3.1 Sicherheit von Gefahrgutverpackungen und Batterien
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Paper des Monats
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The potential release of hazardous substances from polymer-based products is currently in the focus of environmental policy. Environmental simulations are applied to expose such products to selected aging conditions and to investigate release processes. Commonly applied aging exposure types such as solar and UV radiation in combination with water contact, corrosive gases, and soil contact as well as expected general effects on polymers and additional ingredients of polymer-based products are described. The release of substances is based on mass-transfer processes to the material surfaces. Experimental approaches to investigate transport processes that are caused by water contact are presented. For tailoring the tests, relevant aging exposure types and release quantification methods must be combined appropriately. Several studies on the release of hazardous substances such as metals, polyaromatic hydrocarbons, flame retardants, antioxidants, and carbon nanotubes from polymers are summarized exemplarily. Differences between natural and artificial exposure tests are discussed and demonstrated for the release of flame retardants from several polymers and for biocides from paints. Requirements and limitations to apply results from short-term artificial environmental exposure tests to predict long-term environmental behavior of polymers are presented.
Porous carbons are promising anode materials for next generation lithium batteries due to their large lithium storage capacities. However, their highsloping capacity during lithiation and delithiation as well as capacity fading due to intense formation of solid electrolyte interphase (SEI) limit their gravimetric and volumetric energy densities. Herein we compare a microporous carbide-derived carbon material (MPC) as promising future anode for all solid-state batteries with a commercial high-performance hard carbon anode. The MPC obtains high and reversible lithiation capacities of 1000 mAh g−1carbon in half-cells exhibiting an extended plateau region near 0 V vs. Li/Li+ preferable for full-cell application. The well-defined microporosity of the MPC with a specific surface area of >1500 m2 g−1 combines well with the argyrodite-type electrolyte (Li6PS5Cl) suppressing extensive SEI formation to deliver high coulombic efficiencies. Preliminary full-cell measurements vs. nickel-rich NMC-cathodes (LiNi0.9Co0.05Mn0.05O2) provide a considerably improved average potential of 3.76 V leading to a projected energy density as high as 449 Wh kg−1 and reversible cycling for more than 60 cycles. 7Li Nuclear Magnetic Resonance spectroscopy was combined with ex-situ Small Angle X-ray Scattering to elucidate the storage mechanism of lithium inside the carbon matrix. The formation of extended quasi-metallic lithium clusters after electrochemical lithiation was revealed.
Täglich werden mehrere tausend Tonnen in Säcken verpackter Gefahrgüter über die Straßen transportiert. Laut den internationalen Gefahrgutvorschriften für den innerstaatlichen und grenzüberschreitenden Verkehr ADR müssen Gefahrgutsäcke aus Papier „staubdicht“ sein. Die Autobahnpolizei Münster wies bei einem Vortrag in der BAM darauf hin, dass im Rahmen polizeilicher LKW-Kontrollen Ladeflächen voller Staub vorgefunden wurden, ohne dass ein Defekt an einem Gefahrgutsack festgestellt werden konnte.
Ziel der Arbeit war es, eine Prüfkammer zu entwickeln, welche in der Lage ist, nach Fallversuchen mit Gefahrgutsäcken aus Papier den freigesetzten luftgetragenen Staub zu bestimmen. Eine anschließende Bewertung soll die gesundheitlichen Gefahren des entstandenen Aerosols aufzeigen. Durch die Auswertung erster Fallversuche wurde exemplarisch die „Dichtheit“ vorhandener Gefahrgutsäcke bestimmt und die Fraktionen der entstandenen Aerosole wurden mit den Arbeitsplatzgrenzwerten verglichen.
Im Zusammenhang mit den Untersuchungen zu den Möglichkeiten von gekühlten Transporten von Lithiumbatterien werden unterschiedliche Zerstörungsmethoden vorgestellt und diskutiert. Insbesondere wird dabei das neu entwickelte Nageltool und die vorläufigen Untersuchungen für den Einfluss von Ultratiefkühlung auf unbeschädigte Lithiumbatterien vorgestellt.
Due to their increasing energy density, lithium-ion-batteries (LIBs) play a key role in the traffic energy transition. Regarding their safety behavior, the main challenge of LIB-cells remains the thermal runaway (TR) process. In situ/operando investigations of the TR on commercial cells is possible with radiographic and computer tomographic measurements. Nonetheless, high resolution visualization of the TR persists as a challenge due to the high progression speed of the TR-process itself. Generally, performing abuse tests at cryogenic temperatures allows to slow down or even prevent the TR. Nevertheless, not all abuse methods are suitable for TR investigations at low temperatures. Nail penetration is an appropriate option, however, contains numerous unknown parameters and therefore suffers regarding reproducibility.
Herein, a self-developed high precision nail-penetration-setup is introduced, approaching the necessary mechanically reproducibility with controlled temperatures down to -190°C. The setup allows the preparation of critically abused, however, at cryogenic temperatures stable LIB-cells. These cells were controlled rethermalized to room temperature during synchrotron x-ray computer tomography (SXCT) with a pixel size up to 0.7 μm. During this measurement, the temperature and voltage of the cell is monitored allowing the visualization of the initial internal cell reactions. This study reveals the relation between internal reactions and cell voltage. Finally, the developed set-up enables in-depth analysis of thermal runaway behavior down to material level for various commercial battery cells in the future.
Lithium batteries are the key technology for the successful implementation of the energy transition. Nevertheless, the consequences of thermal runaway of lithium batteries pose the greatest safety risk. In particular, the transport of damaged lithium batteries poses special challenges in order to minimize the effects of thermal runaway. By developing a precision nail test rig, the positive effects of cooling damaged lithium batteries can be investigated and safe transport temperatures identified.
A high precision nail‐penetration (NP) tool for characterizing the mechanically induced thermal‐runaway (TR) of lithium‐ion battery (LIB) cells in a defined range of temperatures down to −140 °C was developed. To understand the cell specific behavior at low temperatures aiming at the determination of safe handling conditions, different scenarios are analyzed. First, accuracy tests of the NP‐tool regarding motion and penetration depth are conducted with cylindrical cells at different temperatures. Thus, postmortem computer tomographic (CT) images are compared to the data measured with the newly integrated 3‐axis force sensor which is further combined with a high‐resolution position sensor. The herein developed setup allows evaluation of the NP‐metrics at an accuracy of ±1 pierced electrode layer without CT‐scans. Further NP examinations at 20 °C of fully charged cylindrical lithium nickel manganese cobalt oxide cells reveal a reproducible minimum damage as a reliable TR‐trigger. Moreover, NP‐tests at low temperature disclose a relation of the short circuit conductivity and TR‐reactions during subsequent rethermalization to room temperature. Finally, the implementation of a novel fixture for a controlled very fast cooling of LIB‐cells during critical damage opens the way to investigate the individual steps during a TR and, thus, to gain important information of the specific TR‐mechanism of different LIB‐cells.
AbstractLithium‐ion cells connected in series are prone to an electrical safety risk called overdischarge. This paper presents a comprehensive investigation of the overdischarge phenomenon in lithium‐ion cells using operando nondestructive imaging. The study focuses on understanding the behavior of copper dissolution and deposition during overdischarge, which can lead to irreversible capacity loss and internal short‐circuits. By utilizing synchrotron X‐ray computed tomography (SXCT), the concentration of dissolved and deposited copper per surface area is quantified as a function of depth of discharge, confirming previous findings. The results also highlight for the first time a nonuniform distribution pattern for copper deposition on the cathode. This research provides insights for safer battery cell design.
Adopting X-ray computed tomography (XCT) for ex-situ characterization of battery materials has gained interest in the past decade. The main goal of this paper is to demonstrate the effectiveness of several X-ray computer tomography techniques to study commercial batteries. General guidelines are provided to select the most suitable imaging equipment and parameters for investigations of lithium-ion batteries, spanning the length scales from cell to electrode, down to particle level. Relevantly, such parameters would also be suitable for operando experiments.
Safety mechanisms and manufacturing inconsistencies at cell level as well as defects and inhomogeneity in cathode and anode is illustrated and quantified. Furthermore, relation of beam energy and sample-detector-distance on contrast retrieved from attenuation and phase shift is inspected using Synchrotron XCT.
Ziel des Vorhabens war es, den Einfluss der realen Temperaturbelastung auf Atemschutzflaschen und Lithiumbatterien in Funkgeräten (FG) im Löscheinsatz von Rettungskräften zu ermitteln und deren Auswirkung auf die Alterung und Lebensdauer sowie die potenziellen Gesundheitsgefahren bei deren Nutzung besser beurteilen zu können und Handlungshilfen abzuleiten.
Im Rahmen dieses Vorhabens wurden zum einen unterschiedlich thermisch gealterte Composite-Atemluftflaschen systematisch hinsichtlich ihrer Restfestigkeiten untersucht. Zum anderen wurden Lithiumbatterien aus FG hinsichtlich der Einwirkung von kritischen Temperaturen untersucht, ab denen es zu einem thermischen Durchgehen der Batterien kommen kann. Für diese beiden wichtigen Komponenten, Lithiumbatterien und Composite-Atemluftflaschen, wurden kritische Temperatur-Zeit-Profile ermittelt, die Auswirkungen durch geeignete Methodiken untersucht und die sich ergebenden Gefährdungen für den Träger bewertet.
Als Methodische Vorgehensweise wurden durch Realversuche die tatsächlichen und zuvor durch Literatur-recherche ermittelten Temperaturprofile verifiziert und auf deren Grundlage die Laborbelastungen abgeleitet. Um den Eigenschaften der aus Faserverbundwerkstoffen hergestellten Composite-Atemluftflaschen Rechnung zu tragen, wurden an zwei repräsentativen Baumustern unterschiedlicher Hersteller Stichprobengruppen unterschiedlicher thermischer Belastung ausgesetzt und hinsichtlich ihrer verbleibenden Restfestigkeitsabnahme geprüft und mit thermisch unbelasteten Baumustern verglichen. Neben den statischen Berstversuchen wurden auch kombinierte Alterungs- und Restfestigkeitsuntersuchungen an zyklisch belasteten Behältern durchgeführt.
Die FG wurden thermisch sowohl statischen als auch zyklischen Belastungen ausgesetzt und mit Kapazitätsmessungen begleitet. Die statischen Versuche dienten dem Zweck, die maximale thermische Belastbarkeit der Akkus zu ermitteln, bei der noch kein Versagen auftritt. Bei den zyklischen Versuchen wurde der Temperaturverlauf bei Löscheinsätzen so nah wie möglich im Labor nachgestellt. Hierbei wurden die Akkus wiederholt einem Belastungsprofil mit konstanter Temperatur ausgesetzt und nach einigen Intervallen die Restkapazitäten am Akku gemessen und so die Degradation bestimmt.
Als Fazit der im Rahmen dieses Vorhabens durchgeführten Untersuchungen an zwei repräsentativen Baumustern von Atemschutzflaschen kann gefolgert werden, dass die thermischen Belastungen abhängig vom Baumuster einen z.T. deutlichen Einfluss auf die Restfestigkeiten der Atemschutzflaschen haben. Höhere thermische Exposition ist, zumindest an den untersuchten Atemschutzflaschen, deutlich zu erkennen und die Flaschen können durch die zuständigen Gerätewarte leicht ausgesondert und ersetzt werden. Die thermischen Belastungen, wie sie im Rettungseinsatz auftreten, waren für die untersuchten Atemschutzflaschen und die Rettungskräfte nicht kritisch sind. Die langjährige Erfahrung etablierter Hersteller dürfte hier aber nicht ohne Einfluss sein. Es ist somit kein Grund erkennbar, von der Verwendung der leichteren Typ 4 Atemschutzflaschen abzuraten, wenn Atemschutzflaschen, die visuell erkennbare thermische Einwirkungen (Farbänderungen, Materialschmelzungen o.ä.) aufweisen, unmittelbar ersetzt werden.
