Molecular insights into the ‘defects’ network in the thermosets and the influence on the mechanical performance

The introduction of ‘defects’ to the thermoset crosslinking network is one of the most applicable strategies for improving the modulus and toughness simultaneously. However, the reinforcement effect disappears when the ‘defects’ proportion exceeds the threshold. The speculated mechanism was that the aggregation and entanglement of the ‘defects’ chains changed the matrix topology, making the stacking structure more compact. However, the ‘defects’ are hardly directly observed in the experiment. As the result, the relationship between the ‘defects’ proportion and the package state of the matrix, and the effect on the material's mechanical performance was not explored. Herein, the network of bisphenol-A diglycidyl (DGEBA) with diethyltoluenediamine (DETDA) as the hardener was constructed using MD simulation, and n-butylamine was decorated on the matrix by replacing a proportion of DETDA acting as the ‘defects’. The results indicated that the aliphatic chains aggregated and entangled at a low concentration, occupying the voids in the rigid aromatic crosslinking structure, thus lowering the free volume. The strong non-bonding interactions drew the matrix segments close together, thus reinforcing the resin. However, the microphases formed by the aliphatic chains no longer filled the voids but created a new free volume and loosened the network when the content increased, which reduced the mechanical performance of the material. The experimental results were consistent with the findings in the simulations. The moduli of the resin increased with the increase in the n-butylamine content first and then declined. The maximum moduli of the thermosets was 3.4 GPa in S(30), which was about 25% higher compared with the control; the corresponding elongation at break was 8.9%, which was about 46% improved compared with the control.