Investigation of local order in unreacted DGEBA epoxy resin monomers by light scattering

Abstract

The existence of local order in two epoxy resins of the diglycidyl ether of bisphenol‐A (DGEBA) type has been investigated using Rayleigh scattering and Brillouin spectroscopy. The resins differ in their molecular weight distributions and their relative concentrations of epoxide and hydroxyl groups. The complementary use of both techniques in elucidating the thermal behavior of local order is illustrated, and the use of the latter technique to study thermal acoustic phonons and hypersonic relaxation is discussed. Both techniques independently show that molecular aggregates exist in each resin system. The scattering‐envelope dissymmetry shows that the resin with the high epoxide/hydroxyl group ratio contains aggregates up to 20 nm in size, and the low‐ratio resin exhibits sizes up to 70 nm. These aggregates are thermally unstable in the temperature range studied (293–443 K). Dissolution in chloroform shows that these aggregates are reduced in size and that further structural changes occur which are dependent on solvent concentration. Aggregate volume fractions were determined for a range of aggregate size. Brillouin spectroscopy indicated that both resins exhibit hypersonic relaxation in the temperature range studied. The complex longitudinal moduli of the resins were superimposable under a WLF temperature transformation comparable to the difference in their static glass transition temperatures. Molecular aggregate size, number, and stability are related to the epoxide/hydroxyl ratio of the resins and the degree of intermolecular hydrogen bonding.