Nanoscale confinement effects on the relaxation dynamics in networks of diglycidyl ether of bisphenol-A and low-molecular-weight poly(ethylene oxide).

Thermoplastic poly(ethylene oxide) (PEO) (Mw(PEO) approximately 4000) has been used to prepare thermosetting nanocomposites incorporating diglycidyl ether of bisphenol A (DGEBA) epoxy oligomer. Blends with various PEO/DGEBA weight ratios were cured using stoichiometric portions of 4,4'-diaminodiphenylmethane. The resulting semi-interpenetrating polymer networks were studied by several techniques. Nanoscale confinement effects, thermal (glass transition, melting and crystallization temperatures) and structural features of our materials are similar to those for networks with much higher Mw(PEO) and different curing agents; however, the polyether crystallization onset occurs in our case at a lower PEO concentration; shorter PEO chains organize themselves more easily into crystalline domains. Very low estimates of the k parameter of the Gordon-Taylor equation, used to fit the compositional dependences of the dielectric and calorimetric glass transition temperatures, and a strong plasticization of the motion of the glyceryl segments (beta-relaxation) in the epoxy resin were observed. These illustrate an intensified weakening in the strength of the intermolecular interactions in the modified networks, as compared to the high strength of the self-association of hydroxyls in the neat resin. The significance of hydrogen-bonding interactions between the components for obtaining structurally homogeneous thermoset-i-thermoplastic networks is discussed.