Die Ergebnisse an den FG zeigen, dass trotz hoher Temperaturen keine Selbstentzündung der Lithiumbatterien ausgelöst wird. Der Kapazitätsverlust der Batterien infolge der Belastung führt ebenfalls nicht zu einem Funktionsausfall. Es konnte gezeigt werden, dass die Kapazitätsbestimmung als zuverlässiges und geeignetes Kriterium für die Sicherheitsbewertung der Akkus herangezogen werden kann, wenn die Kapazitätsmessung bei gleichbleibenden Bedingungen (gleiche Raumtemperaturen, gleiche Messgeräte, etc.) stattfindet. Es wird empfohlen, die Akkus ab einer Restkapazität von unter 80% zu tauschen. Als schnelle und sehr einfache Überprüfung kann eine Sichtprüfung an den FG stattfinden. Die im Projekt verwendeten FG zeigten eine Verformung der Kunststoffhülle bei zu hohen Belastungen.
In practice, checks on dangerous goods transports often detect leaks of powdered dangerous goods from valved bags. In this work, the influence factors of a sudden release of powdery substances from the valves of valved bags were investigated. Drop tests were carried out on paper bags of UN design type 5M2 with internal sleeve valve using two different powdery substances (Esplas H130 and zinc oxide “Rotsiegel”). The internal sleeve valves of all test samples were not sift-proof with respect to both filling substances. For almost all test samples, the Esplas H130 powder already leaked out of pasted joints during manual filling. This is a contradiction to the requirement in UN 6.1.4.18.1, according to which closures and joints of paper bags 5M2 should be sift-proof. In the drop tests, longer valve lengths had a greater sealing effect for both filling substances (for filling degrees of at least 95% and for test samples which had already been mechanically loaded). As an extreme example, at the drop height of 1.20 m and a filling degree of 100%, the released amount of zinc oxide powder from a 10 cm long valve was about 16 times higher than from a valve length of 12.5 cm. The valve length is therefore a safety-relevant parameter and should be specified by the manufacturer. To ensure that only filling goods with similar physical properties in comparison to the test substance are used for valved bags, the user must be informed of the particle size of the test substance.
Die BAM ist zuständige Behörde in Deutschland für bestimmte Aufgaben im Gefahrgutbereich, die u. a. in § 8 der Gefahrgutverordnung Straße, Eisenbahn und Binnenschifffahrt (GGVSEB) und § 12 der Gefahrgutverordnung See (GGVSee) aufgeführt sind und hauptsächlich von den Abteilungen 2 und 3 wahrgenommen werden. So ist die BAM bspw. die in Deutschland für die Zulassung von Verpackungen und Tanks oder auch die Einstufung bestimmter gefährlicher Güter zuständige Stelle. Die BAM arbeitet des Weiteren als Kompetenzbehörde national und international in den entsprechenden Gremien mit und berät das BMDV in der Rechtsfortentwicklung der internationalen Vorschriften für den Gefahrguttransport. Dies geschieht u. a. durch die Mitarbeit im Ständigen Ausschuss Gefahrgutbeförderung (AGGB) des Gefahrgut-Verkehrs-Beirats beim BMDV und den zugehörigen Arbeitsgruppen, oder auch das Erstellen von Anträgen für Rechtsänderungen in den internationalen Vorschriften der Vereinten Nationen (UN) bzw. der Wirtschaftskommission für Europa der UN (UNECE) im Auftrag des BMDV. Die Beratung der betroffenen Wirtschaft und die Normungsarbeit sind weitere wichtige Themen. Die Expertise der BAM wird insbesondere durch Forschung im Gefahrgutbereich erhalten und weiter ausgebaut. Im Rahmen des Vortrags werden drei Forschungsbereiche vorgestellt, von denen zwei für die Energiewende von großer Bedeutung sind.
Die Vorteile bei der Erstellung von Beförderungspapieren mit dem Modul der Datenbank GEFAHRGUT werden dargestellt. Dazu zählen u.a. die einfache Erstellung eines Beförderungspapieres für Stückgut im Straßenverkehr durch Nutzung eines Schritt-für-Schritt-Assistenten, bei dem z. B. grundsätzliche Verbote der Zusammenladung und -packung geprüft werden. Bei der Auswahl der Verpackung werden bei Einzelverpackungen und IBCs nur Verpackungen/IBCs angeboten, die für den jeweiligen Stoff zulässig sind.
Depending on the specific plastic’s ageing sensitivities, the durations which plastic components remain in the environment can be very long. As, in the past, the advantages in ageing resistance and durability were highly evaluated, we now face the problem of quite stable plastic waste within the environment.
However, there is only little knowledge on the real timescales until macroscopic fragmentation for the different kinds of plastic under various environmental conditions.
Here, weathering methods are presented, which have been used for the failure prediction in specific outdoor conditions. Issues of uncertainty, reproducibility, or validation are discussed.
For the prediction of the plastic’s fragmentation, much longer time scales have to be considered. To do this within a limited project life span, various processes as well as their acceleration potential have to be evaluated separately, such as temperature increase or spectral shift.
The possibilities and limitations of such controlled acceleration will be discussed.
Bei der Bestrahlung und Bewitterung von polymeren Werkstoffen wird die Degradation durch eine Absorption von Strahlung initiiert und meistens durch weitere Klimagrößen, wie z.B. Wärme, Feuchte und atmosphärische Gase beeinflusst. Die Messung einer effektiven Bestrahlungsstärke und ihre zeitliche Integration sind deshalb von großer Bedeutung.
Photochemische Prozesse werden beim Sehen oder allgemeiner bei Farbstoffen schon durch sichtbare (VIS) Strahlung, dagegen bei der Erythembildung der Haut und der Photodegradation von Polymeren erst durch die energiereicheren Photonen der ultravioletten (UV) Strahlung initiiert. Die spektrale Empfindlichkeit des Auges und die Erythembildung sind im VIS- bzw. UV-Bereich sehr stark wellenlängenabhängig, was durch die Angabe der mit der spektralen Hellempfindlichkeit V() des Auges bewerteten VIS-Strahlung in Lux (lx) bzw. die mit der Erythem-Wirkfunktion bewertete UV Strahlung als dimensionsloser UV-Index berücksichtigt wird. Spektrale Empfindlichkeiten.
Die Photodegradation von Polymeren ist im UV-Bereich ebenfalls stark wellenlängenab-hängig, was bisher nicht berücksichtigt wurde. Seit Mitte der 70er Jahre, als die lx- bzw lxh- Messung bei der Strahlungsbeanspruchung langsam durch die Ermittlung der radiometrischen UV-Bestrahlungsstärke bzw. der UV-Bestrahlung im gesamten UV-Bereich abgelöst wurde, gab es hier bei der Bewitterungsprüfung keine weiteren Fortschritte auf dem Gebiet der Charakterisierung der Strahlungsbeanspruchung im UV-Bereich.
Seit Jahren liegen zahlreiche Ergebnisse über die spektrale Empfindlichkeit von Photo-degradationsprozessen vor, die zeigen, dass die spektrale Empfindlichkeit im Bereich der Globalstrahlung bei ca. 300 nm, am größten ist und im langwelligen UV-Bereich bei ca. 400 nm gegen Null geht. Die Messungen der radiometrischen Größen UV-Gesamt-bestrahlungsstärke und UV-Gesamtbestrahlung erfasst deshalb über weite Wellen-längenbereiche Strahlungsanteile, die für die Photodegradation bedeutungslos sind und mittelt über potenziell bedeutsame Änderungen im kurzwelligen UV-Bereich hinweg.
Es wird das Konzept eines neuen UV-Radiometers vorgestellt, dessen spektrale Empfindlichkeit einer mittleren spektralen Empfindlichkeit der Photodegradation von Polymeren entspricht. Die effektive UV-Bestrahlungsstärke und UV-Bestrahlung kann dadurch wesentlich genauer erfasst werden.
Weathering reference materials are used to characterize the harshness of an exposure, aiming on either reproducibility of a specific exposure or on the comparability between various kinds of weathering exposure.
The materials that are used as weathering reference materials differ in their sensitivities (as well as in interactions and interferences of the latter), conditioned by the different processes which lead to the respective property change. It is also essential to take into account the necessary measurement equipment for the respective property change, in order to allow timely intervention.
What are the key issues on choosing a weathering reference material?
What can be learned from the weathering reference materials, investigated so far?
Possibilities and limitations are discussed on the basis of existing weathering reference materials. Conclusions are drawn, for establishing new weathering reference materials.
Depending on the specific plastic’s ageing sensitivities, the durations which plastic components remain in the environment can be very long. As, in the past, the advantages in ageing resistance and durability were highly evaluated, we now face the problem of quite stable plastic waste within the environment.
However, there is only little knowledge on the real timescales until macroscopic fragmentation for the different kinds of plastic under various environmental conditions.
Here, weathering methods are presented, which have been used for the failure prediction in specific outdoor conditions. Issues of uncertainty, reproducibility, or validation are discussed.
For the prediction of the plastic’s fragmentation, much longer time scales have to be considered. To do this within a limited project life span, various processes as well as their acceleration potential have to be evaluated separately, such as temperature increase or spectral shift.
The possibilities and limitations of such controlled acceleration will be discussed.
Die Umweltwirkungen auf ein Material werden als Überlapp der Funktionskurven von Materialempfindlichkeit und einwirkenden Umweltparametern betrachtet. Wenn entweder die Empfindlichkeit oder die Beanspruchungen Null sind, ergibt sich auch keine Umweltwirkung und bei beidseitig Werten größer Null das jeweilige Produkt der beiden. Die Akkumulation der nicht-reversiblen Effekte über die Zeit und allen Eigenschaftsänderungen entspricht der Alterung des Materials für den jeweiligen Expositionszeitraum.
Die digitale Umweltsimulation gliedert sich hier in drei Teilaspekte. Ein erster, rein materialwissenschaftlicher Teil hat die Aufgabe, alle relevanten Materialempfindlichkeiten experimentell zu quantifizieren. Ein zweiter – unter Umständen numerischer Teil – hat die Aufgabe, das Bauteil und seine Einbaulage zu digitalisieren und aus den makroskopischen Umgebungsbedingungen die relevanten mikroklimatischen Umweltparameter für alle Oberflächen- oder Volumenelemente zu bestimmen. In einem dritten Teil werden die Einwirkungen über den betrachteten Zeitraum berechnet und kumuliert. Dieses Konzept, das auf den so genannten Expositions-Reaktions-Funktionen (ERF) basiert, wird an Beispielen der Photoxidation erläutert. Dieses Vorgehen wurde schon beim ViPQuali-Projekt als Numerische Umweltsimulation umgesetzt.
Überprüft werden muss das Modell unbedingt an einer realitätsnahen Validierungsbeanspruchung. Hier werden die ermittelten ERFs mit über den kompletten Beanspruchungszeitraum geloggten Umweltparametern gekoppelt, um die berechnete mit der experimentell erfahrenen Alterungswirkung zu vergleichen. Nur so kann sichergestellt sein, dass alle für die Anwendungsumgebung relevanten Materialempfindlichkeiten einbezogen wurden.
Drei grundlegend verschiedene Ansätze für Umweltsimulation werden an Beispielen illustriert:
(i) Ganzheitlicher Ansatz - Nachstellen von Umweltmilieus im Labor
Ziel ist hier das Nachstellen von (kombinierten) Umweltbedingungen im Labor; die Umweltparameter werden mit all ihren Wechselwirkungen aufgebracht.
Hauptnutzen ist eine gegenüber der natürlichen Beanspruchung erhöhte Reproduzierbarkeit der Umweltbedingungen. Hat man sein Laborsetup entwickelt, ist es auf verschiedene Materialien anwendbar.
Unter solchen Laborbedingungen ermittelte Lebensdauern sind dabei nicht auf die typischerweise sehr variablen Real-Umweltbedingungen übertragbar.
