Unveiling the nanoscale heterogeneity controlled deformation of thermosets

The deformation behavior of polymer materials below their glass transition temperature involves a complex intermingling of elasticity, of viscoplastic yielding with softening and large strain hardening, and of significant rate, temperature and pressure dependency. During unloading, the response exhibits large non-linearity as well, combining forward and backward creep. Even though the nature of the atomistic underlying mechanisms is relatively well understood, a full picture of the interactions between the elementary distortion mechanisms and their collective organization capturing the complexity of the macroscopic behavior is still lacking. Here, we propose a mesoscale approach based on the heterogeneous activation of molecular level shear transformation zones and we show that it is rich enough to unravel the physical origin of most aspects of the macroscopic viscoplastic response. The study is based on a wide micro- and macro-mechanical test campaign on a thermoset material. In addition to providing a full characterization of all macroscopic properties, evidence of a complex rate reversal mechanism upon unloading is given. Other experiments provide insights about the characteristic length scales at play. Compared to existing continuum models involving typically more than 25 parameters, the present formalism is based on only 7 physical parameters while allowing quantitative predictions of all the experimental data. The present approach opens new avenues for the prediction of the mechanical response of a variety of polymer applications in confined state such as in composites or in adhesive joints. It also offers a new line of thought to address the mechanics of polymers at small and intermediate length scales.