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Predictive Methods for Determining the Thermal Decomposition Properties of Hazardous Substances
(2019)
Due to the fast development and availability of computers, predictive approaches are increasingly used in the evaluation process of hazardous substances complementary to experiments. Their use was recommended as alternative to experimental testing by the REACH regulation to complete the lack of knowledge on properties for existing substances that must be registered before 2018 (upon quantities). Among the proposed predictive approaches, Quantitative Structure Property Relationships (QSPR) are powerful methods to predict macroscopic properties from the only molecular structure of substances. In that context, the HAZPRED project (2015-2018, founded by the SAF€RA consortium) aims to develop theoretical models (e.g. QSPR) and small-scale tests to predict complex physico-chemical properties (e.g. thermal stability, explosivity) of hazardous substances to complete the lack of knowledge on these hazardous substances quickly or to understand their decomposition behaviour better. In particular, this contribution will present the work done in this project on the physical hazards of organic peroxides and self-reactive substances: gathering of existing experimental data, new experimental campaigns, review of existing models and proposition of new estimation methods.
Explosion and decomposition limits of flammable and chemically unstable gases were determined experimentally in a closed autoclave with an ignition energy higher than the standard 10 J a 20 J. The ignition source was a lightning arc caused by an exploding wire igniter as described in EN 1839 B. With a newly developed ignition system a graded ignition energy between 3 J and 1000 J was generated. Different types of gases were studied with this ignition system: methane as a typical fuel gas and reference gas for some standards for explosion limit determination, the refrigerant R32 (difluoromethane) as a mildly flammable gas with low burning velocity and high minimum ignition energy compared with methane as well as the chemical unstable gases acetylene, nitrous oxide and ethylene oxide, which can decompose explosively in the absence of air or other oxidizers. It was found that the influence of strong ignition sources on explosion and decomposition limits can be very different for different systems. In case of methane only the upper explosion limit was influenced significantly by the ignition energy, whereas the lower explosion limit was constant. In a standard test vessel with an inner volume of 14 dm3 it was difficult to quantify the upper explosion limit of methane exactly with the strong ignition source, because the explosion pressure did not increase abruptly near the explosion limit, but steadily over a large concentration range. Probably a larger explosion vessel is more appropriate in this case. In case of R32 however, it was the lower explosion limit that was influenced significantly by the ignition energy and not the upper explosion limit. A particularly strong dependency from the ignition energy was found for the decomposition limits of the chemically unstable gases in nitrogen. Here special regard is necessary in practical applications, if uncommonly strong ignition sources cannot be excluded.
CEQAT-DGHS Interlaboratory tests for method validation and measurement uncertainty determination
(2019)
An explosion in a chemical plant or a fire on a dangerous goods vessel - the reason for such accidents can be numerous. Prevention starts in the laboratory where chemicals are tested for their hazardous properties in order to be able to assess the risks involved in their handling. For this purpose, test methods have been developed and published. They are applied globally nowadays. Safety experts, manufacturers, suppliers, importers, employers or consumers must be able to rely on the validity of safety-related test methods and on correct test results and assessments in the laboratory.
Interlaboratory tests play a decisive role in assessing the reliability of test results. Participation in interlaboratory tests is not only a crucial element of the quality assurance of laboratories; as such it is explicitly recommended in DIN EN ISO/IEC 17025. In addition, interlaboratory tests are also used to develop and validate test methods and can be used for the determination of the measurement uncertainty.
Interlaboratory tests on different test methods have been performed by Bundesanstalt für Materialforschung und –prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB) in collaboration with the QuoData GmbH during the last 10 years. Significant differences between the results of the participating laboratories were observed in all interlaboratory tests. The deviations of the test results were not caused only by laboratory faults but also by deficiencies of the test method (see interlaboratory test reports of the CEQAT-DGHS Centre for quality assurance for testing of dangerous goods and hazardous substances: www.ceqat-dghs.bam.de).
In view of the interlaboratory test results the following conclusions can be drawn:
• To avoid any discrepancy on classification and labelling of chemicals it should become state of the art to use validated test methods and the results accompanied by the measurement uncertainty.
• A need for improvement is demonstrated for all examined test methods. Thus, interlaboratory tests shall initially aim at the development, improvement and validation of the test methods (including the determination of the measurement uncertainty) and not on proficiency tests.
• The laboratory management and the practical execution of the tests need to be improved in many laboratories.
• The term "experience of the examiner" must be seen critically: A "long experience with many tests" is not necessarily a guarantee for correct results.
CEQAT-DGHS Interlaboratory Test Programme for Chemical Safety - Need of Test Methods Validation -
(2019)
Safety experts, manufacturers, suppliers, importers, employers or consumers must be able to rely on the validity of safety-related test methods and on correct test results and assessments in the laboratory. Via the eChemPortal lots of data from the REACH registration dossiers are available. However, the quality and correctness of the information remains in the responsibility of the data submitter. Unfortunately, we found more or less appropriate information on physicochemical properties and concluded that more quality or adequacy of any data submitted will be needed.
Interlaboratory tests play a decisive role in assessing the reliability of test results. Interlaboratory tests on different test methods have been performed by Bundesanstalt für Materialforschung und –prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB) in collaboration with the QuoData GmbH during the last 10 years. Significant differences between the results of the participating laboratories were observed in all interlaboratory tests. The deviations of the test results were not caused only by laboratory faults but also by deficiencies of the test method.
In view of the interlaboratory test results the following conclusions can be drawn:
• To avoid any discrepancy on classification and labelling of chemicals it should become state of the art to use validated test methods and the results accompanied by the measurement uncertainty.
