Product-specific kinetics reveal effect of epoxy crystallization on thermoset thermal degradation

Dwyer, Derek B.; Gallego, Nidia C.; Isbill, Sara; Miskowiec, Andrew; Niedziela, Jennifer L.

doi:10.1016/j.polymer.2024.127003

Product-specific kinetics reveal effect of epoxy crystallization on thermoset thermal degradation

Journal Article · Thu Apr 04 04:00:00 EDT 2024 · Polymer

DOI:https://doi.org/10.1016/j.polymer.2024.127003· OSTI ID:2338285

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Crystallization is a common problem for epoxy resins, which are ubiquitous in industrial and commercial use. Integration of crystallized epoxy monomers into cured thermosets has been shown to alter the thermosets’ final mechanical properties. However, no studies have investigated the impact of these crystals on the thermal stability of the thermoset. Here we investigate the degradation kinetics of a bisphenol F–based epoxy thermoset with and without crystallized monomers using Product-Specific Kinetic (PSK) analysis coupled with Evolved Gas Analysis-Mass Spectrometry (EGA-MS). PSK analysis revealed significant differences in evolved product ion kinetics, suggesting changes in the degradation kinetics between thermoset configurations. Further, it was concluded that early stages of degradation are influenced most by crystal presence due to the high concentration of unreacted epoxy monomers and lower cross-linking density of the cured network. After post-cure annealing, significant changes are observed in the degradation kinetics of thermosets without crystal inclusions. Conversely, post-cure annealing procedures of crystal integrated thermosets showed little change in the thermoset degradation kinetics across all conversion extents. These findings suggest that post-cure annealing of thermosets with crystals present at the onset does not alter the cross-linking density of the polymer network enough to significantly change the degradation kinetics. We hypothesize this is because the excess monomers from the melted crystals are unable to find suitable reaction sites for complete binding into the polymer network, which has direct implications for the material properties and final thermal stability of the thermoset.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2338285

Alternate ID(s):: OSTI ID: 2369015

Journal Information:: Polymer, Journal Name: Polymer Journal Issue: 1 Vol. 301; ISSN 0032-3861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Bisphenol F
Crystallized epoxy resin
EGA-MS
Product-specific kinetics
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Product-specific kinetics reveal effect of epoxy crystallization on thermoset thermal degradation

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