(ii) Parametrisierter Ansatz - Ermittlung einzelner Materialempfindlichkeiten
Hierbei werden im Labor die Wirkungen separater Umweltparameter auf Materialien nachgestellt. Für eine solche Separation der Einflussfaktoren ist insbesondere die Aufschlüsselung möglicher Wechselwirkungen der Umwelt-parameter (z.B. Mikroklima an bestrahlten Oberflächen) erforderlich. Einzelne (meist Alterungs-) Empfindlichkeiten können qualitativ nachgewiesen werden oder sogar – als Beanspruchungs-Wirkungs-Funktionen – quantifiziert werden, was einen wesentlichen Schritt in Richtung der Digitalisierung der Material¬prüfung darstellt. Insbesondere ist dann auch eine Lebensdauer-vorhersage für vorgegebene Zeitreihen der Beanspruchungs¬parameter umsetzbar.
(iii) Rückwirkungen auf die Umwelt
Umweltbeanspruchungen können zur Freisetzung von Schadstoffen in die Umwelt führen. Durch die Nachstellung kritischer, aber realitätsnaher Einsatzszenarien kann die Menge an freigesetzten Substanzen abgeschätzt werden.
Egal, welcher Ansatz verfolgt wird – ein Vergleich mit der oder einer Real-beanspruchung ist unerlässlich, ebenso wie die Messdatenaufzeichnung (data logging) aller potenziell relevanten Beanspruchungsparameter während dieser Realbeanspruchung.
Obwohl die naturnahe Umwelt – sowohl in der BAM als auch bei der GUS – gegenüber der technischen Umwelt eher untergeordnet auftritt, werden zur Illustration Beispiele aus der naturnahen Umwelt verwendet.
In der Gesellschaft für Umweltsimulation GUS e.V. erarbeiten Fachleute aus Wissenschaft und Industrie in freiwilliger Selbstverantwortung Leitfäden und Bücher zur, Umweltsimulation und zur Wirkungssimulation von Umwelteinflüssen.
Diese beschreiben den Stand der Technik bzw. Stand der Wissenschaft und dienen als Anleitung für Umweltingenieure und Personen, die sich in die Arbeitsgebiete Produktqualifikation und Umweltsimulation einarbeiten und einiesen wollen.
Folgende Themenschwerpunkte werden in diesem Leitfaden behandelt: Wasser und seine Eigenschaften, Phasenübergänge, Transportvorgänge, Änderung von Materialeigenschaften durch Wasser, Messmethoden.
In a laboratory test, transparent high‐density polyethylene (HDPE) jerrycans have been exposed to both UV radiation and 55 wt‐% nitric acid solution at (41 ± 2)°C, for up to 20 days. For comparison, UV radiant exposure (21 days) and nitric acid exposure (up to 6 weeks) were performed separately, at nearly equal temperatures. The damages are compared with FTIR spectroscopy in ATR and HT‐gel permeation chromatography(GPC) on a molecular level and with hydraulic internal pressure testing as a component test. For the used jerrycans, relevant oxidation can only be found after the combined exposure. This is caused by the decomposition of nitric acid into nitrous gases by UV radiation, which is also observed at lower concentrations (28 wt‐%). After 6 days of laboratory exposure, this is rated as critical, which corresponds to about 1/10 year in Central Europe, according to the UV radiant exposure. The gradual increase in oxidative damage shows the reproducibility of the test.
Unpigmented HDPE jerrycans filled with nitric acid (55%) and water respectively had been exposed to outdoor conditions for one Berlin summer season. As both liquids underwent equal temperature progression, exposure effects of UV radiation and nitric acid as well as of their combination can be separated and compared. On the basis of various property changes after these exposures, synergistic action is evaluated and compared to a damaged Intermediate Bulk Container (IBC) from a transport accident.
It is found that carbonyl formation goes along with lightness increase in color measurement due to microcracking and with a worsening in mechanical behavior, all of them showing synergistic effects of UV and nitric acid exposure. In contrast, embedding nitrogen compounds goes along with yellowing of the material but cannot be correlated to oxidation.
The reason for intensified damaging is the decomposition of the 55-percent nitric acid and formation of nitrogen oxides even at ambient temperatures, caused by UV radiation. Thus, damaging effects become similar to those caused by fuming nitric acid exposure at temperatures above 60 °C, with the result of strong oxidative degradation of the polyethylene.
In contrast, exclusive exposure to the 55-percent nitric acid at 40 °C does not cause any failure.
It can therefore be assumed that also the damaged IBC had been exposed to both UV radiation and nitric acid, probably outdoors.
Exposure response function for a quantitative prediction of weathering caused aging of polyethylene
(2019)
The exposure response function of the carbonyl formation over the bulk has been determined for a high-density polyethylene of a thickness of 200 μm, which was used as a weathering reference material according to ISO TR 19032. To this end, spectral sensitivity was studied by local measurement of the effect of spectrally dispersed irradiation. Both the exposure device and the methodology of determination are described.
The temperature dependency of photooxidation was determined by UV exposure at various temperatures between 23 and 80 °C. Deviations from linearity and thus reciprocity below 40 °C are discussed and assumed to be related to diffusion limitations. An Arrhenius approach –based on data of linear carbonyl formation – has been incorporated into the exposure response function. Using this exposure response function, aging in terms of the distribution of a quantitative property change over a plastic component can be predicted for a specific outdoor location with real chronologic weather data as input for the exposure. Thus, artificial and natural weathering can be linked and compared. The established exposure response function has been validated by outdoor exposure results from the literature. If an estimated diffusion limitation is taken into consideration, calculations and published data are in good agreement.
Weathering reference materials (WRMs) are used to characterize the harshness of an exposure, aiming on either reproducibility of a specific exposure or on the comparability between various kinds of natural or artificial weathering exposure.
The materials that are used as weathering reference materials differ in their sensitivities (as well as in interactions and interferences of the latter), conditioned by the different processes which lead to the respective property change. It is also essential to take into account the necessary measurement equipment for the respective property change, in order to allow timely intervention.
What are the key issues on choosing a weathering reference material?
What can be learned from the weathering reference materials, investigated so far?
Possibilities and limitations are discussed on the basis of existing weathering reference materials. Conclusions are drawn, for establishing new weathering reference materials.
Aufgrund des tieferen Eindringens der solaren Strahlung treten bei transparenten und bei transluzenten (durchscheinenden) Kunststoffen veränderte Bedingungen gegenüber opaken Proben auf. Dies kann zu speziellen Effekten und damit zu einem abweichenden Bewitterungsverhalten führen. Auch aus Mangel an geeigneten Normen werden diese Effekte häufig vernachlässigt. Deshalb initiiert der DIN-FNK auf ISO-Ebene ein entsprechendes Dokument.
Die Norm ist in der Form eines Technical Reports geplant. In einem ersten Teil sollen die Besonderheiten transparenter oder transluzenter Kunststoffe erläutert werden, um den Nutzer für mögliche Probleme zu sensibilisieren. Im zweiten Teil werden Empfehlungen für Bestrahlung oder Bewitterung herausgearbeitet. In einem dritten Teil geht es dann um Besonderheiten bei der Messung von Eigenschaftsänderungen transparenter bzw. transluzenter Kunststoffe. In informativen Anhängen sollen verschiedene Beispiele die Thematik illustrieren.
As industrial demand for graphene-based materials (GBMs) grows, more attention falls on potential environmental risks. The present article describes a first assessment of the environmental releases of GBMs using dynamic probabilistic material flow analysis. The model considered all current or expected uses of GBMs from 2004 to 2030, during which time there have already been significant changes in how the graphene mass produced is distributed to different product categories. Although the volume of GBM production is expected to grow exponentially in the coming years, outflow from the consumption of products containing GBMs shows only a slightly positive trend due to their long lifetimes and the large in-use stock of some applications (e.g., GBM composites used in wind turbine blades). From consumption and end-of-life phase GBM mass flows in 2030, estimates suggest that more than 50% will be incinerated and oxidized in waste plants, 16% will be landfilled, 12% will be exported out of Europe, and 1.4% of the annual production will flow to the environment. Predicted release concentrations for 2030 are 1.4 ng/L in surface water and 20 μg/kg in sludge-treated soil. This study’s results could be used for prospective environmental risk assessments and as input for environmental fate models.
Die BAM ist nahezu über die gesamte Wertschöpfungskette hinweg wissenschaftlich tätig. Von der sicheren und effizienten Wasserstofferzeugung (POWER-to-GAS), über die (Zwischen-)Speicherung von Wasserstoff in Druckgasspeichern bis hin zum Transport bspw. mittels Trailerfahrzeug zum Endverbraucher.
Komplettiert werden die Aktivitäten der BAM durch die sicherheitstechnische Beurteilung von wasserstoffhaltigen Gasgemischen, die Verträglichkeitsbewertung von Werkstoffen bis hin zur Detektion von Wasserstoffkonzentrationen über geeignete Sensorik, auch mittels ferngesteuerter Messdrohnen (sog. UAV-Drohnen).
Zudem untersucht die BAM proaktiv Schadensrisiken und Unfallszenarien für die Sicherheitsbetrachtung, um mögliche Schwachstellen aufzeigen und potenzielle Gefährdungen erkennen zu können.
Carbons doped with iron and nitrogen (Fe–N–Cs) are highly promising electrocatalysts for energy conversion reactions in the oxygen, nitrogen and carbon cycles. Containing no platinum group metals, they nevertheless compete with platinum-based catalysts in crucial fuel cell reactions, such as oxygen reduction in acid. Yet deployment of Fe–N–Cs in fuel cells requires also a flow-enhancing pore structure, and a scalable synthesis procedure – a rarely-met combination of requirements. We now report such a simple synthesis of over 10 g of an Fe–N–C catalyst with high activity towards oxygen reduction in acid. Atomically-dispersed Fe–N4 active sites were designed orthogonally and simultaneously with hierarchical micro-, meso- and macroporosity, by exploiting a dual role of magnesium ions during pyrolysis. Combining the “active site imprinting” and “self-templating” strategies in a single novel magnesium iminodiacetate precursor yielded a catalyst with high specific surface area (SSA > 1600 m2 g−1), a flow-enhancing hierarchical porosity, and high relative abundance of the most desirable D1-type Fe–N4 sites (43%, by Mössbauer spectroscopy at 4.2 K). Despite the relatively low iron contents, the catalysts feature halfwave potentials up to 0.70 V vs. RHE at pH 1 and a mass activity of 1.22 A g−1 at 0.8 V vs. RHE in RDE experiments. Thanks to the simple and scalable synthesis, this active and stable catalyst may serve as a workhorse in academic and industrial research into atomically-dispersed ORR electrocatalysis.
Lithium-ion battery (LIB) powered devices, such as laptops, mobile phones and power tools are ubiquitous in our daily lives. Moreover, LIBs are essential for the electrification of vehicles, and play an important role for stationary storage units needed for grid-balancing. The improvement of LIBs, in terms of increasing energy density as well as cycle-life and decreasing costs, is tackled by numerous research groups all over the world. In the last years, research regarding safety aspects has steadily gained more interest. The safety of LIBs can be implemented at different levels, such as material, cell, battery and system level.
The abuse/misuse of an LIB can lead to an internal increase in heat which can trigger a chain of exothermic reactions on cell level. Thus, the cell temperature increases dramatically causing the so-called thermal runaway (TR). This process can lead to flames and/or explosion of the cell. Furthermore, the TR of one cell can initiate the TR of adjacent cells causing the so-called propagation, possibly, leading to the TR of the whole battery.
Herein, we will show the latest result of our safety tests on cell level employing an external heater as TR-trigger. Regarding single cell tests, we will compare different hazardous features during the TR, e.g., cell temperature, occurrence of flames, peak pressure, and toxic gases, depending on the cell format, cell energy and the cathode type. The same cell parameters will be used to discuss the results of the propagation tests. Moreover, the influence of the state of charge (SOC) and the present atmosphere (air vs. N2) as well as the repeatability will be discussed. Overall, the study comprises over 180 tests on cell level.
The findings regarding the TR behaviour can be used to create a hazard-classification scheme of LIBs, e.g., allowing the definition of (cell type specific) conditions for a safe transport. Furthermore, the results can increase the general understanding of the TR mechanism promoting the development of advanced measures to enhance the safety on cell level in the future.
