicht, wie beim konventionellen Test manuell, sondern automatisch in entsprechend ausgerüsteten Prüfbehältern gemessen. Neben einer Reduzierung des Messaufwands bringt die automatisierte Prüfung im Minireaktor weitere Vorteile. Die Dehnungssignale werden, anders als bei der konventionellen Messung, quasi-kontinuierlich aufgezeichnet und bilden das Expansionsverhalten der Prismen detailliert ab. Außerdem bleiben Unterbrechungen der AKR-provozierenden Lagerung aus, die bei der konventionellen Prüfung notwendig sind. Im Beitrag werden die automatisierte und konventionelle Prüfung anhand der Dehnungen von Prismen zweier Gesteinskörnungen verglichen. In Übereinstimmung mit vorhergehenden Untersuchungen sind im Minireaktor gemessene Dehnungen systematisch kleiner als manuell gemessene. Als mögliche Ursache werden Unterschiede im Auslaugverhalten experimentell untersucht. Zur Überprüfung der Einstufung der zwei Gesteinskörnungen erfolgen außerdem Referenzprüfungen in der Nebelkammerlagerung bei 40 °C.
The potential of lowered surface features as well as the application of wear resistant coatings have been known for many years to improve the tribological behavior of forming tools. More recent studies also discuss the capability of protruded microfeatures for adjusting the tribological behavior between contacting surfaces. The demand for a high wear resistance of such structures as well as their economical and reliable production, however, often limits the industrial application. The laser implantation process can overcome these limitations. In contrast to conventional cw-laser dispersing processes, where the formation of uniform metal matrix composite layers is intended, this surface engineering technique aims to improve the tribological behavior of contacting surfaces by a localized dispersing of pre-placed hard ceramic particles. This enables the formation of deterministic textures composed of separated wear resistant dome- or ring-shaped microstructures (implants).
Since TaC shows very promising material properties for improving the wear resistance of tools exposed to severe operating conditions, this paper analyzes its suitability for pulsed laser implantation on X38CrMoV5-3 tool steel for the first time. In the experiments, the influence of the particles and the laser parameters (pulse power, pulse duration and focal diameter) on the material properties of the localized dispersed zones was studied by optical microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. The composite´s (micro-) hardness was measured and calculated by using a rule of mixture. Additionally, the influence of the laser parameters and the TaC particles on the geometrical properties of the implants was studied by optical microscopy and white light interferometry.
The results showed that defect-free implants with hardness values of ~900 HV1 can be obtained at the focal spot, since a localized dispersing of the TaC particles is possible using a pulsed millisecond laser. However, in dependence of the laser intensity, also a partial dissolution of the initial particles occurs. This leads to the precipitation of new dendritic TaC nanoparticles and to varying contents of retained austenite in the matrix. Both effects have a strong influence on the implant hardness and must be considert by the rule of mixture. Regarding the geometrical response it was pointed out that protruded microfeatures with heights up to 10 µm can be created. In comparison to laser remelted zones, the implanted zones showed significantly altered weld pool profiles due to the influence of the particles on the melt convection. A transition of the implant shape from predominantly dome-shaped to predominantly ring-shaped was observed for intensities >1.7∙106 W/cm2 due to the onset of the keyhole effect.
Friction stir welding (FSW) of high-melting temperature alloys, such as steel and Inconel, requires tooling that can survive under the applied loads at the elevated temperatures. Tungsten-Rhenium (W-Re) alloys are a suitable candidate for this application; however, the costs typically associated with achieving the required densities and grain structure for the tooling are high due to the lengthy traditional processing required. Further costs are incurred in machining the starting bar stock to the final FSW tooling configuration. An alternate processing method is used in this study to shorten the fabrication time using direct current sintering which rapidly consolidates the starting powders at lower temperatures than used in traditional powder metallurgy. Although this process enables retention of the fine grain size, the sintering time is too short to form the desired single, solid phase. Therefore, the specimens were subjected to a post-consolidation heat treatment to fully solutionize the W matrix. Once the desired density and solid solution phase was verified in coupons, the final processing parameters were used to consolidate a net shape tool for FSW.
The laser-based direct energy deposition (DED) as a technology for additive manufacturing allows the production of near net shape components. Industrial applications require a stable process to ensure reproducible quality. Instabilities in the manufacturing process can lead to faulty components which do not meet the required properties.
