Assessing Heat Accumulation Conditions

The situation is similar to class 1, except that the MTT is above Tm4. This means that under heat accumulation conditions, the activity of secondary reactions cannot be neglected, leading to a slow but significant pressure increase, or gas or vapor release. Nevertheless, the situation may become critical only if the reaction mass is left for a longer time at the level MTT. The assessment can be made using the same procedure as for criticality class 1, represented in Figure 10.8. The gas or vapor flow rate is an important parameter for the design of the required protection measures such as condenser, scrubber, or other treatment units. 

A practical approach of heat balance, often used in assessment of heat accumulation situations, is the time-scale approach. The principle is as in any race the fastest wins the race. For heat production, the time frame is obviously given by the time to maximum rate under adiabatic conditions. Then the removal is also characterized by a time that is dependent of the situation and this is defined in the next sections. If the TMRld is longer than the cooling time, the situation is stable, that is, the heat removal is faster. At the opposite, when the TMRld is shorter than the characteristic cooling time, the heat release rate is stronger than cooling and so runaway results. 

Phosphorus is known as an effective char promoter. Charring limits the release of fuels to the flame and therefore reduces the heat released. Moreover, the char accumulates on the surface of the material and can act as a protective layer which limits the heat transfer from the flame to the condensed phase and the gas transfer from the pyrolysis zone to the flame. This phenomenon is called the barrier effect. Nevertheless, it should be noted that the presence of char is not a sufficient condition to observe an effective barrier effect. Its structure (cohesion, porosity, thickness) is also veiy important but rarely studied. Thermal stability is another important parameter to assess the reaction to fire of a material. Indeed, the higher is the degradation temperature of a polymer, the greater is the heat required to start its pyrolysis. Table 12.2 lists the effects of phosphorus-containing groups on the thermal stability and charring for a variety of polymers. 

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