Next to performance features, safety aspects of lithium-ion batteries (LIBs) are a crucial research field. The abuse/misuse of a LIB can trigger a chain of exothermic reactions on cell level. Hence, the cell temperature increases dramatically, causing the so-called thermal runaway (TR). Moreover, the TR of one cell can initiate the TR of adjacent cells leading to a TR-propagation. Due to the risk of a TR, special measures need to be applied while handling, storing, and transporting batteries. According to current transport regulations, all different types of lithium-ion and lithium metal cells/batteries (by means of cell format, cathode chemistry, etc.) require the same transport conditions regardless of the intensity of their reaction during abuse tests. To allow more differentiated transport requirements, the United Nations (UN) Subcommittee Transport of Dangerous Goods created an Informal Working Group (IWG) on the topic of a hazard-based classification of LIBs. BAM is one of nine laboratories working on the development of a respective classification scheme including appendant test protocols.
Herein, we discuss the latest results of our safety tests on commercial LIB-cells employing the test protocols developed in the UN-IWG. Single cell tests are analysed regarding different hazardous features during the TR, e.g., cell temperature, flame occurrence, and gas amount. Next to the general occurrence of a propagation, the propagation speed is analysed by propagation tests. In total, the presented results are gathered from over 200 tests. Next to the classification of the tested cells, the data set obtained is analysed in respect to the cells’ key features, such as cell energy, state of charge and cathode type. Generally, the presented results can increase the overall understanding of the TR-mechanism supporting the design of advanced safety measures on cell level in the future.
Lithium-ion batteries usually consist of numerous individual cells. There is ongoing discussion about enhancing sustainability by considering the replacement of heavily aged or damaged cells. Nevertheless, the planned replacement of individual cells poses significant challenges in ensuring the required reliability and safety of the refurbished device.
Lithium-ion batteries (LIBs) are essential for the electrification of vehicles and play an important role for stationary storage units needed for grid-balancing. Research groups all over the world work on the improvement of LIBs regarding an increase in energy density as well as cycle-life and a decrease in costs. Next to these research topics, a continuously uprising and crucial field is safety features of LIBs, which can be implemented at different levels, such as material, cell, battery and system level.
The abuse/misuse of a LIB can cause an internal release of heat which can trigger a chain of exothermic reactions on cell level. Hence, the cell temperature increases dramatically, causing the so-called thermal runaway (TR), possibly leading to flames and/or explosion of the cell. Moreover, the TR of one cell can initiate the TR of adjacent cells leading to a so-called propagation, possibly, causing the TR of the whole battery. Ideally, easily obtainable key features of a certain cell – such as cathode type, cell format, cell energy and state of charge (SOC) - could allow the prediction of its behaviour under abuse conditions. In the present study, we will discuss the latest result of our safety tests on cell level employing an external heater as TR-trigger. Single cell tests will be analysed regarding different hazardous features during the TR, e.g., cell temperature, occurrence of flames, peak pressure, gas amount and gas composition. Moreover, the possibility of a TR-propagation and the respective propagation speed will be gained from propagation tests utilizing six cells with identical SOC. In total, the study comprises over 200 tests on cell level. The gained data set is analysed in respect to the cell parameters, such as cell format, cell energy, SOC and the cathode type as well as the atmosphere (air vs. N2) present during the test. A special focus is put on the discussion of general conclusions linking cell parameters to TR-effects and propagation behaviour.
The findings regarding common conclusions between key features and TR-effects can enable a rather facile selection process of cells/batteries for certain applications according to specific safety targets. Moreover, it allows to choose cell-specific safety measures, suitable during operation. In further works, the study will be extended to end-of-first life cells yielding important conclusions regarding crucial safety aspects for the implementation of those cells in 2nd-life application. Generally, the presented results can increase the overall understanding of the TR mechanism supporting the design of advanced measures to enhance the safety on cell level in the future.
The mechanical and geometrical properties of impact targets greatly influence the outcome of a drop test. The International Agreement concerning the International Carriage of Dangerous Goods by Road (ADR) as well as ISO 2248 describe the characteristics of impact targets for drop tests of dangerous goods packagings.
According to these regulations, the impact target’s surface needs to be unyielding, under testing conditions non-deformable, flat, and integral with a mass at least 50 times that of the heaviest packaging to be tested. The problem is that many production facilities, especially manufacturers of corrugated fibreboard boxes, do not have their own testing device with the required 50 times mass ratio of the impact target for a regulation compliant drop test during series production. Furthermore, at UN level it is considered necessary to revise these requirements.
In the present paper, the impact target requirements are examined in detail and compared with those in other technical areas (e.g., impact target for container for the transport of radioactive materials). A research method is being developed to investigate the dependency between the mass ratio of the packaging and the target as well as the damage resistance of a drop tested package in relation to specific design characteristics. The results are of high relevance for industry purposes and intended to ensure a uniform level of safety assessment for the mechanical testing of dangerous goods packagings.
Due to the high damping mechanical properties of fibreboard materials, corrugated fibreboard boxes are widely used as transport packages of dangerous goods.
Since there is a hazard of vertical impact within the distribution system, drop tests are performed as design type tests to assess the package’s ability to withstand damage. However, there is little information in this context regarding the mechanical response of a filled fibreboard box.
This work aims to propose a concept utilizing experimental drop test results by means of finite-element (FE) analyses in order to predict the damage resistance of complete, filled corrugated fibreboard boxes which are ready for transportation.
Due to the high damping mechanical properties of fiberboard materials, corrugated fiberboard boxes are widely used as transport packagings of dangerous goods. Since there is risk of vertical impact within the distribution system, drop tests are performed as design type tests to assess a package’s ability to withstand damage. In this context, however, little is known regarding the transient mechanical response of a filled fiberboard box. The reason is that the nature of the packaging material presents challenges in identifying the deformation mechanisms experimentally. The aim of this work is to provide a framework for predicting the damage resistance of complete, filled corrugated fiberboard boxes which are ready for transportation. Therein, drop test finite-element simulations are used and validated by experimental results. These numerical calculation models are a valuable tool for virtual product development and contribute to the optimization of the design cycle.
For dangerous goods packagings, drop testing onto an essential unyielding target can be used to assess the mechanical resistance to impact loads. Adopted regulations like ADR/RID require that the impact surface provided shall be integral with a mass at least 50 times than that of the heaviest package to be tested. The problem is that many manufacturers do not possess impact targets that satisfy the required 50 times mass ratio for regulative drop tests during series production. The objective of this work is to verify existing and define improved criteria for impact target structures based on systematic investigations. Previous evidence highlights the relevance of other parameters in addition to the mass ratio. Therefore, in this research, a variation of drop test parameters was carried out experimentally. Furthermore, numerical vibration analysis was applied to investigate the deformability of the impact surface. The results conclude that the mass ratio of 1:50 cannot be defined as a decisive criterion. In order to determine the influence of further drop test parameters, the research findings were used to validate a parametric model which assesses impact target deflection. An approximation quality of over 90 % was achieved. As a result, new evaluation criteria are proposed. Firstly, a method for identifying critical impact target designs is provided. Secondly, a new comprehensive formula compares the approximated maximum deflection of a real impact target to the respective theoretical threshold derived from a worst-case assumption. In practice, this leads to great advantages in the evaluation of already installed impact targets for dangerous goods packagings.
For dangerous goods packagings, drop testing onto an essential unyielding target can be used to assess the mechanical resistance to impact loads. Adopted regulations like ADR/RID require that the impact surface provided shall be integral with a mass at least 50 times than that of the heaviest package to be tested. The problem is that many manufacturers do not possess impact targets that satisfy the required 50 times mass ratio for regulative drop tests during series production. The objective of this work is to verify existing and define improved criteria for impact target structures based on systematic investigations. Previous evidence highlights the relevance of other parameters in addition to the mass ratio. Therefore, in this research, a variation of drop test parameters was carried out experimentally. Furthermore, numerical vibration analysis was applied to investigate the deformability of the impact surface. The results conclude that the mass ratio of 1:50 cannot be defined as a decisive criterion. In order to determine the influence of further drop test parameters, the research findings were used to validate a parametric model which assesses impact target deflection. An approximation quality of over 90 % was achieved. As a result, new evaluation criteria are proposed. Firstly, a method for identifying critical impact target designs is provided. Secondly, a new comprehensive formula compares the approximated maximum deflection of a real impact target to the respective theoretical threshold derived from a worst-case assumption. In practice, this leads to great advantages in the evaluation of already installed impact targets for dangerous goods packagings.
Packagings for the transport of dangerous goods need to meet special requirements to get an approval. This includes free fall drop testing onto an essentially unyielding surface as a means to assess a package’s resistance to mechanical damage. A main requirement for drop tests is that the impact target’s mass shall be at least 50 times that of the heaviest package to be tested. Nevertheless, many manufacturers do not possess foundation structures with the required mass ratio. Previous evidence highlights that the mass ratio is not a decisive criterion on its own. Parameters such as the impact target foundation’s connection and the impulse experienced by the impacting object are essential as well. However, these factors are not easily verifiable since experimental measurements are not possible at most facilities. The objective of this work is to provide a detailed analysis on the interaction between impact target foundation and subgrade in dynamic impact testing using validated finite-element (FE) models. This research is highly beneficial for industrial application since it allows manufacturers to make informed predictions about the mechanical response of installed impact target foundations.
The mechanical and geometrical properties of impact targets greatly influence the outcome of a drop test. The International Agreement concerning the International Carriage of Dangerous Goods by Road (ADR) as well as ISO 2248 describe the characteristics of impact targets for drop tests of dangerous goods packagings.
According to these regulations, the impact target’s surface needs to be unyielding, under testing conditions non-deformable, flat, and integral with a mass at least 50 times that of the heaviest packaging to be tested. The problem is that many production facilities, especially manufacturers of corrugated fibreboard boxes, do not have their own testing device with the required 50 times mass ratio of the impact target for a regulation compliant drop test during series production. Furthermore, at UN level it is considered necessary to revise these requirements.
In the present paper, the impact target requirements are examined in detail and compared with those in other technical areas (e.g., impact target for container for the transport of radioactive materials). A research method is being developed to investigate the dependency between the mass ratio of the packaging and the target as well as the damage resistance of a drop tested package in relation to specific design characteristics. The results are of high relevance for industry purposes and intended to ensure a uniform level of safety assessment for the mechanical testing of dangerous goods packagings.
Deconvoluting the impact of early-life abuse conditions on the degradation of lithium-ion cells
(2023)
The successful repurposing of degraded lithium-ion (Li-ion) batteries in second-life applications is a vital step towards achieving a circular economy. While reusing aged Li-cells is a promising way of mitigating their overall environmental footprint, it is crucial to anticipate their future safety and performance characteristics . Unfortunately, predicting these properties is a cumbersome task, essentially caused by limited knowledge of the interference of different degradation modes in the cells’ first life.
To still enable estimating of these parameters from a current state, the present study systematically investigates the impacts of abusive conditions in an early phase of the cells’ life on their subsequent degradation behavior. For this purpose, individual Li-cells are initially stressed by different measures such as overcharging, deep-discharging, plating, and deliberate combinations of the aforementioned methods. Electrochemical performance indicators are monitored during subsequent cycling of the cells which provides insights into the interdependencies of different degradation modes induced by specific stress conditions. In this manner, it is clarified whether or not the total degradation can be determined by a convolution or a superposition of individual deterioration effects and, thus, be described as a multidimensional state function.
This knowledge will finally contribute to a better understanding of the performance and safety behavior of degraded Li-ion batteries which can help to successfully implement them into second-life applications.
Understanding the safety characteristics of aged Lithiumion
(Li-ion) batteries is essential for their effective
integration into second-life applications. The SafeLiBatt
project is a research initiative focused on evaluating
safety-related parameters of these batteries.
The presented study elucidates the impact of a cells’
state of health (SOH) on its safety behavior. Four highpower
pouch cells (Li-NMC622) were exposed to elevated
temperatures to achieve accelerated ageing. Subsequent
thermal abuse tests were utilized to assess crucial
parameters related to the thermal runaway (TR).
