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Evaluate tank car PRV behavior under realistic fire conditions Subject 1/3 scale tank with full size PRV to engulfing pool fire Initial tests with water lading. Current tests with flammable lading (Ethanol). Document PRV performance with respect to opening pressure, reclosing, and evacuating the tank
This paper is based mainly on the results of two different projects performed in the group of the author recently (2016-2019). The three external partners involved in these two projects are competent in the preparation of FPUF (ICL IP America), RPUF (Department of Industrial Engineering, Padova University), and TPU (Fraunhofer-Institut für Betriebsfestigkeit und Systemzuverlässigkeit LBF, Darmstadt) as well as for the specimen preparation. Systematically varied sets of materials were prepared as the key basic for scientific discussion, varying the kind and combination of flame retardant, PUR structure, density, and blowing agent.
A multimethodical approach based on thermogravimetry (TGA), TGA coupled with evolved gas analysis (TGA-FTIR) and pyrolysis GC-MS was used for investigating the pyrolysis. The flammability was addressed using oxygen index (OI) and testing in UL 94 burning chamber in vertical and horizontal set-up. The fire behaviour was addressed by using a cone calorimeter. Beyond these methods according to the state of the art, key experiments were performed. We addressed the dripping and the two-stage burning of TPU using a self-designed apparatus and specific data evaluation, the foam burning through quenching burning samples, using different special sample holders, and measuring temperature profiles within the burning foams. The investigation is made round by intensive analysis of the fire residues, such as comprehensive investigation of the morphology.
Result on the pyrolysis (TGA-FTIR, Pyrolysis-GC/MS), flammability (UL 94, LOI), and fire behaviour (cone calorimeter) of TPU and flame retardant TPUs are shown. We discuss in detail the characteristic of PUR decomposition: the low tendency to char, and the specific two step decomposition and how these characteristics control the regimes in fire behaviour. We demonstrate that the different burning regimes are controlled by different pyrolysis products and effective heat of combustions. The resulting formation of pool fires as well as the formation of dripping is discussed in detail. The latter quite important to understand the flame retardancy applied with respect to achieve the UL 94 classification V0 nondripping or V0 non-flaming dripping.
Rigid and flexible PUR foams and their flame retarded versions are investigated for different densities. Water and pentane-blown foams are compared as well as PUR and polyisocyanurate-polyurethane (PIR) foams. Horizontal testing in the cone calorimeter is used and the vertical foam specimen holder as well. Self-designed set-ups within the cone calorimeter enable a better inside in the pyrolysis front running through the foam samples as well as the development of the temperature gradient inside the foam during the fire test. The morphology change during burning was characterised by the means of quenching burning foams with liquid nitrogen and investigating the cross sections with scanning electron microscope. In sum, a rather comprehensive study was performed to work out the principle fire phenomena controlling the fire behaviour of PUR foams in a very systematic and significant way.
Promising flame retardancy approaches are discussed. The importance of either combining the drain of fuel and flame inhibition or charring into an effective protection layer/multicellular structure is underlined.
This contribution focusses the general conclusions and trends. It tries to increase the understanding of the specific and demanding challenge to develop flame retardant PUR materials.
Transport safety depends in great extent of what happens to the cargo once the carrying vehicle derails or rollovers. The exposure of tanks to direct fire is a condition that potentially involves catastrophic consequences. Studying the behavior of the contained fluid under these drastic circumstances, is critical to develop methods and techniques to mitigate the serious consequences of many mishaps. In this paper, the experimental potentials of a Particle Image Velocimetry data acquisition system are described, for providing experimental data that could be used to calibrate mathematical models. As an example of the situations that need to be modelled, an experiment is described concerning the effect of the boundary conditions and protecting devices, on the rate of variation of pressure and temperature of the fluid in a tank exposed to a direct fire. In this regard, the results emphasize the importance of equipping the vessels with both thermal insulation and safety valves.
Thermoplastic polyurethane - How thespecific two-stage decompositioncontrols its fire behavior
(2018)
Thermoplastic polyurethanes (TPUs) are one of the major classes of thermoplastic elastomers used in the cable and wire industry. Due to their chemical structure, they are considered as linear block copolymers with alternating hard and soft segments. This specific structure is not only responsible for the excellent mechanical properties of TPU like high tensile strength or abrasion resistance, but it also influences the pyrolysis and burning behavior. TPU is a highly flammable polymer which forms liquid pool fires or burning drops which results in intensive flame spread. Because of that, TPU often does not meet the strict requirements for indoor applications given by the cable market.
Under thermal stress, TPU decomposes in a specific way. At first, the hard segments decompose and the material becomes soft and melts. Subsequently, pool fires are formed and melted material burns extensively. There are not many works addressing this problem in detail especially in terms of suitable flame retardant solutions. It is crucial to understand at which stage the flame retardants are working and how they affect the thermal decomposition of TPU. Hence, the focus of this work was put on the identification of the reactions occurring during each stage of TPU decomposition and the contribution of released products to the effective heat of combustion (EHC). Moreover, the detailed analysis of the melt dripping behavior was performed to better understand the influence of the decomposition degree on the viscosity.