The DED process is adjusted by various parameters such as laser power, velocity, powder mass flow and spot diameter, which interact with each other. A frequently used comparative parameter in welding is the energy per unit length and is calculated from the laser power and the velocity in laser welding. The powder per unit length comparative parameter in the DED process has also be taken into account, because this filler material absorbs energy in addition to the base material.
This paper deals with the influence of mass energy as a comparative parameter for determining the properties of additively manufactured parts. The same energy per unit length of 60 J/mm as well as the same powder per unit length of 7.2 mg/mm can be adjusted with different parameter sets. The energy per unit length and the powder per unit length determine the mass energy. The laser power is varied within the experiments between 400 W and 900 W. Energy per unit length and powder per unit length are kept constant by adjusting velocity and powder mass flow. Using the example of Inconel 718, experiments are carried out with the determined parameter sets. In a first step, individual tracks are produced and analyzed by means of micro section. The geometry of the tracks shows differences in height and width. In addition, the increasing laser power leads to a higher dilution of the base material. To determine the suitability of the parameters for additive manufacturing use, the individual tracks are used to build up parts with a square base area of 20x20 mm². An investigation by Archimedean principle shows a higher porosity with lower laser power. By further analysis of the micro sections, it can be seen that at low laser power, connection errors occur between the tracks.
The results show that laser power, velocity and powder mass flow have to be considered in particular, because a constant mass energy can lead to different geometric as well as microscopic properties.
Bei der Explosion in einer Herstellungsstätte für ein Pulver zur Reinigung industrieller Feuerungsanlagen in Deutschland ist eine Person tödlich verunglückt. Die BAM wurde gebeten, beschlagnahmte Muster des Reinigungspulver zu bewerten. Dafür wurden verschiedene Untersuchungen durchgeführt. Diese sollten klären, ob die stoffliche Einstufung des Reinigungspulvers in die Stoffklasse 5.1 für die sichergestellten Pulverproben zutreffend ist. Es konnte nachgewiesen werden, dass die untersuchten Pulverproben explosionsgefährliche Eigenschaften aufweisen. Die von explosionsgefährlichen Stoffen ausgehenden Gefährdungen müssen ermittelt und bei der Herstellung und Verwendung berücksichtigt werden. Die Gefährdungen sind entsprechend neu eingeführter sicherheitstechnischer Kennzahlen ermittelt und anschließend klassifiziert worden. Die Klassifizierung erfolgte durch die Zuordnung zu einer s.g. Gefahrgruppe.
Vor 30 Jahren wurde die erste BAM-Zulassung für ein Geokunststoffprodukt in der Deponietechnik ausgestellt. Seither wurden immer wieder eigene wissenschaftliche Untersuchungen durchgeführt, neue Forschungsergebnisse herangezogen und die Prüftechnik weiterentwickelt, um die Eignung und Funktionsdauer von Kunststoffdichtungsbahnen, Schutzschichten, Kunststoff-Dränelementen, geotextilen Filtern oder Bewehrungsgittern beurteilen zu können. Einige dieser Entwicklungen werden hier diskutiert.
A novel mixed matrix composite has been prepared using solution-casting method at different volume concentrations of polyvinyl alcohol; PVA (50, 67, 75 and 80 %) and fixed amount of Dimethoxydimethylsilane in air atmosphere. The hydrolyzed dimethyldisilanol acts as in-situ cross linker through a wet-out condensation between the hydroxyl moieties of SiOH and PVAOH. Such process improves the mechanical properties of composite membranes as compared to pristine PVA which has been determined as function of varied membrane components to evaluate the structure/property relationships.
Furthermore, DFT (B3LYP)/6-31G(d) geometry and frequency computations were carried out for the suggested dimeric PVA structures via 1,3-diol linkage followed by condensation and hydrogen bonding interaction. Vibrational interpretations of composite membranes were proposed based on the computed wavenumbers, Cartesian coordinates displacements for the suggested hydrolyzed products involving the dominant PVA/SiOH/SiOC/SiOSi functional groups compared with those given in literatures. FTIR and EDX provide clear evidences for incorporating silicon to 3D network. Meanwhile, the infrared de-convoluted spectral interpretations ensure 17-30% cross-linked SiOC within the network of Composite membranes.