When compared to their non-aged (begin of life, BOL)
analogs, the aged cells implicated a TR-onset lowered by
about 10 – 20 K.
Exploring the electrochemical and physical stability of lithium-ion cells exposed to liquid nitrogen
(2024)
The transport and storage of lithium-ion (Li-ion) batteries — damaged or in an undefined state — is a major safety concern for regulatory institutions, transportation companies, and manufacturers. Since (electro)chemical reactivity is exponentially temperature-dependent, cooling such batteries is an obvious measure for increasing their safety.
The present study explores the effect of cryogenic freezing on the electrochemical and physical stability of Li-ion cells. For this purpose, three different types of cells were repeatedly exposed to liquid nitrogen (LN2).
Before and after each cooling cycle, electrical and electrochemical measurements were conducted to assess the impact of the individual freezing steps. While the electrochemical behavior of the cells did not change significantly upon exposure to LN2 , it became apparent that a non-negligible number of cells suffered from physical changes (swelling) and functional failures. The latter defect was found to be caused by the current interrupt device of the cylindrical cells. This safety mechanism is triggered by the overpressure of expanding nitrogen which enters the cells at cryogenic temperatures.
This study underlines that the widely accepted reversibility of LN2 -cooling on a material scale does not allow for a direct extrapolation toward the physical integrity of full cells. Since nitrogen enters the cell at cryogenic temperatures and expands upon rethermalization, it can cause an internal overpressure. This can, in turn, lead to mechanical damage to the cell. Consequently, a more appropriate temperature condition — less extreme than direct LN2 exposure — needs to be found
The BAMline at the synchrotron X-ray source BESSY II (Berlin, Germany) is supporting researchers especially in materials science. As a non-destructive characterization method, synchrotron X-ray imaging, especially tomography with hard X-Rays, plays an important role in structural 3D characterization. The imaging capabilities allow for in-situ and operando experiments. In this presentation the equipment, data handling pipeline as well as various examples from material science are presented.
Combining the abundance and inexpensiveness of their constituent elements with their atomic dispersion, atomically dispersed Fe−N−C catalysts represent the most promising alternative to precious-metal-based materials in proton Exchange membrane (PEM) fuel cells. Due to the high temperatures involved in their synthesis and the sensitivity of Fe ions toward carbothermal reduction, current synthetic methods are intrinsically limited in type and amount of the desired, catalytically active Fe−N4 sites, and high active site densities have been out of reach (dilemma of Fe−N−C catalysts). We herein identify a paradigm change in the synthesis of Fe−N−C catalysts arising from the developments of other M−N−C single-atom catalysts. Supported by DFT calculations we propose fundamental principles for the synthesis of M−N−C materials. We further exploit the proposed principles in a novel synthetic strategy to surpass the dilemma of Fe−N−C catalysts. The selective formation of tetrapyrrolic Zn−N4 sites in a tailor-made Zn−N−C material is utilized as an active-site imprint for the preparation of a corresponding Fe−N−C catalyst.
By successive low- and high-temperature ion exchange reactions, we obtain a phase-pure Fe−N−C catalyst, with a high loading of atomically dispersed Fe (>3 wt %). Moreover, the catalyst is entirely composed of tetrapyrrolic Fe−N4 sites. The density of tetrapyrrolic Fe−N4 sites is more than six times as high as for previously reported tetrapyrrolic single-site Fe−N−C fuel cell catalysts.
Nowadays, in every terrestrial and aquatic ecosystem, even in the remotest areas, small residues of plastics, the so called microplastic (MP) can be found. MPs are particles with a size of 1-1000 µm (ISO/TR 21960:2020), mainly containing synthetic polymers like polyethylene (PE), polypropylene (PP), polystyrene (PS) or polyethylene terephthalate (PET). Even styrene-butadiene rubber (SBR) as an indication for tire wear is included due to similar particle formation. To understand the MPs consequences to the environment, it is of high priority to capture its extent of contamination. It is surprising that in the analysis of polymer masses in environmental samples, PE, PS and SBR are often detected, but only small amounts of PP, although this is the second most commonly produced standard plastic and many MP particles originate from carelessly disposed packaging materials.
This presentation provides hypotheses about the reasons of rare PP identification and mass quantification in environmental samples. Different investigations of pristine PP and representative environmental samples, including the pre-treatment by Accelerated Solvent Extraction (ASE) or with density separation followed by the thermal extraction / desorption gas chromatography-mass spectrometry (TED-GC/MS) are presented. The results are discussed according to the material properties and a possible degradation mechanism under different weathering conditions which indicate less stability under relevant storage conditions.
High-resolution absorption isotopic spectrometry as a tool for aging studies of Li-ion batteries
(2022)
Lithium (Li) is the key element in the manufacturing of batteries. Isotopic study of Li may help to identify the causes of battery aging due to isotopic fractionation during charge/discharge cycles.
Isotopic ratio determination is based on monitoring the isotopic components of lithium by their spin-orbit coupling and its isotopic shift of about 15 pm for the 22P←22S electronic transition around 670.788 nm. In this work, we propose improvements to our previous work [1] by using a higher-resolution double echelle modular spectrometer (HR-DEMON II) coupled to a continuum source graphite furnace atomic absorption spectrometer (HR-CS-GF-AAS) for the isotopic analysis of Li.
The data analysis was carried out by using a decision-tree-based ensemble machine learning (ML) algorithm (XGBoost). A set of samples with 6Li isotope amount fractions ranging from 0.0004 to 0.99 mol mol-1 was used for the algorithm's training. Subsequently, the procedure was validated by a set of stock chemicals (Li2CO3, LiNO3, LiCl, and LiOH) and a BAM candidate reference material, a cathode material (NMC111). Finally, the ML model was applied to determine the isotope ratio of geological samples, including anorthosite, granite, soil, rhyolite, nepheline syenite, and basalt and battery samples. These samples were measured as digested without any further purification step.
Improvements in the optical resolution resolve the lithium isotopic components of the atomic spectra. In the studied geological samples, were found δ7Li values between -0.5 and 4.5 ‰ with a precision range of 1 to 2 ‰. In addition, the proposed method was validated with multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), and these results are comparable and compatible.
Im Vortrag wird der Stand der Weiterentwicklung der ISO 16103 dargestellt, in der Regelungen zur Qualitätssicherung bei der Herstellung von Recycling-Kunststoffen und daraus hergestellter Gefahrgutverpackungen enthalten sind. Darüber hinaus wird auf die Verbindungen zu den UN Model Regulations und zum ADR eingegangen und welche Konsequenzen sich daraus für die Zulassung und die Anerkennung des Qualitätssicherungsprogramms ergeben.
Evaluation of marker materials and spectroscopic methods for tracer-based sorting of plastic wastes
(2022)
Plastics are a ubiquitous material with good mechanical, chemical and thermal properties, and are used in all industrial sectors. Large quantities, widespread use, and insufficient management of plastic wastes lead to low recycling rates. The key challenge in recycling plastic waste is achieving a higher degree of homogeneity between the different polymer material streams. Modern waste sorting plants use automated sensor-based sorting systems capable to sort out commodity plastics, while many engineering plastics, such as polyoxymethylene (POM), will end up in mixed waste streams and are therefore not recycled. A novel approach to increasing recycling rates is tracer-based sorting (TBS), which uses a traceable plastic additive or marker that enables or enhances polymer type identification based on the tracer’s unique fingerprint (e.g., fluorescence). With future TBS applications in mind, we have summarized the literature and assessed TBS techniques and spectroscopic detection methods. Furthermore, a comprehensive list of potential tracer substances suitable for thermoplastics was derived from the literature. We also derived a set of criteria to select the most promising tracer candidates (3 out of 80) based on their material properties, toxicity profiles, and detectability that could be applied to enable the circularity of, for example, POM or other thermoplastics.
Das Verhalten von Batteriezellen bei Beschädigung ist von hoher Bedeutung für die Einschätzung der Sicherheit bei Transport, Lagerung sowie Verwendung. Vor allem im Zusammenhang mit dem exponentiell wachsenden Sektor der Lithium-Batterien kam es in der Vergangenheit immer wieder zu kritischen Vorfällen. Hierbei haben Lithium-Metall-Batterien, welche elementares Lithium enthalten, den Ruf besonders gefährlich zu sein. Um dieses Thema bewerten zu können, werden im Vortrag die Unterschiede zwischen Lithium-Ionen- und Lithium-Metall-Batterien erläutert und experimentelle Studien des Verhaltens von aktuellen Systemen bei Schädigung verglichen. Darüber hinaus wird auf die Eigenschaften sowie das Sicherheitsverhalten von zukünftigen Lithium- bzw. Natrium-Batterien eingegangen.
Das Verhalten von Batteriezellen bei Beschädigung ist von hoher Bedeutung für die Einschätzung der Sicherheit bei Transport, Lagerung sowie Verwendung. Die Auswirkungen bei Schädigung hängen natürlich von der Art der Zelle, jedoch auch vom Ladezustand und der Schädigungsmethode ab.
Im Vortrag werden die Schädigungsversuche von Einzelzellen sowie Propagationsversuche an der BAM für verschieden Ladezustände präsentiert. Des Weiteren werden die aktuellen Vorgaben/Empfehlungen bezüglich der Lagerung von Lithium-Batterien kurz dargestellt. Darüber hinaus werden die neusten Entwicklung bezüglich der Vorgaben für den Transports von Natrium-Ionen-Batterien vorgestellt und diskutiert.
Lithium ion batteries (LIBs) are omnipresent in our daily lives. LIBs power our laptops and mobile phones, are the energy storage of choice for the electrification of vehicles, and play a vital role in the layout of the storage devices needed for the balancing of the grid.
Research groups all over the world work on the improvement of LIBs, e.g., an increase in energy density and cycle-life as well as a decrease in costs. In recent years, investigations concerning the LIB’s safety continuously gain importance, especially, pushed by incidents with electric vehicles. They are multiple levels at which safety measures can be implemented, i.e., material, cell, battery and system level. Accordingly, the behaviour of LIBs under abuse/misuse conditions are often investigated on those levels.
Here, we focus on the safety on cell level. Generally, the abuse/misuse leads to an increase in heat in the cell at worst triggering a chain of exothermic reactions. Hence, the cell’s temperature rapidly increases leading to the so-called thermal runaway (TR) possibly accompanied by flames and/or explosion of the cell. Herein, different hazardous features during the TR of different commercial cells are analysed such as temperature, flames, projectiles and toxic gases. In order to gain further insights on the parameters influencing the TR, different type of initiation modes, e.g., external heating, overcharging, nail penetration and external short circuiting are utilized. Moreover, the state of charges (SOCs) are varied to differ the amount of electrical energy present in the cells.
Next to the characteristic of the TR of a single cell, the investigation of the propagation of the TR from one cell to another is an important parameter, as a battery is usually composed of multiple cells. Due to the close packaging of the single cells, the TR of one cell is often able to initiate the TR of the surrounding cells, finally, causing the TR of the whole battery. Herein, the propagation ability is studied depending on the cell type and SOC. Finally, the results will be used to formulate (cell specific) conditions for a safe transport of LIBs. Moreover, the gained knowledge can support the development of advanced measures to increase the safety on cell level in the future.
Meta-analysis of heat release and smoke gas emission during thermal runaway of lithium-ion batteries
(2023)
Herein a meta-analysis of 76 experimental research papers from 2000 to 2021 is given about possible effects on the thermal runaway of lithium-ion battery cells. Data on the hazards of gas emissions and released heat are related to each other and differentiated by cell properties such as, cell geometry, cathode type or state of charge. Quantitative information on the total heat release in the range of 2.0–112.0 kJ Wh−1, the peak heat release rate in the range of 0.006–2.8 kW Wh−1and the smoke gas emission were extracted, normalized in terms of cell energy (Wh), combined in a data library and compared graphically. The total amount of gas emitted (3–48 mmol Wh−1) as well as the released amount of carbon monoxide (1–161 mg Wh−1) and hydrogen fluoride (2–197 mg Wh−1) were investigated as a function of the state of charge and cell geometry. The analysis reveals that the measured values are significantly influenced by the types of calorimeters and smoke gas analyzers used as well as by the type of thermal runaway trigger. This meta-analysis can serve as an important basis for any risk assessment of lithium-ion batteries.