The use of melamine cyanurate (MC) in combination with other additives was reported to be a promising flame retardant solution for TPU, especially in cable jacket applications. Hence, the combinations of MC with various flame retardants were used in TPU (Elastollan® 1185A10) and were investigated in terms of fire behavior, flammability, pyrolysis and decomposition products. As flame retardants, common ones were used including aluminum trihydrate (ATH), melamine polyphosphate (MPP), or aluminum diethylphosphinate (AlPi). Moreover, commercial product TPU-FR (Elastollan® 1185A10FHF) was investigated as a reference.
The burning behaviour and thermal radiation of pool fires of organic peroxides (OP) have
been studied by several authors in the past. It was shown that mass burning rates, flame
temperatures and thus the Surface Emissive Power (SEP) of OP exceed to that of hydrocarbons
considerably. These facts lead to further investigations of even dangerous worst
case scenarios i.e. related to storage and transportation. A metal drum containing 200 l of
DTBP (Di-tert-butyl peroxide) is investigated under a surrounding wood fire. Due to a
higher heat flux to the substance, the mass burning rate reaches multiples of an equivalent
pool fire and results in several fireballs. The analyses of thermographic camera images
and radiometer measurements show higher flame lengths, higher temperatures and therefore
increased thermal radiation compared to OP pool fires. The resulting greater safety
distances for a DTBP fireball event are discussed.
Fire and explosion hazards associated with storage and transportation of flammable materials have been a matter of great interest in the recent times. There are numerous studies on pool fires, BLEVEs and fireballs of hydrocarbon fuels, whereas BLEVEs and fireballs of organic peroxides (OP) are not investigated in detail yet. Fireball is a scenario that can occur when an OP filled drum is subjected to a surrounding fire. This presentation tries to extend the first investigations of OP BLEVEs presented on IGUS EOS Meeting 2015 in Ottawa. The following aspects are shown: Experimental investigation of a fired drum filled with 200 L DTBP; analyses of flame characteristics, e.g. temperatures, mass burning rates, SEP, thermal radiation properties and an overall comparison with DTBP pool fires; presentation of recommended safety distances.
Dampening of energetic properties and the effects of blending proportions of isododecane on the diffusive burning behaviour of peroxy-fuels are experimentally studied. Blended peorxy-fuels are obtained by adding isododecane in the proportions of 25 wt.%, 50 wt.% and 75 wt.%, respectively, in technical pure peroxy-fuels. The fuels were burned in form of pool fires with diameters 0.02 m ≤ d ≤ 1 m. The mass burning rates and relative flame lengths are found to be weakened with increasing diluent proportions. By measuring the mass burning rates and visible flame lengths of pool fires of different samples of fuel blends an optimum blending criterion is developed. Furthermore, it is shown that the dilution proportions and flame characteristics can be correlated by empirical equations.
A simple model that divides the heat flux to the bodies engulfed in a diffusion flame into different components, namely radiation and convection is studied. Different sizes of brass and stainless steel (SS 304L) rods varying from 25.4 mm to 50.8 mm in length and 25.4 mm in diameter are used as specimens in this study. Experiments are conducted with each body inside a diesel pool fire of different diameters, namely 0.5 m, 0.7 m and 1.0 m. The temperature history of the body engulfed in a pool fire is measured to compute the thermal energy absorbed by the lumped body. Using an energy balance, the total energy is divided into three different components. The gas velocity in the flame is measured to be 1.53 m/s to 1.79 m/s for the diesel pool fires of 0.5 m to 1.0 m in diameter. The dominant mode of heat transfer in this study is radiative in nature. This simple model is reasonably able to predict the heat flux incident on to the lumped bodies engulfed by diesel pool fires using the measured temperature history. A three dimensional formulation for an axi-symmetric pool fire of a measured flame shape, flame temperature and a gray flame absorption coefficient is employed to predict the temperature of the body engulfed in pool fires. This formulation has to be modified to capture the absolute temperature values of the flame.
Limiting distances for flame merging of multiple n-heptane and di-tert-butyl peroxide pool fires
(2013)
Experiments to determine the limiting distances for flame merging of multiple pool fires are presented. As model substances n-heptane and di-tert-butyl peroxide are used. Laboratory scale tests with a Diameter d = 6 cm and relative distances between the pools of 0.08 ≤ D/d ≤ 4 are described and complemented with field experiments with a diameter d = 1.5 m and relative distances between the pools of 0.17 ≤ D/d ≤ 1.
Three regions for flame merging are observed and limiting distances are determined. A merging Region with the limiting distance Dmerg/d within which all flames merge together over the complete burning time. A transition region with the limiting distance Dtran/d within which some flames merge together while other flames are separated from each other. A separated region within which all flames are completely separated from each other. A correlation against the number of burning pools is presented to predict the limiting distances Dmerg/d und Dtran/d.
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.