Simulation Study of the Effects of Interfacial Bonds on Adhesion and Fracture Behavior of Epoxy Resin Layers

The adhesion and fracture behavior of tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM)/4,4′-diaminodiphenyl sulfone (44DDS)–bisphenol A diglycidyl ether (DGEBA)/44DDS layer interfaces were investigated by molecular dynamics (MD) simulation, mainly focusing on the role of covalent and noncovalent interactions. To accurately investigate the bond dissociation processes, the force field parameters of several bond potentials of the epoxy resin polymers were optimized by density functional theory calculations. In the MD simulations under a tensile load, small voids gradually developed without covalent bond dissociation in the plateau region. In the final large strain region, the stress rapidly increased with bond breaking, leading to failure. When the chemical bonds across the interface between the two layers were removed, the stress–strain curve in the initial elastic region was almost the same as that with interfacial bonds. This showed that the nonbonded interactions governed adhesion strength in the initial elastic region. In contrast, the bonded interactions at interfaces played important roles in the hardening regions because the bonded interactions made the major contribution to the fracture energies. We also investigated the effect of the etherification reaction in cross-linking. It was found that the etherification reaction mainly contributed to the behavior in the late region with large strain. These simulation results revealed that the nonbonded interactions, especially, van der Waals interactions, are important factors for adhesion of the different polymer layers in the small strain region up to the yield point.