For the realization of a sustainable energy economy, it is of great importance to develop CO2 -neutral methods producing multi-carbon organic chemicals used as feedstock in the chemical industry as well as carbon-neutral fuels. A promising method to alleviate the greenhouse effect and thereby forming value-added chemicals or syngas as an energy carrier, is through the electrochemical CO2 reduction reaction (CO2RR). In this work, a bioelectrotechnological approach is developed, in which the CO2RR reaction products (CO and H2) are directly fed to bacteria (acetogens), who use them as “reduction equivalents” to further metabolize CO2 to valuable carbon compounds. Therefore, a bio-electrochemical system consisting of a bioreactor coupled to a CO2 electrolysis cell will be established. Currently, scarce catalysts such as Ag and Au are used as for the CO2RR which may hamper the use of decentral CO2 conversion technology for cost reasons.
The technological viability of the bacteria-assisted electrolysis depends on the usage of efficient, biocompatible, and selective electrocatalysts prepared from inexpensive precursors. Porous transition metal and nitrogen co-doped carbons (M-N-Cs) have emerged as precious-metal free electrocatalysts for the direct electrochemical reduction of CO2 into CO and are excellent candidates for scale-up and deployment in technological applications. Furthermore, Co/Ni/Zn functioning as the catalytically active sites will be used, as they are expected to depict non-bactericidal properties in contrast to Cu and Ag catalysts. The non-bactericidal property could e.g., allow for application within the hybrid device (bio-electrochemical system), without the need to separate bacteria and cathode catalyst. The MNCs with the most promising electrocatalytic activity and selectivity will be evaluated in abiotic conditions in the hybrid bio-electrochemical reactor system.
For the realization of a sustainable energy economy, it is of great importance to develop CO2 -neutral methods producing multi-carbon organic chemicals used as feedstock in the chemical industry as well as carbon-neutral fuels. A promising method to alleviate the greenhouse effect and thereby forming value-added chemicals or syngas as an energy carrier, is through the electrochemical CO2 reduction reaction (CO2RR). In this work, a bioelectrotechnological approach is developed, in which the CO2RR reaction products (CO and H2) are directly fed to bacteria (acetogens), who use them as “reduction equivalents” to further metabolize CO2 to valuable carbon compounds. Therefore, a bio-electrochemical system consisting of a bioreactor coupled to a CO2 electrolysis cell will be established. Currently, scarce catalysts such as Ag and Au are used as for the CO2RR which may hamper the use of decentral CO2 conversion technology for cost reasons.
The technological viability of the bacteria-assisted electrolysis depends on the usage of efficient, biocompatible, and selective electrocatalysts prepared from inexpensive precursors. Porous transition metal and nitrogen co-doped carbons (M-N-Cs) have emerged as precious-metal free electrocatalysts for the direct electrochemical reduction of CO2 into CO and are excellent candidates for scale-up and deployment in technological applications. Furthermore, Co/Ni/Zn functioning as the catalytically active sites will be used, as they are expected to depict non-bactericidal properties in contrast to Cu and Ag catalysts. The non-bactericidal property could e.g., allow for application within the hybrid device (bio-electrochemical system), without the need to separate bacteria and cathode catalyst. The MNCs with the most promising electrocatalytic activity and selectivity will be evaluated in abiotic conditions in the hybrid bio-electrochemical reactor system.
To ensure safety when transporting dangerous goods, it is important to specify the flow properties of the respective solid filling substance of the packagings. For this purpose, the angle of repose is currently used for the UN approvals in Germany. Measurements were carried out on 12 powdery or granular substances applying the angle of repose measuring methods customary in the test centres. The results of the methods differ significantly from each other. In addition, some of the techniques cannot be applied for very cohesive or coarse-grained materials. The results for the angle of repose show a strong scatter for some constellations (coefficient of variation more than 20 %). Safety during transport of dangerous goods cannot be guaranteed with this currently practiced system of measuring the angle of repose. As a consequence, an alternative parameter to characterize the flow properties of bulk materials should be used in the recognized test centers for dangerous goods packagings, such as the Hausner ratio. This approach leads to more precise test results for the substances examined (maximum coefficient of variation 2.8 %). It also has advantages in terms of applicability and occupational safety.
Since the flow properties are safety-relevant, both in terms of mechanical safety and safety against the release of dangerous substances, the testing practice in the recognized test labs should be improved and standardized.
In den von der BAM anerkannten Prüfstellen kommen derzeit unterschiedliche Methoden der Schüttwinkelmessung zum Einsatz. Es ist unklar, welche dieser Methoden sich prinzipiell für welche Füllgüter eignen. Daher werden derzeit systematische Untersuchungen an der BAM durchgeführt, die im folgenden vorgestellt werden.
The leaks of dangerous goods from actually intact bags detected in the years 2018 to 2020 tend to be at an almost constant high level. These releases of powdery or granular dangerous goods represent violations of the sift-proofness required in the dangerous goods regulations. This article first analyzes the causes. The components of the bags that are affected by leaks are micro-perforations, joins and closures, in particular internal sleeve valves. A distinction must be made between bags closed in conformity with or contrary to the manufacturer's instructions. The particle release is determined by a number of influencing factors of the filling substance, the packaging and other boundary conditions. Therefore, a comprehensive test concept is developed in this work, which takes all these factors into account. The application of this test concept facilitates the planning of the test setup and the experiments. On this basis, the complex mechanisms involved in the release of solid substances can be systematically investigated in the test laboratory. To prevent releases of powdery or granular substances from intact bags, it is necessary that the user has access to the closing instructions and the relevant properties of the test substance used for the design type approval. Further experimental investigations are needed to assess whether filling substances change their properties during transport and whether this enables them to escape.
Fazit:
Nachteile der Schüttwinkel-Messmethoden:
Einschränkungen bei der Anwendbarkeit auf Füllgüter mit bestimmten Eigenschaften;
Die einzelnen Methoden liefern dann unterschiedliche Ergebnisse (statist. signifikante Abweichung der Mittelwerte);
Schlechte Wiederholbarkeit;
Bedienereinfluss spielt Rolle;
Gewährleistung des Arbeitsschutzes schwierig;
Bestimmung des Hausner-Faktors:
Keins dieser Defizite
Mögliche Abhilfemaßnahmen:
Prüfbericht und Zulassungsschein sollten zumindest die Methode angeben, die zur Messung des Schüttwinkels 𝛼 eingesetzt wurde;
Einheitliches Verfahren zur Schüttwinkelmessung (DIN-Methode)?
Umstellung des Systems auf einen alternativen Parameter zur Bestimmung der Fließeigenschaften:
Hausner-Faktor 𝐻:
Bessere Wiederholbarkeit der Ergebnisse;
Zuverlässige Anwendbarkeit auch auf Extremfälle von Schüttgütern;
Sicherere Handhabung von Gefahrgütern
This work focuses on the question if the bubble test prescribed in the Dangerous Goods Regulations has sufficient sensitivity to detect leakage rates which could result in the formation of explosive atmospheres during transport. The sensitivity of the bubble test is not directly comparable with other leak testing methods because of its different flow conditions.
Therefore, a normalized minimum detectable leakage rate under Helium test conditions is calculated for the bubble test. This sensitivity of the bubble test under reference conditions is compared with limit leakage rates for a worst-case transport scenario. The sensitivity of the bubble test is not sufficient to prove the limit leakage rates for 6-L packagings. The Formation of explosive vapour-air-mixtures cannot be excluded. Therefore, more sensitive leak testing methods should be considered for smaller packaging design types.
The Dangerous Goods Regulations currently do not include limit leakage rates or sensitivity requirements for industrial leak testing procedures that are equivalent to the bubble test, which is the prescribed test method for design type testing of dangerous goods packagings. During series production of such packagings, various methods are used which often do not reach the sensitivity of the bubble test. Based on a suitable pragmatic approach, its sensitivity under industrial conditions can be considered 10-4 Pa m³/s (SLR).
For the selection of a suitable industrial leak testing method, however, factors other than the sensitivity are also important, for example flow direction, pressure level and automatability. The following methods are in principal suitable and equally effective as the bubble test: pressure rise test (vacuum chamber), ultrasonic bubble leak detection and gas detection methods (pressure technique by accumulation and vacuum chamber technique).
To ensure a uniform test level during design type testing and production line leak testing and therefore a comparable safety level as required by the Dangerous Goods Regulations, it is necessary to include a more precise specification in these regulations. On the one hand, this requires an information about the sensitivity of the bubble test, on the other hand, the inclusion of a list of suitable, equally effective industrial test methods with their specific boundary conditions
Vergleichende Fallversuche zur Bewertung von Fallfundamenten - Ausblick auf Untersuchungen der BAM
(2020)
Oft verfügen Produktionsstätten über bereits verbaute Fallfundamente, die nicht das geforderte Massenverhältnis von 1:50 aufweisen. Gemäß ADR ist jedoch auf dem Niveau der Musterprüfung zu prüfen. Es ist daher fraglich, ob die Prüfungen im Rahmen der Eigenüberwachung und die Baumusterprüfungen vergleichbare Ergebnisse liefern, wenn die Fallfundamente unterschiedlich beschaffen sind. Ziel der Untersuchungen ist daher die Entwicklung eines Untersuchungs- und Prüfkonzepts für bereits verbaute Fallfundamente für Gefahrgutverpackungen im Rahmen einer ingenieurwissenschaftlichen Promotionsarbeit.
Es ist bislang noch keine einheitliche Vorgehensweise und kein bestimmtes Prüfverfahren für die Schüttwinkelmessung festgelegt. Bei den Prüffüllgütern handelt es sich nicht nur um gefährliche Ersatzfüllgüter, sondern zum Teil auch um gefährliche Originalfüllgüter. Es liegen noch keine systematische Untersuchungen darüber vor, welche der in den Prüfstellen gängigen Methoden sich prinzipiell für die Anwendung bei bestimmten Extremfällen von Füllgütern eignen. Ziel der Untersuchungen ist daher ein systematischer Vergleich bei der Anwendung verschiedener in den Prüfstellen gängiger Schüttwinkelmessmethoden.
Der derzeit in den Gefahrgutvorschriften genannte Bubble Test ist keine geeignete Prüfmethode, um für alle Verpackungsvolumina ein Dichtheitsniveau sicherzustellen, welches auf Sicherheitsbetrachtungen unter Beförderungsbedingungen basiert. Für kleinere Verpackungsbauarten müssten theoretisch empfindlichere Prüfmethoden angewandt werden. Auf der anderen Seite sollten Bauartprüfungen für Gefahrgutverpackungen nicht zu kompliziert sein. Daher sollte die Auswahl einer Methode erfolgen, die sowohl eine ausreichende Empfindlichkeit aufweist als auch über eine einfache Art der Durchführung verfügt.
Es werden die Ergebnisse von Leckageratenmessungen an den Verschlüssen von Gefahrgutverpackungen unterschiedlicher Bauarten vorgestellt. Die Prüfungen wurden mit dem Überdruckverfahren mit Ansammlung unter Verwendung des Prüfgases Helium vorgenommen. Die gemessenen Deckelleckageraten zeigen Größenordnungsunteschiede von mehreren Zehnerpotenzen. Durch einen Vergleich mit berechneten Grenzwerten lässt sich die Indentifizierung kritischer Bauarten vornehmen.
Untersuchung der stoßartigen Freisetzung pulverförmiger Füllgüter aus Ventilsäcken für Gefahrgüter mit Innenventil. Fallprüfungen an einem Papiersack 5M2 mit zwei Füllgütern (Esplas H130 und Zinkoxid). Variation von Ventillänge, Fallhöhe und Füllgrad in Kombination mit der Anzahl der Fallversuche pro Prüfmuster. Bei Esplas H 130 war ein Pulveraustritt aus den Klebestellen bereits beim Befüllen zu verzeichnen. Dies ist ein Widerspruch zu UN 6.1.4.18.1 (Staubdichheit). Bei beiden Substanzen waren die Ventile aller Prüfmuster nach der Fallprüfung nicht mehr staubdicht. Es wird auf erste mögliche Lösungsvorschläge eingegangen.