Crack detection in metallic samples at high surface temperature, hostile and hazardous environments, etc. is challenging situation in any manufacturing industries. Most of the present NDE methods are suitable only for lower surface temperatures, especially room temperature. In this situation, we need a fast and non-contact NDT method which can be applied even in high sample surface temperature. Laser thermography is one of the techniques having a high potential in non-contact inspection. As a preliminary investigation, in this article, we have studied the potentiality of laser line thermography in crack detection at room temperature. In laser line thermography, a continuous wave (CW) laser is used to generate a laser line, which in turn is used to scan the metal surface. The heat distribution over the sample surface is recorded by an infrared thermal (IR) camera. Two different approaches are reported in this work. Firstly, a stationary laser line source and its interaction with cracks; secondly, moving laser line source scanning over a surface with crack. When the distance between crack centre to laser line centre increases, crack detectability will decrease; and when laser power increases, crack detectability will increase. A dedicated image processing algorithm was developed to improve the detectability of the cracks. To understand the heat transfer phenomenon, a simplified 3D model for laser thermography was developed for the heat distribution during laser heating and was validated with experimental results. Defects were incorporated as a thermally thin resistive layer (TTRL) in numerical modeling, and the effect of TTRL in heat conduction is compared with experimental results.
Explosion and decomposition limits of flammable and chemically unstable gases were determined experimentally in a closed autoclave with an ignition energy higher than the standard 10 J a 20 J. The ignition source was a lightning arc caused by an exploding wire igniter as described in EN 1839 B. With a newly developed ignition system a graded ignition energy between 3 J and 1000 J was generated. Different types of gases were studied with this ignition system: methane as a typical fuel gas and reference gas for some standards for explosion limit determination, the refrigerant R32 (difluoromethane) as a mildly flammable gas with low burning velocity and high minimum ignition energy compared with methane as well as the chemical unstable gases acetylene, nitrous oxide and ethylene oxide, which can decompose explosively in the absence of air or other oxidizers. It was found that the influence of strong ignition sources on explosion and decomposition limits can be very different for different systems. In case of methane only the upper explosion limit was influenced significantly by the ignition energy, whereas the lower explosion limit was constant. In a standard test vessel with an inner volume of 14 dm3 it was difficult to quantify the upper explosion limit of methane exactly with the strong ignition source, because the explosion pressure did not increase abruptly near the explosion limit, but steadily over a large concentration range. Probably a larger explosion vessel is more appropriate in this case. In case of R32 however, it was the lower explosion limit that was influenced significantly by the ignition energy and not the upper explosion limit. A particularly strong dependency from the ignition energy was found for the decomposition limits of the chemically unstable gases in nitrogen. Here special regard is necessary in practical applications, if uncommonly strong ignition sources cannot be excluded.
Cadmium benzylphosphonate Cd(O3PBn)·H2O and its fluorinated derivates Cd(O3PBn-3F)·H2O, Cd(O3PBn-4F)·H2O, and Cd(O3PBn-F5)·H2O were synthesized mechanochemically. The Crystal structures of the compounds were determined based on powder X-ray diffraction (PXRD) data. The influence of the ligand substitution on the crystal structure of the metal phosphonate was determined. The hydrophobicity as a function of degree of fluorination was investigated using dynamic vapor sorption.
Molecular mobility of cyanophenyl alkylbenzoates (CPnBs) (n = 2, 3, 7 – number of carbon atoms in the alkyl chain) in the bulk and in composites with aerosil A380 is investigated by broadband dielectric spectroscopy, while thermal analysis and infrared spectroscopy were applied to characterise the molecular species. The work completes preliminary results obtained for the members with n = 4 … 6. An interaction by hydrogen bonding, between aerosil surface – OH groups and – CN or ester groups of the CPnB molecules takes place. It slows down the relaxation process as observed for related composites in comparison to the pure materials. The existence of two types of bonding might be the reason that Vogel temperature for the relaxation process in the surface layer does not show the odd-even effect. Temperature dependence of the relaxation rates for composites
shows a crossover behaviour from a high to a low temperature regime. Moreover, the temperature dependence of the dielectric strength is unusual. As the loading degree is similar, comparison of the dielectric, spectroscopic and thermal data obtained here and with the results obtained for the composites with n = 4 … 6 can be directly done. Increasing the number of the members of the homologous series confirms and hardens the preliminary conclusions.
