Quantifying bond rupture during indentation fracture of soft polymer networks using molecular mechanophores

Understanding the resistance of soft materials to puncture bears relevance to many fields. However, the complex mechanics during deep indentation make it difficult to disentangle how the different dissipation processes contribute to the fracture energy and how this depends on the molecular structure of the material. To investigate this, we perform deep indentation experiments with a flat-ended cylindrical probe on polymer networks containing the covalently incorporated mechanoluminescent bond rupture sensor 1,2-dioxetane. By carrying out the experiments inside an integrating sphere, we are able to quantify the number of ruptured bonds during puncture nucleation and propagation. We find that puncture is associated with significant diffuse damage, both prior to nucleation of the main crack and during crack propagation. Moreover, in agreement with earlier results for uniaxial extension, we show that puncture of double networks leads to strongly enhanced rupture in the prestretched sacrificial network, while fracture of the matrix network is much more localized. Finally, we complement the experiments with MD simulations that allow us to link the rupture processes to the distribution of tension in the networks.