Untersuchung der stoßartigen Freisetzung pulverförmiger Füllgüter aus Ventilsäcken für Gefahrgüter mit Innenventil. Fallprüfungen an einem Papiersack 5M2 mit zwei Füllgütern (Esplas H130 und Zinkoxid). Variation von Ventillänge, Fallhöhe und Füllgrad in Kombination mit der Anzahl der Fallversuche pro Prüfmuster. Bei Esplas H 130 war ein Pulveraustritt aus den Klebestellen bereits beim Befüllen zu verzeichnen. Dies ist ein Widerspruch zu UN 6.1.4.18.1 (Staubdichheit). Bei beiden Substanzen waren die Ventile aller Prüfmuster nach der Fallprüfung nicht mehr staubdicht. Es wird auf erste mögliche Lösungsvorschläge eingegangen.
Derzeit existieren für Gefahrgutverpackungen in den internationalen Gefahrgutvorschriften keine Festlegungen für quantitative Grenzleckageraten, die sich an Sicherheitsbetrachtungen während der Beförderung orientieren. Für die Dichtheitsprüfung im Rahmen der Bauartzulassung von Gefahrgutverpackungen für flüssige Füllgüter ist das Standardprüfverfahren das Eintauchverfahren in Wasser („Bubble Test“). Hierbei handelt es sich um ein lokalisierendes Prüfverfahren. Seine Anwendung lässt keine quantitative Aussage darüber zu, ob unter Beförderungsbedingungen aufgrund von strömungsbedingter Stofffreisetzung durch Leckstellen der Gefahrgutverpackungen die Gefahr der Bildung einer explosionsfähigen Atmosphäre besteht. Zentrales Ziel der vorliegenden Arbeit ist daher, zunächst quantitative Dichtheitsanforderungen an Gefahrgutverpackungen im Hinblick auf die Entstehung explosionsfähiger Dampf-Luft-Gemische während des Transports zu entwickeln. Im Anschluss werden strömungsbedingte Leckageraten der Verschlüsse verschiedener Bauarten von Gefahrgutverpackungen gemessen. Der Vergleich der Messwerte mit den berechneten Grenzwerten ermöglicht die Einschätzung hinsichtlich der Bildung einer explosionsfähigen Atmosphäre. Dieser quantitative Ansatz zur Beurteilung der Dichtheit ist für Gefahrgutverpackungen derzeit noch nicht etabliert. Die Grenzleckageraten werden für das Szenario des interkontinentalen Transports von Gefahrgutverpackungen in einem 20-Fuß-Frachtcontainer im Hinblick auf die untere Explosionsgrenze abgeleitet. Dies geschieht unter Annahme einer Worst-Case-Betrachtung für Beförderungsdauer, Beladung und Luftwechselrate. Als mittlere Beförderungstemperatur wird 30 °C angesetzt. Eine vollständige Durchmischung im freien Luftraum des Containers wird angenommen. Es werden drei repräsentative Baugrößen von Gefahrgutverpackungen gewählt, mit einem Volumen von ca. 6 L, ca. 60 L und ca. 220 L. Als Füllgüter werden die 23 meistbeförderten flüssigen Gefahrgüter betrachtet. Die treibende Kraft für die Strömung durch Leckstellen ist der sich in der Verpackung ausbildende Überdruck. Die Berechnung des Überdrucks erfolgt durch analytische Modellgleichungen in Abhängigkeit der spezifischen Stoffdaten, Füllgrad, Befülltemperatur, Transporttemperatur und Nachgiebigkeit der Verpackungsbauart. Die quantitative Leckageratenmessung der Gefahrgutverpackungen wird mit dem Überdruckverfahren mit Ansammlung (Akkumulationsverfahren) unter Verwendung von Helium als Prüfgas vorgenommen. Zusätzlich erfolgt die Detektion weiterer potentieller Leckstellen außerhalb des Verschlussbereiches mit dem Schnüffelverfahren. Bei allen untersuchten Bauarten, mit Ausnahme des 6 L-Feinstblechkanisters, ist der Verschluss die einzige systematische Leckstelle der Verpackung. Die Messung der Helium-Leckageraten und der anschließende Vergleich mit den berechneten Helium-Grenzleckageraten zeigt, dass folgende Bauarten hinsichtlich des Erreichens der unteren Explosionsgrenze (UEG) durch eine Leckageströmung als kritisch einzuschätzen sind: Kunststoffverpackungen mit Schraubverschlüssen mit Flachdichtung, wenn bei diesen bestimmte Schädigungsmuster im Verschlussbereich vorliegen; Feinstblechkanister, da bei ihnen nicht nur der Verschlussbereich eine Leckstelle darstellt; Kunststoffverpackungen mit Schraubverschlüssen mit Flachdichtung, wenn diese auch für Füllgüter der Verpackungsgruppe I zugelassen sind. Als Konsequenz sollten bei diesen kritischen Bauarten entweder Modifikationen in Bezug auf die Verpackung selbst oder auf die Transportbedingungen im Frachtcontainer vorgenommen werden. Bei Kunststoffverpackungen ist auch die Füllgutpermeation als Freisetzungsmechanismus relevant. Es wird der prinzipielle Rechenweg zur Berücksichtigung dieses Quellterms exemplarisch gezeigt. Diese Arbeit leistet einen grundlegenden Beitrag für die Etablierung einer systematischen quantitativen Dichtheitsbetrachtung von Gefahrgutverpackungen mit dem Ziel der Verbesserung der Sicherheit beim interkontinentalen Gefahrguttransport im Frachtcontainer.
Derzeit existieren für Gefahrgutverpackungen in den internationalen Gefahrgutvorschriften keine Festlegungen für quantitative Grenzleckageraten, die sich an Sicherheitsbetrachtungen während der Beförderung orientieren. Für die Dichtheitsprüfung im Rahmen der Bauartzulassung von Gefahrgutverpackungen für flüssige Füllgüter ist das Standardprüfverfahren das Eintauchverfahren in Wasser („Bubble Test“). Hierbei handelt es sich um ein lokalisierendes Prüfverfahren. Seine Anwendung lässt keine quantitative Aussage darüber zu, ob unter Beförderungsbedingungen aufgrund von strömungsbedingter Stofffreisetzung durch Leckstellen der Gefahrgutverpackungen die Gefahr der Bildung einer explosionsfähigen Atmosphäre besteht. Ziel der vorliegenden Untersuchungen ist daher, zunächst quantitative Dichtheitsanforderungen an Gefahrgutverpackungen im Hinblick
auf die Entstehung explosionsfähiger Dampf-Luft-Gemische während des
Transports zu entwickeln. Im Anschluss werden strömungsbedingte Leckageraten der Verschlüsse verschiedener Bauarten von Gefahrgutverpackungen gemessen. Der Vergleich der Messwerte mit den berechneten Grenzwerten ermöglicht die Einschätzung hinsichtlich der Bildung einer explosionsfähigen Atmosphäre. Dieser quantitative Ansatz zur Beurteilung der Dichtheit ist für Gefahrgutverpackungen derzeit noch nicht etabliert.
Die quantitative Leckageratenmessung der Gefahrgutverpackungen wird mit dem Überdruckverfahren mit Ansammlung (Akkumulationsverfahren) unter Verwendung von Helium als Prüfgas vorgenommen. Zusätzlich erfolgt die Detektion weiterer potentieller Leckstellen außerhalb des Verschlussbereiches mit dem Schnüffelverfahren. Bei allen untersuchten Bauarten, mit Ausnahme des 6 L-Feinstblechkanisters, ist der Verschluss die einzige systematische Leckstelle der Verpackung. Die Messung der Helium-Leckageraten und der anschließende Vergleich mit den berechneten Helium-Grenzleckageraten zeigt, dass folgende Bauarten hinsichtlich des Erreichens der unteren Explosionsgrenze (UEG) durch eine Leckageströmung als kritisch einzuschätzen sind: Kunststoffverpackungen mit Schraubverschlüssen mit Flachdichtung, wenn bei diesen bestimmte Schädigungsmuster im Verschlussbereich vorliegen; Feinstblechkanister, da bei ihnen nicht nur der Verschlussbereich eine Leckstelle darstellt; Kunststoffverpackungen mit Schraubverschlüssen mit Flachdichtung, wenn diese auch für Füllgüter der Verpackungsgruppe I zugelassen sind. Als Konsequenz sollten bei diesen kritischen Bauarten entweder Modifikationen in Bezug auf die Verpackung selbst oder auf die Transportbedingungen im Frachtcontainer vorgenommen werden.
In den internationalen Gefahrgutvorschriften ist vorgeschrieben, dass Säcke und flexible Großpackmittel (Flexible Intermediate Bulk Container – FIBC) staubdicht sein müssen. Eine quantitative Definition des Terminus Staubdichtheit, wie in anderen Technikgebieten üblich, ist jedoch nicht gegeben. Auch geeignete Prüfverfahren zum Nachweis der Staubdichtheit sind in den Vorschriften nicht genannt.
In der Praxis der stichpunkartigen Kontrollen von Gefahrguttransporten durch die Schwerlastgruppe der Autobahnpolizei Münster werden immer wieder Austritte von pulverförmigen oder körnigen Gefahrgütern aus eigentlich intakten Säcken und FIBC detektiert. Es wird ein Überblick über die im Jahr 2018 festgestellten Gefahrgutaustritte aus diesen Gefahrgutverpackungen sowie eine systematische Einordnung hinsichtlich betroffener Bauarten und möglicher Ursachen gegeben.
Bei der Stofffreisetzung aus intakten Gefahrgutverpackungen liegt ein mechanischer Transport von Partikeln durch Leckkanäle, z. B. im Verschluss-, Naht- oder Wandungsbereich, vor. Generell kommen zwei Freisetzungswege in Frage: Einerseits eine Langzeit-Freisetzung während des Transports, hervorgerufen durch eine kombinierte Wirkung von Stapellast des Füllguts und Transportvibrationen; andererseits eine stoßartige Freisetzung.
Auf Grundlage von durchgeführten Untersuchungen hinsichtlich der stoßartigen Freisetzung pulverförmiger Stoffe aus Gefahrgutsäcken werden erste Lösungsansätze hin zu einer Verbesserung der Staubdichtheit von Gefahrgutsäcken und -FIBC vorgestellt. Es wird ein Ausblick auf nachfolgende Arbeiten gegeben.
The flow properties of powdery or granular filling substances for dangerous goods packagings are safety-relevant parameters. To specify the flow behavior, the angle of repose is measured in the recognized test centers for dangerous goods packagings in Germany. Previous investigations performed on non-hazardous substances revealed that some of the methods currently used have disadvantages in application. Additionally, for occupational health and safety reasons, it was generally viewed critically to carry out measurements of the angle of repose for dangerous goods at all. Instead, the dimensionless Hausner ratio to describe the flow behavior was proposed.
In this work, the investigations were extended to real hazardous substances to concretize the assessment. Five exemplary hazardous substances were tested for their angle of repose using the methods commonly applied in the test centers. The Hausner ratio was also determined. In addition, the influence of a different climatic preconditioning on the angle of repose measurement was examined using three selected non-hazardous bulk materials.
The results show that the measurement of the angle of repose is not fundamentally excluded for dangerous goods. However, for reasons of applicability, repeatability and occupational health and safety, only the ISO method can be applied for dangerous filling substances. This method provides conservative results regarding a safety-related evaluation of flow properties for the transport of dangerous goods.
In principle, both the ISO method and the determination of the Hausner ratio can be used for dangerous goods. It is also essential especially with finely powdered filling goods, to carry out controlled preconditioning.
