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M−N−C electrocatalysts are considered pivotal to replace expensive precious group metal-based materials in electrocatalytic conversions. However, their development is hampered by the limited availability of methods for the evaluation of the intrinsic activity of different active sites, like pyrrolic FeN4 sites within Fe−N−Cs. Currently, new synthetic procedures based on active-site imprinting followed by an ion exchange reaction, e.g. Zn-to-Fe, are producing single-site M−N−Cs with outstanding activity. Based on the same replacement principle, we employed a conservative iron extraction to partially remove the Fe ions from the N4 cavities in Fe−N−Cs. Having catalysts with the same morphological properties and Fe ligation that differ solely in Fe content allows for the facile determination of the decrease in density of active sites and their turn-over frequency. In this way, insight into the specific activity of M−N−Cs is obtained and for single-site catalysts the intrinsic activity of the site is accessible. This new approach surpasses limitations of methods that rely on probe molecules and, together with those techniques, offers a novel tool to unfold the complexity of Fe−N−C catalyst and M−N−Cs in general.
Abstract: In this work, a conceptual framework is suggested for analyzing thermorheologically simple and complex behavior by using just one approach. Therefore, the linear relation between master time and real time which is required in terms of the time-temperature superposition principle was enhanced to a nonlinear equivalent relation. Furthermore, we evaluate whether there is any relation among well-known existing time-temperature equivalent formulations which makes it possible to generalize different existing formulations. For this purpose, as an example, the power law formulation was used for the definition of the master time. The method introduced here also contributes a further framework for a unification of established time-temperature equivalent formulations, for example the time-temperature superposition principle and time-temperature parameter models. Results show, with additional normalization conditions, most of the developed time-temperature parameter models can be treated as special cases of the new formulation. In the aspect of the arrow of time, the new defined master time is a bended arrow of time, which can help to understand the corresponding physical meaning of the suggested method.
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.
Atemluftflaschen aus Faserverbundwerkstoffen werden bei einem Brandeinsatz situationsabhängig hohen thermischen Belastungen ausgesetzt. Die Grenzen der sicheren thermischen Belastbarkeit dieser Behälter werden jedoch heutzutage nicht abgeprüft. Deshalb hat es sich die Bundesanstalt für Materialforschung und -prüfung (BAM) im Austausch mit der Bergischen Universität Wuppertal zur Aufgabe gemacht, die Auswirkungen dieser Betriebslasten zu untersuchen.
In diesem vierten und letzten Teil dieser Aufsatzreihe werden die Ergebnisse der analytischen Beanspruchungsanalysen vorgestellt, die mit dem entwickelten Hybrid-Behältermodell berechnet wurden. Unter simulierten Einsatzbedingungen des Brandeinsatzes wird dabei ein bisher nicht hinreichend beachtetes thermisches Degradationsverhalten berücksichtigt. Zur Bewertung der realen Degradation einer Atemluftflasche im Feuerwehrbetrieb, werden zudem die Ergebnisse von 90 zerstörenden Prüfungen vorgestellt, die an altersbedingt ausgesonderten Atemluftflaschen durchgeführt wurden. Die Erkenntnisse dieser Untersuchungsreihe werden final in einer sicherheitstechnischen Bewertung kondensiert.
Compressed natural gas (CNG) is a widely used automotive fuel in a variety of countries. In case of a vehicle fire where the safety device also malfunctions, a failure of the CNG automotive cylinder could occur. Such a cylinder failure is associated with severe hazards for the surrounding environment. Firstly, a comprehensive analysis is given below, summarizing various accidents involving CNG automotive cylinders and their consequences. In an extensive experimental program, 21 CNG automotive cylinders with no safety device were tested. Of the 21, burst tests were carried out on 5 Type III and 5 Type IV cylinders. Furthermore, fire tests with 8 Type III and 3 Type IV cylinders were conducted. Apart from cylinder pressure, inner temperature and cylinder mantle temperature, the periphery consequences, such as nearfield blast pressure and fragmentation are documented. The maximum measured overpressure due to a Type III cylinder failure was p = 0.41 bar. Each traceable fragment was georeferenced. All-in-all, fragment throw distances of d > 300 m could be observed. As one key result, it can be stated that the tested Type IV CNG cylinders showed less critical failure behavior then the Type III cylinders under fire impingement.
