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Zur Bestimmung der Deflagrationsfähigkeit von energiereichen Stoffen/ Gemischen wurde zuletzt ein Vier-Liter-Autoklav vorgeschlagen, der im Vergleich zu den derzeit gängigen Prüfmethoden eine Reihe von Vorteilen bietet. In diesem Beitrag wird der Frage nachgegangen, wie nicht-atmosphärische Bedingungen das Deflagrationsverhalten beeinflussen. Zur Beantwortung dieser Frage wurden weitere Experimente im genannten Autoklaven und in einem kleineren Autoklaven durchgeführt. Im Wesentlichen lässt sich feststellen, dass der Druck im Probengefäß vor Versuchsbeginn, insbesondere reduzierter Ausgangsdruck < 1 bar Auswirkungen auf das Deflagrationsverhalten hat. Das Vorhandensein einer reinen Stickstoffatmosphäre hingegen, beeinflusst das Deflagrationsverhalten nicht.
Many substances react with water in such a way that flammable gases are formed. For transport issues this reaction may possess a considerable hazard especially if the cargo is wetted by rain or by water from other sources. In the UN Recommendations on the Transport of Dangerous Goods these kinds of problems are addressed. The UN test N.5 'Test method for substances which in contact with water emit flammable gases' corresponds to this hazard. Classification according to the test method is done by measurement of the gas evolution rate of the flammable gas by any suitable procedure. At BAM a gravimetric approach is used to measure the gas evolution rate. In this paper we present the evaluation of the apparatus by means of an absolute calibration routine utilizing a reaction where a known amount of gas is produced as well as the evaluation of important parameters influencing the gas evolution rate using different substances. It can be shown that the apparatus is capable of measuring absolute gas volumes as low as 6 mL with an acceptable error of about 17% as determined from the reaction of Mg with demineralized water.
For the determination of deflagration capability of energetic substances, the test methods
according to VDI 2263-1, part 1.6 and UN-Manual, C.1- und C.2-test are used. These
methods are suited to evaluate the intrinsic material property deflagration. For
evaluation of deflagration behavior in closed systems, for example in production sites, an
appropriate test apparatus is missing. Because of this, the BAM Federal Institute for
Materials Research and Testing developed a four-liter-autoclave for conducting the
deflagration test under isochoric conditions. Deflagration behavior was evaluated under
different parameters e. g. pressure and temperature. On the basis of results it can be
seen, that the four-liter-autoclave is suited for the determination of deflagration behavior.
On the one hand, the same characteristics as in the standard test methods are obtained.
On the other hand, there are additional characteristics, like pressure rise and
decomposition velocity. On the basis of pressure measurement, the emerging gas volume
and the rate of gas evolution, that are used to design protection measures, can be
estimated. The measurements are conducted with the deflagrating substance
Azodicarboxamide (ADCA). It is concluded that the four-liter-autoclave is a good
alternative for conducting deflagration tests.
UN-Test N.5
(2009)
One of the fundamental principles of the UN-GHS (Globally Harmonized System of Classification and Labelling of Chemicals) is that all hazards of a chemical should be assigned and communicated. There is no general prioritization of hazards in the sense that certain hazard classes are not applicable if another one has been assigned. In contrast to health and environmental hazards, there are physical or chemical factors which preclude certain combinations of physical hazard classes. So far, there is no common understanding as to which combinations are relevant and which not. For example, should a pyrophoric liquid be classified as flammable liquid in addition, or is this redundant and unnecessary? In the course of the implementation of the GHS by countries or sectors and the actual application by industry all over the world, such questions become more and more important.
This publication systematically discusses all combinations of the UN-GHS physical hazard classes and assesses them with regard to the relevance of possible simultaneous assignment to a chemical. For many of the combinations an unambiguous decision based on theGHS alone is not possible, thus confirming that the question which physical hazard classes might be assigned simultaneously to a chemical is not trivial. As one more milestone on the path to a globally harmonized system for the classification of hazardous chemicals, this should be discussed and ultimately solved on a global basis. It is the hope that this publication might serve as an impetus for such discussions.