• A need for improvement is demonstrated for all examined test methods. Thus, interlaboratory tests shall initially aim at the development, improvement and validation of the test methods and not on proficiency tests.
• The laboratory management and the practical execution of the tests need to be improved in many laboratories.
• The term "experience of the examiner" must be seen critically: A "long experience with many tests" is not necessarily a guarantee for correct results.
Predictive Methods for Determining the Thermal Decomposition Properties of Hazardous Substances
(2019)
Due to the fast development and availability of computers, predictive approaches are increasingly used in the evaluation process of hazardous substances complementary to experiments. Their use was recommended as alternative to experimental testing by the REACH regulation to complete the lack of knowledge on properties for existing substances that must be registered before 2018 (upon quantities). Among the proposed predictive approaches, Quantitative Structure Property Relationships (QSPR) are powerful methods to predict macroscopic properties from the only molecular structure of substances.
In that context, the HAZPRED project (2015-2018, founded by the SAF€RA consortium) aims to develop theoretical models (e.g. QSPR) and small-scale tests to predict complex physico-chemical properties (e.g. thermal stability, explosivity) of hazardous substances to complete the lack of knowledge on these hazardous substances quickly or to understand their decomposition behaviour better.
In particular, this contribution will present the work done in this project on the physical hazards of organic peroxides and self-reactive substances: gathering of existing experimental data, new experimental campaigns, review of existing models and proposition of new estimation methods.
CEQAT-DGHS Interlaboratory Test Programme for Chemical Safety - Need of Test Methods Validation
(2019)
Safety experts, manufacturers, suppliers, importers, employers or consumers must be able to rely on the validity of safety-related test methods and on correct test results and assessments in the laboratory. Via the eChemPortal lots of data from the REACH registration dossiers are available. However, the quality and correctness of the information remains in the responsibility of the data submitter. Unfortunately, we found more or less appropriate information on physicochemical properties and concluded that more quality or adequacy of any data submitted will be needed.
Interlaboratory tests play a decisive role in assessing the reliability of test results. Interlaboratory tests on different test methods have been performed by Bundesanstalt für Materialforschung und –prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB) in collaboration with the QuoData GmbH during the last 10 years. Significant differences between the results of the participating laboratories were observed in all interlaboratory tests. The deviations of the test results were not caused only by laboratory faults but also by deficiencies of the test method.
In view of the interlaboratory test results the following conclusions can be drawn:
• To avoid any discrepancy on classification and labelling of chemicals it should become state of the art to use validated test methods and the results accompanied by the measurement uncertainty.
• A need for improvement is demonstrated for all examined test methods. Thus, interlaboratory tests shall initially aim at the development, improvement and validation of the test methods and not on proficiency tests.
• The laboratory management and the practical execution of the tests need to be improved in many laboratories.
• The term "experience of the examiner" must be seen critically: A "long experience with many tests" is not necessarily a guarantee for correct results.
Since the early drafting of the European standards for civil explosives, harmonised under directive 93/15/EEC and 2014/28/EU, blasting technology has developed notably. This is particularly evident for electronic detonators and electronic firing systems, and the EU commission agreed to initiate a standardisation initiative, also noting that the currently existing document on electronic detonators is “only” a Technical Specification (CEN/TS). This paper addresses the current activities in the area of standardisation. The EU is about to launch a formal standardisation request to cover the most recent technological developments not addressed by the current standards. The request would also include various adjustments of references to the new Directive for civil explosives, and in addition the task of developing a Technical Specification for on-site mixed explosives and corresponding manufacturing units. The latter has been included to address the nowadays frequently found mobile production on the basis of ammonium nitrate prills or emulsions.
Several decades have passed since the initial drafting of the European standards for explosives subject to European Directive 2014/28/EU, and this field as experienced some substantial technical innovations. While at the turn of the millenium the concept of electronic detonators had just been conceived, and it is mentioned in a Technical Specification, today electronic detonators exist in many variants, also regarding communication means between shotfirer and the detonating cap. Questions regarding safe functioning and prevention of inadvertent ignition have to be asked in a quite different way, where delicate electronic circuits are used, and where information is transmitted by radio waves. In addition, the safety of functioning is partly found in software components and the corresponding standards need to be reviewed thoroughly on these grounds.
A different but in recent times more and more popular technology, is the on-site production of explosives, being mostly emulsion explosives, ANFO, or combined products. Also here software in the machinery is starting to play an important role. The on-site produced explosive must fulfil safety requirements and has to be, in addition, quality controlled. This cannot solely be left to the hopefully proper design of the software and machinery, but needs to be made accessible to verification. Since this area seems broader in approach, it is not going to be addressed by a new standard. The state of the art technology shall be described in a Technical Specification with a perspective from requirements of the above mentioned European Directive.
The explosion regions of 1-propanol, 2-propanol, acetone and 1-butanol in air were measured in the presence of CO2, He, N2 and Ar in accordance with EN1839 method T at high temperatures and at atmospheric pressure. The experimental results show that 1-propanol, 2-propanol and acetone have very similar lower explosion limits (LELs). 1-Butanol shows a slightly wider explosion area near the LEL line. In addition, the explosion regions of all combustible/inert gas/air mixtures were calculated with the method of constant adiabatic flame temperature profiles (CAFTP), using the flame temperature profile along the explosion region boundary curve of each combustible/N2/air mixture as a reference to determine the explosion regions of combustible/inert gas/air mixtures with inert gases other than N2 at different initial temperatures. To calculate the explosion regions for systems containing He, the calculation method was modified to include the very different physical transport properties of He. Moreover, the procedure for calculating the apexes in the ternary explosion diagrams was modified. The calculation results show good agreement with the experimental results.