Material response models for phenolic-based thermal protection systems (TPSs) for atmospheric entry are limited by the lack of knowledge of the nonequilibrium processes that may govern the decomposition pathways of phenolic resin at heating rates up to tens of degrees Celsius per second. We have investigated the pyrolysis of phenolic impregnated carbon ablator (PICA) by measuring the molar yields of the volatile decomposition products as a function of temperature at four nominal heating rates of 3.1, 6.1, 12.7, and 25 °C s^-1, over the temperature range of 100-1200 °C. A mass spectrometer was used to probe the 14 significant gaseous products directly as PICA samples were heated resistively in vacuum. Four products, H₂, CH₄, H₂O, and CO, overwhelmingly dominated the molar yields. However, in terms of mass yield, phenol and its methylated derivatives, cresol and dimethyl phenol, were significant. The temperature-dependent molar yields of the observed products exhibited a marked dependence on heating rate. The heating-rate-dependent behavior of the molar yields has been attributed to two main competing decomposition processes that occur as the temperature passes from roughly 300 to 500 °C: (1) cross-linking reactions that produce ether functional groups and carbon-carbon bonds and eliminate H₂O and (2) breakdown of the polymer backbone through scission of methylene bridges and liberation of phenol and its methylated derivatives. The latter process competes more effectively with the former as the heating rate increases. The relative rates of these processes appear to have a significant effect on the molar yields of volatile products from subsequent decomposition processes as the temperature is increased further. Thus, the heating rate strongly affects the pathways taken during the pyrolysis of the phenolic resin in PICA. The new data may be used to test nonequilibrium models that are designed to simulate the response of TPS materials during atmospheric entry of spacecraft.

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