Product specific thermal degradation kinetics of bisphenol F epoxy in inert and oxidative atmospheres using evolved gas analysis–mass spectrometry

Dwyer, Derek B.; Gallego, Nidia C.; Niedziela, Jennifer L.; Kapsimalis, Roger J.; Duckworth, Douglas C.

doi:10.1016/j.jaap.2022.105563

Title: Product specific thermal degradation kinetics of bisphenol F epoxy in inert and oxidative atmospheres using evolved gas analysis–mass spectrometry

Journal Article · Wed May 18 00:00:00 UTC 2022 · Journal of Analytical and Applied Pyrolysis

DOI: https://doi.org/10.1016/j.jaap.2022.105563 · OSTI ID:1870249

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Knowledge of the degradation kinetics for polymer materials is important for understanding thermal stability. In this study, evolved gas analysis–mass spectrometry and pyrolysis gas-chromatography-mass spectrometry were evaluated for the potential to deliver additional insight into thermal degradation kinetics of diglycidal ether of bisphenol F (DGEBF) epoxy thermoset under inert and oxidative atmospheres. Degradation products of selected precursor ions were evaluated for their uniqueness to the specific precursor using extracted ion thermographs. Unique mass peaks, solely attributed to a single reaction pathway of a specific product, were determined from extracted ion thermographs and used to determine both activation energy (E_a) and pre-exponential factors for the specific primary reaction pathways. These primary reaction pathways for DGEBF epoxy degradation were then evaluated in the context of transition state theory (TST) and related transition state enthalpies (ΔH^‡) and entropies (ΔS^‡) of activation to further elucidate the degradation process. It was determined under pyrolysis conditions, as suggested by the E_a, the formation of bisphenol F monomer was the rate-limiting step toward the formation of xanthene and phenol. In contrast, under thermo-oxidative conditions, reactions involving oxygen containing species were identified as the rate-limiting step for all observed products based on the large negative ΔS^‡ calculated from TST. This work demonstrates a powerful combination of technique and theory that can provide new insight into the degradation of polymer materials.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1870249

Journal Information:: Journal of Analytical and Applied Pyrolysis, Journal Name: Journal of Analytical and Applied Pyrolysis Journal Issue: 1 Vol. 165; ISSN 0165-2370

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bisphenol F epoxy
kinetics
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Title: Product specific thermal degradation kinetics of bisphenol F epoxy in inert and oxidative atmospheres using evolved gas analysis–mass spectrometry

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