Weakly non-linear creep of amorphous polymers near their glass transition, comparisons between models and experiment

Abstract

The non-linear mechanics of amorphous polymers near the glass transition reveals a stress-induced acceleration of stress relaxation of nanometric sub-units. Recent theoretical work predicts that the local acceleration within these nano-domains should scale as the exponential of the squared local stress, a behavior now supported by experiments. However, this local dynamics has some complex consequences on the macroscopic mechanical response, as dynamical heterogeneities generate complex stress and strain fields in polymers close to the glass transition. In this study we consider the non-linear creep of an amorphous polymer near its glass transition and evaluate the relation between local and global acceleration and the emerging load-carrying structure, by comparing experimental data with predictions of three models of increasing complexity: a two-states (2S) model, a self-consistent (SC) model and a finite-element (FEM) model. The experimentally observed trend of accelerated creep under increasing applied stress is reproduced by the SC and FEM models, while the 2S model overestimates stress localization. The macroscopic, homogenized acceleration is predicted to be close to the microscopic one, albeit with an apparent yield stress that depends on compliance. The FEM model evidences the development of a load carrying sub-structure that occupies a small fraction of the total material volume driven by the interaction of sub-domains. This work shows that complexity and heterogeneity emerge due to non-linear interactions and that their adequate representation is essential for predicting the macroscopic mechanical response of amorphous polymers near their glass transition.