Die in den von der BAM anerkannten Prüfstellen für Gefahrgutverpackungen gängigen Schüttwinkel-Messmethoden werden verglichen, anhand der Messung an fünf pulverförmigen oder körnigen Stoffen mit gefährlichen Eigenschaften. Zusätzlich wird die Untersuchung des Einflusses einer unterschiedlichen klimatischen Vorlagerung vorgenommen.
The flow properties of powdery or granular filling substances for dangerous goods packagings are safety-relevant parameters. To specify the flow behavior, the angle of repose is measured in the recognized test centers for dangerous goods packagings in Germany. Previous investigations performed on non-hazardous substances revealed that some of the methods currently used have disadvantages in application. Additionally, for occupational health and safety reasons, it was generally viewed critically to carry out measurements of the angle of repose for dangerous goods at all. Instead, the dimensionless Hausner ratio to describe the flow behavior was proposed.
In this work, the investigations were extended to real hazardous substances to concretize the assessment. Five exemplary hazardous substances were tested for their angle of repose using the methods commonly applied in the test centers. The Hausner ratio was also determined. In addition, the influence of a different climatic preconditioning on the angle of repose measurement was examined using three selected non-hazardous bulk materials.
The results show that the measurement of the angle of repose is not fundamentally excluded for dangerous goods. However, for reasons of applicability, repeatability and occupational health and safety, only the ISO method can be applied for dangerous filling substances. This method provides conservative results regarding a safety-related evaluation of flow properties for the transport of dangerous goods.
In principle, both the ISO method and the determination of the Hausner ratio can be used for dangerous goods. It is also essential especially with finely powdered filling goods, to carry out controlled preconditioning.
To ensure safety when transporting dangerous goods, it is important to specify the flow properties of the respective solid filling substance of the packagings. For this purpose, the angle of repose is currently used for the UN approvals in Germany. Measurements were carried out on 12 powdery or granular substances applying the angle of repose measuring methods customary in the test centres. The results of the methods differ significantly from each other. In addition, some of the techniques cannot be applied for very cohesive or coarse-grained materials. The results for the angle of repose show a strong scatter for some constellations (coefficient of variation more than 20 %). Safety during transport of dangerous goods cannot be guaranteed with this currently practiced system of measuring the angle of repose. As a consequence, an alternative parameter to characterize the flow properties of bulk materials should be used in the recognized test centers for dangerous goods packagings, such as the Hausner ratio. This approach leads to more precise test results for the substances examined (maximum coefficient of variation 2.8 %). It also has advantages in terms of applicability and occupational safety.
Since the flow properties are safety-relevant, both in terms of mechanical safety and safety against the release of dangerous substances, the testing practice in the recognized test labs should be improved and standardized.
Abstract: The leaks of dangerous goods from actually intact bags detected in the years 2018 to 2020 tend to be at an almost constant high level. These releases of powdery or granular dangerous goods represent violations of the sift-proofness required in the dangerous goods regulations. This article first analyzes the causes. The components of the bags that are affected by leaks are micro-perforations, joins and closures, in particular internal sleeve valves.
A distinction must be made between bags closed in conformity with or contrary to the manufacturer's instructions.
The particle release is determined by a number of influencing factors of the filling substance, the packaging and other boundary conditions. Therefore, a comprehensive test concept is developed in this work, which takes all these factors into account. The application of this test concept facilitates the planning of the test setup and the experiments. On this basis, the complex mechanisms involved in the release of solid substances can be systematically investigated in the test laboratory. To prevent releases of powdery or granular substances from intact bags, it is necessary that the user has access to the closing instructions and the relevant properties of the test substance used for the design type approval. Further experimental investigations are needed to assess whether filling substances change their properties during transport and whether this enables them to escape.
The leaks of dangerous goods from actually intact bags detected in the years 2018 to 2020 tend to be at an almost constant high level. These releases of powdery or granular dangerous goods represent violations of the sift-proofness required in the dangerous goods regulations. This article first analyzes the causes.
The components of the bags that are affected by leaks are micro-perforations, joins and closures, in particular internal sleeve valves. A distinction must be made between bags closed in conformity with or contrary to the manufacturer's instructions. The particle release is determined by a number of influencing factors of the filling substance, the packaging and other boundary conditions.
Therefore, a comprehensive test concept is developed in this work, which takes all these factors into account. The application of this test concept facilitates the planning of the test setup and the experiments. On this basis, the complex mechanisms involved in the release of solid substances can be systematically investigated in the test laboratory.
To prevent releases of powdery or granular substances from intact bags, it is necessary that the user has access to the closing instructions and the relevant properties of the test substance used for the design type approval. Further experimental investigations are needed to assess whether filling substances change their properties during transport and whether this enables them to escape.
In practice, checks on dangerous goods transports often detect leaks of powdered dangerous goods from valved bags. In this work, the influence factors of a sudden release of powdery substances from the valves of valved bags were investigated. Drop tests were carried out on paper bags of UN design type 5M2 with internal sleeve valve using two different powdery substances (Esplas H130 and zinc oxide “Rotsiegel”).
The internal sleeve valves of all test samples were not sift-proof with respect to both filling substances. For almost all test samples, the Esplas H130 powder already leaked out of pasted joints during manual filling. This is a contradiction to the requirement in UN 6.1.4.18.1, according to which closures and joints of paper bags 5M2 should be sift-proof.
In the drop tests, longer valve lengths had a greater sealing effect for both filling substances (for filling degrees of at least 95% and for test samples which had already been mechanically loaded). As an extreme example, at the drop height of 1.20 m and a filling degree of 100%, the released amount of zinc oxide powder from a 10 cm long valve was about 16 times higher than from a valve length of 12.5 cm. The valve length is therefore a safety-relevant parameter and should be specified by the manufacturer.
To ensure that only filling goods with similar physical properties in comparison to the test substance are used for valved bags, the user must be informed of the particle size of the test substance.
In practice, checks on dangerous goods transports often detect leaks of powdered dangerous goods from valved bags. In this work, the influence factors of a sudden release of powdery substances from the valves of valved bags were investigated.
Drop tests were performed on paper bags of UN design type 5M2 with internal sleeve valve using 2 different powdery substances (Esplas H130 and zinc oxide “Rotsiegel”).
The internal sleeve valves of all test samples were not sift‐proof with respect to both filling substances. For almost all test samples, the Esplas H130 powder already leaked out of pasted joints during manual filling. This is a contradiction to the requirement in UN 6.1.4.18.1, according to which closures and joints of paper bags 5M2 should be sift‐proof.
In the drop tests, longer valve lengths had a greater sealing effect for both filling substances (for filling degrees of at least 95% and for test samples which had already been mechanically loaded). As an extreme example, at the drop height of 1.20 m and a filling degree of 100%, the released amount of zinc oxide powder from a 10‐cm‐long valve was about 16 times higher than from a valve length of 12.5 cm.
The valve length is therefore a safety‐relevant parameter and should be specified by the manufacturer.
To ensure that only filling goods with similar physical properties in comparison with the test substance are used for valved bags, the user must be informed of the particle size of the test substance.
Gemäß den internationalen Gefahrgutvorschriften müssen Säcke und flexible Großpackmittel (Flexible Intermediate Bulk Container - FIBC) für feste Gefahrgüter staubdicht sein.
In der Praxis der stichpunktartigen Kontrollen von Gefahrguttransporten durch die Autobahnpolizei Münster werden jedoch immer wieder Austritte von pulverförmigen oder körnigen Gefahrgütern aus eigentlich intakten Säcken und FIBC detektiert.
Es wird ein Überblick über die im Jahr 2019 festgestellten Gefahrgutaustritte aus diesen Arten von Gefahrgutverpackungen gegeben. Darauf aufbauend wird eine systematische Einordnung hinsichtlich betroffener Bauarten und eine Diskussion möglicher Lösungsansätze vorgenommen.
In den internationalen Gefahrgutvorschriften ist vorgeschrieben, dass Säcke und flexible Großpackmittel (Flexible Intermediate Bulk Container – FIBC) staubdicht sein müssen. Eine quantitative Definition des Terminus Staubdichtheit, wie in anderen Technikgebieten üblich, ist jedoch nicht gegeben. Auch geeignete Prüfverfahren zum Nachweis der Staubdichtheit sind in den Vorschriften nicht genannt.
In der Praxis der stichpunkartigen Kontrollen von Gefahrguttransporten durch die Schwerlastgruppe der Autobahnpolizei Münster werden immer wieder Austritte von pulverförmigen oder körnigen Gefahrgütern aus eigentlich intakten Säcken und FIBC detektiert. Es wird ein Überblick über die im Jahr 2018 festgestellten Gefahrgutaustritte aus diesen Gefahrgutverpackungen sowie eine systematische Einordnung hinsichtlich betroffener Bauarten und möglicher Ursachen gegeben.
Bei der Stofffreisetzung aus intakten Gefahrgutverpackungen liegt ein mechanischer Transport von Partikeln durch Leckkanäle, z. B. im Verschluss-, Naht- oder Wandungsbereich, vor. Generell kommen zwei Freisetzungswege in Frage: Einerseits eine Langzeit-Freisetzung während des Transports, hervorgerufen durch eine kombinierte Wirkung von Stapellast des Füllguts und Transportvibrationen; andererseits eine stoßartige Freisetzung.
Auf Grundlage von durchgeführten Untersuchungen hinsichtlich der stoßartigen Freisetzung pulverförmiger Stoffe aus Gefahrgutsäcken werden erste Lösungsansätze hin zu einer Verbesserung der Staubdichtheit von Gefahrgutsäcken und -FIBC vorgestellt. Es wird ein Ausblick auf nachfolgende Arbeiten gegeben.
Sift-proofness is a requirement for different types of dangerous goods packagings for solid substances according to the international Dangerous Goods Regulations. In these regulations, a sift-proof packaging is defined as a packaging that is completely impermeable to dry contents. This means indirectly that absolutely no mass transport of solid substances is allowed. Moreover, this requirement applies both to the original filling substance and to fine solid material generated during transport. Further specifications, test conditions or tolerable limit values are not given. This is in contrast to physical principles and the usual practice in other fields of technology in which sift-proofness is relevant. This paper shows the necessary steps for how the requirements for sift-proofness of dangerous goods packagings can be defined more precisely. Physical basics of the term ‘sift-proofness’ are explained. A qualitative as well as a quantitative approach is possible. In any case, it is essential to carry out appropriate vibration tests to assess the siftproofness. There is a need for systematical investigations of the sift-proofness of dangerous goods packagings.
This work focuses on the question if the bubble test prescribed in the Dangerous Goods Regulations has sufficient sensitivity to detect leakage rates, which could result in the formation of explosive atmospheres during transport. The sensitivity of the bubble test is not directly comparable with other leak testing methods because of its different flow conditions. Therefore, a normalized minimum detectable leakage rate under Helium test conditions is calculated for the bubble test. This sensitivity of the bubble test under reference conditions is compared with limit leakage rates for a worst‐case transport scenario. The sensitivity of the bubble test is not sufficient to prove the limit leakage rates for 6‐L packagings. The formation of explosive vapour‐air‐mixtures cannot be excluded. Therefore, more sensitive leak testing methods should be considered for smaller packaging design types.
The Dangerous Goods Regulations currently do not include limit leakage rates orsensitivity requirements for industrial leak testing procedures that are equivalent tothe bubble test, which is the prescribed test method for design type testing ofdangerous goods packagings. During series production of such packagings, variousmethods are used, which often do not meet the requirements of the bubble test withregard to important criteria.Sensitivity, flow direction, pressure level and automatability are particularly importantfactors when selecting a suitable industrial leak testing method.The following methods are in principle both suitable and equally effective as thebubble test: pressure rise test (vacuum chamber), ultrasonic bubble leak detectionand gas detection methods (pressure technique by accumulation and vacuumchamber technique).To ensure a uniform test level during design type testing and production line leaktesting and therefore a comparable safety level as required by the Dangerous GoodsRegulations, it is necessary to include a more precise specification in these regula-tions. This requires, on the one hand, information about the sensitivity of the bubbletest and, on the other hand, the inclusion of a list of suitable, equally effective indus-trial test methods with their specific boundary conditions.