Chemically modified bioactive glasses based on ICIE16 were prepared with the melt-quenching method using water as a quenching medium. The sinterability of these bioactive glasses was investigated and is discussed in this article. The sintering experiments were conducted with different sintering temperatures, sintering times and heating rates. Those parameters are crucial for dense glass with an amorphous structure. The particle size (d50) of the starting glass powder was determined at 88 μm and kept constant. The pre-pressed glass pellets were cold-isostatically pressed at 300 MPa to a green density of around 63 %. Density development, phase identification, shrinkage behavior and the microstructure were investigated to determine the sinterability of the developed glasses. The glass powders were sintered at different temperatures inside the processing window while crystallization was monitored. The results have shown that the sinterability of the developed glasses strongly dependsonthe proposed chemical additions. The highest density reached was 96 %, which belongs to BP1 glass with sintering conditions of 20 K/min heating rate for 60 min at 750 °C.
The simulation of strength experiments by the Monte-Carlo method enables the numerical generation of data representing a complete populations of composite pressure vessels. In the case of composite pressure vessels used for hydrogen storage, properties like burst strength or fatigue cycle strength are of interest. This paper provides comprehensive information on how populations are generated and how samples can be taken and evaluated; it also explains how to determine the acceptance rate of random samples from simulated populations for passing the approval test "minimum burst pressure". A word of caution is also expressed regarding the evaluation of acceptance rates from a small sample.
Advanced high strength steels are usually coated by a zinc layer for an increased resistance against corrosion. During the resistance spot welding of zinc coated steel grades, liquid metal embrittlement (LME)mayoccur. As a result, cracking inside and around the spot weld indentation is observable. The extent of LME cracks is influenced by a variety of different factors. In this study, the impact of the used electrode geometry is investigated over a stepwise varied weld time.
A spot welding finite element simulation is used to analyse and explain the observed effects. Results show significant differences especially for highly increased weld times. Based on identical overall dimensions, electrode geometries with a larger working plane allow for longer weld times, while still preventing LME within the investigated material and maintaining accessibility.
Pirfenidone is an important drug molecule used in the treatment of idiopathic lung fibrosis. Although approved by the USFDA in 2014, pirfenidone’s aqueous solubility is too high and must be mitigated by additives. In this work, the cocrystallization of pirfenidone is explored as an alternative approach to reducing its solubility. Herein, an anhydrous form of pirfenidone is reported, alongside its first two reported cocrystals. The new crystalline solids are thoroughly characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction analysis (PXRD), Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA).
Equilibrium solubility and intrinsic dissolution rates (IDR) are studied for the cocrystals and compared to that of the parent drug. Both cocrystal forms exhibit drastically lower aqueous solubility (by up to 90%) and dissolution rates, rationalized based on both lattice energy calculations and consideration of intermolecular interactions in the solid state. Furthermore, we compare the physicochemical properties of solution-based material with that of material produced mechanochemically. Importantly, no differences are observed between the two production methods. This work demonstrates the strength of crystal Engineering strategies to beneficially modify important pharmaceutical properties and highlights the potential of mechanochemistry to facilitate this in an environmentally benign way.
The laser implantation–named technique aims to address the tribological problems frequently seen on tool surfaces during hot stamping. It is based on the creation of elevated dome- or ring-shaped hard structures on the surface of tool steels by a localized dispersing of hard particles. Therefore, a combination of the two distinct approaches that are normally used in surface Technology for optimizing friction and wear, i.e., surface texturing and surface material optimization, are realized in one processing step. In experimental studies, a localized dispersing of TiB2 particles in the surface layer of the hot work tool steel X38CrMoV5-3 was considered and compared with punctual laser–remelted textures. The structures (micro-) hardness was measured at top- and cross-sections. With the aid of a scanning electron microscope, energy dispersive X-ray spectroscopy and X-ray diffraction the interaction between the hard particles and the substrate material were studied. From the results, an optimal parameter range was identified for laser implantation. To the investigation’s end, the implant geometry was measured by optical microscopy and White light microscopy. Furthermore, a mathematic model was introduced, which allows a prediction of the implant geometry as a response to the laser parameters. It was shown that the implantation of TiB2 particles leads to a significant hardness increase up to 1600 HV1 due to the dispersion of initial particles and an in situ precipitation of new titanium-rich phases. It was possible to create defect-free dome- and ring-shaped microstructures on the surfaces. It was also shown that the implants geometry highly depends on the applied laser parameters. The applied central composite design shows a good agreement with the experimental results.
