Influence of Stretching Boundary Conditions on Fracture in Phantom Star Polymer Networks: From Volume to Cross-sectional Area Conservation

Abstract

This study systematically investigates the effect of stretching boundary conditions, ranging from conservation of cross-sectional area to conservation of volume, on the rupture behavior of phantom star polymer networks using energy-minimizing coarse-grained molecular simulations. By continuously varying the deformation parameter, the simulations reveal that true stress and rupture characteristics, such as strain and stress at break and work for rupture, systematically decrease as the boundary condition approaches cross-sectional area conservation. In contrast, nominal stress and the corresponding rupture characteristics exhibit near-independence from boundary conditions, indicating that bond tension remains largely unaffected for phantom networks under the examined conditions. These results clarify that volume expansion primarily drives deviations in true stress and highlight a critical distinction between true and nominal stress-strain definitions. The difference between true and nominal stress-strain relations also affected the scaling exponent for strand length dependence on stretch at break. The findings stress the importance of specifying both deformation boundary conditions and stress-strain definitions in polymer network simulations for accurate interpretation of mechanical properties.