The polymer network structure of epoxy thermosets plays
a significant
role in its final material properties. However, the effects of mild
thermal exposure on these network structures are poorly studied. In
this work, wide-angle X-ray scattering was used to investigate the
polymer network structure of two epoxy thermosets: homopolymerized
bisphenol A (BPA) epoxy resin and BPA epoxy resin cured with a polyether
amine hardener (BPA/T-403). Using density functional theory and wide-angle
X-ray scattering, insights into the polymer network structure were
obtained. Diffraction features were determined to originate from hardener-to-hardener
molecular distance, perpendicular π–π stacking
of aromatic p-phenylene rings, and the average carbon–carbon
distance in the polymer. Thermal exposure was found to permanently
alter these structural features for both thermosets, with an increase
in the π–π stacking distance. Homopolymerized BPA
had an additional decrease in the hardener-to-hardener distance. These
structural alterations were found to be detectable using Fourier transform
infrared spectroscopy and Raman spectroscopy, with changes in the
hardener-to-hardener distance having the largest variations in the
resulting spectra specifically at the aromatic and ether frequencies.