Antifoulingmittel im Wasser
(2019)
In most chemical reactions, stable isotopes are fractionated in a mass-dependent manner, yielding correlated isotope ratios in elements with three or more stable isotopes. The proportionality between isotope ratios is set by the triple isotope fractionation exponent θ that can be determined precisely for, e.g., sulfur and oxygen by IRMS, but not for metal(loid) elements due to the lower precision of MC-ICP-MS analysis and smaller isotopic variations. Here, using Mg as a test case, we compute a complete metrologically robust uncertainty budget for apparent θ values and, with reference to this, present a new measurement Approach that reduces uncertainty on θ values by 30%. This approach, namely, direct educt-product bracketing (sample−sample bracketing), allows apparent θ values of metal(loid) isotopes to be determined precisely enough to distinguish slopes in three-isotope space. For the example of Mg, we assess appropriate quality Control standards for interference-to-signal ratios and Report apparent θ values of carbonate−seawater pairs. We determined apparent θ values for marine biogenic carbonates, where the foraminifera Globorotalia menardii yields 0.514 ± 0.005 (2 SD), the coral Porites, 0.515 ± 0.006 (2 SD), and two specimens of the giant clam Tridacna gigas, 0.508 ± 0.007 (2 SD) and 0.509 ± 0.006 (2 SD), documenting differences in the uptake pathway of Mg among marine calcifiers. The capability to measure apparent θ values more precisely adds a new dimension to metal(loid) δ values, with the potential to allow us to resolve different modes of fractionation in industrial and natural processes.
Additively manufactured test specimens made of polyamide 12 (PA 12) by Laser Sintering as well as of acrylonitrile butadiene styrene (ABS) by Fused Layer Modelling, were characterised with active thermography directly after manufacturing and after artificial weathering. For this, two different excitation methods (flash and pulse heating) were used and compared, regarding their suitability for the detection of constructed and imprinted defects inside the test specimens. To increase the quality of the thermograms, data processing methods like thermal signal reconstruction (TSR) and Fourier Transformation after TSR were applied. To further investigate the long-term stability of the additively manufactured test specimens towards environmental stress, like UV radiation, heat, humidity, water contact and frost with active thermography, an artificial weathering test over 2000 hours (~3 months) was applied to the specimens. The monitoring of the changes in the optical properties of the weathered plastics was supplemented by spectral reflectance and UV/VIS spectroscopy.
A high-pressure neutron diffraction study was conducted on polycrystalline samples of the two known polymorphs of 2,4,6-trinitrotoluene [monoclinic (m) and orthorhombic (o) TNT] under hydrostatic conditions. Isothermal equations of state were obtained for both polymorphic forms. Neither polymorph was observed to undergo a phase transition in the pressure region 0–5 GPa, with both polymorphs displaying smooth compression behavior across the pressure range. This differs somewhat from previous X-ray diffraction and Raman spectroscopy investigations in which discontinuities were observed in the P–V curves and spectral changes were reported at ∼2 GPa. The high-pressure response of these materials is supported by dispersion-corrected density functional theory calculations which, while overestimating the experimental bulk moduli, give excellent agreement with the observed smooth compression response of both phases.
In this contribution, we present three models to capture singularities in combination with the Spectral Element Method. The first model, the continued-fraction-based Scaled Boundary Finite Element Method, the second model, a new approach based on enrichment with static modes, and the third model, which uses an hp-refinement near the singularity, are compared among each other and evaluated in terms of their respective efficiency and accuracy.
One of the most important goals in civil engineering is to guaranty the safety of constructions. National standards prescribe a required failure probability in the order of 10−6 (e.g. DIN EN 199:2010-12). The estimation of these failure probabilities is the key point of structural reliability analysis. Generally, it is not possible to compute the failure probability analytically.
Therefore, simulation-based methods as well as methods based on surrogate modeling or response surface methods have been developed. Nevertheless, these methods still require a few thousand evaluations of the structure, usually with finite element (FE) simulations, making reliability analysis computationally expensive for relevant applications.
The aim of this contribution is to increase the efficiency of structural reliability analysis by using the advantages of model reduction techniques. Model reduction is a popular concept to decrease the computational effort of complex numerical simulations while maintaining a reasonable accuracy. Coupling a reduced model with an efficient variance reducing sampling algorithm significantly reduces the computational cost of the reliability analysis without a relevant loss of accuracy.