Das Monte-Carlo-Experiment ermöglicht die numerische Simulation von statistischen Grundgesamtheiten und somit auch die Generierung von Festigkeitswerten für eine genau definierte Population von Druckgefäßen. In diesem Beitrag wird möglichst nachvollziehbar gezeigt, wie Werte generiert, Stichproben gezogen und ausgewertet werden. Auf dieser Basis wird auch gezeigt, wie die Wahrscheinlichkeit ermittelt wird, mit der Stichproben aus simulierten Populationen das Zulassungskriterium „Mindestberstdruck“ bestehen.
Hydrogen is an attractive energy carrier that requires high effort for safe storage. For ensuring safety, they must undergo a challenging approval process. Relevant standards and regulations for composite cylinders used for the transport of hydrogen and for its onboard storage are currently based on deterministic (e.g. ISO 11119-3) or semi-probabilistic (UN GTR No. 13) criteria. This paper analysis the properties of such methods with respect to the evaluation of load cycle strength. Their characteristics are compared with the probabilistic approach of the BAM. Based on Monte-Carlo simulations, the available design range (mean value and scatter of strength criteria) of current concepts was exemplarily estimated. The aspect of small sample sizes is analysed and discussed with respect to the evaluation procedures.
Hydrogen is an attractive energy carrier that requires high effort for safe storage. For ensuring safety, storage cylinders must undergo a challenging approval process. Relevant standards and regulations for composite cylinders used for the transport of hydrogen and for its onboard storage are currently based on deterministic (e.g. ISO 11119-3) or to some respect semi-probabilistic criteria (UN GTR No. 13; with respect to burst strength).
This paper provides a systematic analysis of the load cycle properties resulting from these regulations and standards. Their characteristics are compared with the probabilistic approach of the Federal Institute for Materials Research and Testing BAM. The most important aspect of comparing different concepts is the rate for accepting designs with potentially unsafe or critical safety properties. This acceptance rate is analysed by operating Monte-Carlo simulations over the available range of production properties.
In case of a vehicle fire, an installed LPG (liquefied petroleum gas) tank with a malfunctioning safety device poses severe hazards. To investigate the consequences in case of tank failure, we conducted 16 tests with toroidal shaped LPG vehicle tanks. Three tanks were used for a Hydraulic Burst Test under standard conditions. Another three tanks were equipped with a statutory safety device and were subjected to a gasoline pool fire. The safety device prevented tank failure, as intended. To generate a statistically valid dataset on tank failure, ten tanks without safety devices were exposed to a gasoline pool fire. Five tanks were filled to a level of 20 %; the re-maining five were filled to a level of 100 %. In order to gain information on the heating process, three tem-perature readings at the tank surface, and three nearby flame temperatures were recorded. At distances of l = (7; 9; 11) m to the tank, the overpressure of the shock wave induced by the tank failure and the unsteady tem-peratures were measured. All ten tanks failed within a time of t < 5 min in a BLEVE (boiling liquid expanding vapor explosion). Seven of these resulted directly in a catastrophic failure. The other three resulted in partial failure followed by catastrophic failure. A near field overpressure at a distance of l = 7 m of up to p = 0.27 bar was measured. All ten tests showed massive fragmentation of the tank mantle. In total, 50 fragments were found. These 50 fragments make-up 88.6 % of the original tank mass. Each fragment was georeferenced and weighed. Fragment throwing distances of l > 250 m occurred. For the tanks with a fill level of 20 %, the average number of fragments was twice as high as it was for the tanks that were filled completely.
Atemluftflaschen aus Faserverbundwerkstoffen werden bei einem Brandeinsatz situationsabhängig hohen thermischen Belastungen ausgesetzt. Die Grenzen der sicheren thermischen Belastbarkeit dieser Behälter werden jedoch heutzutage nicht abgeprüft. Deshalb hat es sich die Bundesanstalt für Materialforschung und -prüfung (BAM) im Austausch mit der Bergischen Universität Wuppertal zur Aufgabe gemacht, die Auswirkungen dieser Betriebslasten zu untersuchen. Die Erkenntnisse dieser Untersuchungen sollen genutzt werden, um zu beurteilen, wie thermische Betriebsbedingungen in normierten Prüfkriterien sicherheitstechnisch berücksichtigt werden sollten.
Um die Beanspruchungen innerhalb des Behältermaterials berechnen zu können wird in diesem dritten Teil der Aufsatzreihe die Entwicklung eines analytischen Hybrid-Behältermodells vorgestellt, in dem die für den Brandeinsatz zu erwartenden Materialtemperaturen, deren Ermittlung im Fokus des ersten und zweiten Teils dieser Untersuchungsreihe standen, eingebunden werden. Dabei werden im Modell erstmalig Schädigungsmechanismen berücksichtigt, die eine thermische Überbelastung des Faserverbundwerkstoffs einbeziehen.