Pyrolysis of phenolic impregnated carbon ablator (PICA).

Molar yields of the pyrolysis products of thermal protection systems (TPSs) are needed in order to improve high fidelity material response models. The volatile chemical species evolved during the pyrolysis of a TPS composite, phenolic impregnated carbon ablator (PICA), have been probed in situ by mass spectrometry in the temperature range 100 to 935 °C. The relative molar yields of the desorbing species as a function of temperature were derived by fitting the mass spectra, and the observed trends are interpreted in light of the results of earlier mechanistic studies on the pyrolysis of phenolic resins. The temperature-dependent product evolution was consistent with earlier descriptions of three stages of pyrolysis, with each stage corresponding to a temperature range. The two main products observed were H2O and CO, with their maximum yields occurring at ∼350 °C and ∼450 °C, respectively. Other significant products were CH4, CO2, and phenol and its methylated derivatives; these products tended to desorb concurrently with H2O and CO, over the range from about 200 to 600 °C. H2 is presumed to be the main product, especially at the highest pyrolysis temperatures used, but the relative molar yield of H2 was not quantified. The observation of a much higher yield of CO than CH4 suggests the presence of significant hydroxyl group substitution on phenol prior to the synthesis of the phenolic resin used in PICA. The detection of CH4 in combination with the methylated derivatives of phenol suggests that the phenol also has some degree of methyl substitution. The methodology developed is suitable for real-time measurements of PICA pyrolysis and should lend itself well to the validation of nonequilibrium models whose aim is to simulate the response of TPS materials during atmospheric entry of spacecraft.