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Is the UN H.4 test a suitable test to determine the SADT for solids in a 50 kg packaging or not?
(2003)
The main gaseous products and the mass loss during the self-ignition of combustible materials
(2006)
Many self-accelerating decomposition temperatures (SADTs) of solid organic peroxides and self-reactive substances have been determined with the UN test method H.4, which is a scaled down test in a small Dewar vessel. For solid organic peroxides and solid self-reactive substances Fierz has questioned this procedure in a recent paper. Fierz concluded that the Dewar test results should not be extrapolated to beyond 8 l packages, owing to the thermal insulation value of solids. On the other hand, long term experience with the test, with a great variety of solid organic peroxides and self-reactive substances show about equal critical temperatures in the small Dewar vessel and on 50 kg scale. In the present work, we first checked, by numerical simulations, the Dewar scale versus the larger scale, in a way comparable with Fierz method: both scales are simulated by spheres, consisting of a number of annular layers, for the large scale the usual external heat loss term is used but for the small scale the outside heat transfer is strongly limited. The outcome of these simulations, covering a variety of physical parameters, supports the concerns expressed by Fierz. After this, we performed accurate cooling and heating experiments with solid organic peroxide in the usual Dewar vessel, provided with a large set of thermocouples. The results of these experiments showed that the simulation model for the Dewar vessel has to be changed from a spherical analogue to a short cylinder of solid material with heat exchange mainly via its top (Utop 3.5 W/(m2 K), overall heat transfer coefficient) and some heat exchange (Uside 0.29 W/(m2 K)) through its cylindrical and bottom part. With this modified cylinder model (being neither an infinitely long cylinder nor a slab) of the Dewar vessel, we found that the UN method H.4 enables an accurate prediction of the SADT, with small deviations of 0 ± 2.5 °C. Further, by performing a truly three-dimensional (3D) finite element calculation in FEMLAB, the new heat characteristics of the Dewar vessel as well as a 50 kg package of dilauroyl peroxide, a solid organic peroxide, were checked. The outcome was compared with the critical ambient temperatures known for various package sizes, which agreed well.
The exothermic reactions of thermally unstable materials have been studied using self-heating methods in a wire-mesh-reactor as well as temperature-programmed methods utilizing a differential scanning calorimeter (DSC). Samples of lignite coal dust, cork dust, detergent powder and riboflavin (vitamin B2) were investigated. The overall activation energy E could be determined for each method. For lignite coal and cork dust all techniques show very nice agreement in E. For the detergent powder, the values are comparable except for the heat-release (HR) rate method value which is about 5060 kJ/mol higher. Riboflavin on the other hand shows a different behaviour. The DSC-experiments lead to values being significantly higher compared to the self-heating values. The existing differences are clearly worked out.
Data and prediction for the mass burning rate of a tert-butyl-peroxy-benzoat (TBPB) pool fire (pool diameter = 3 m) is presented. The mass burning rates of TBPB fires are up to six times higher and less dependent on pool diameter compared to hydrocarbon pool fires caused by an additional heat release rate due to exothermic decomposition reaction in the liquid phase. This heat release rate is calculated using a 1st order reaction kinetic obtained from micro calorimetric measurements. A new model is derived considering the heat release rate due to the decomposition reaction which is shown to be 100 % of the heat release rate radiated to the pool surface. With the presented model, including also physical quantities, especially the limiting fuel concentration for upward flame propagation, it is possible to predict the mass burning rates of large TBPB pool fires. The predicted values are in very good agreement with the experiments.
For 1H-benzotriazole, no explosive properties are observable, but the relative high exothermic decomposition energy of 1590 J/g should be kept in mind. Nevertheless, an endothermic melting barrier at 100 °C ensures safe handling at lower temperatures. For 1H-1,2,3-triazole, the exothermic decomposition energy is as high as 2600 J/g, but explosive properties are also not detectable. Therefore, both reagents are hazardous with regard to the exothermic decomposition potential and can be handled safely with precautions.