Invariant fractocohesive length in thermally aged elastomers

Abstract

The fractocohesive length - the ratio between fracture toughness and work-to-fracture - provides a material-specific length scale that characterizes the size-dependent fracture behavior of pristine elastomers. However, its relevance to thermally aged materials, where both toughness and work of fracture degrade dramatically, remains unexplored. Here, we demonstrate that despite severe thermal embrittlement, the fractocohesive length remains invariant throughout thermal aging, independent of temperature or duration. We verify this invariance experimentally for two elastomer systems (Styrene Butadiene Rubber and Silicone Rubber) at multiple aging temperatures for aging times up to eight weeks. This finding bridges a critical gap in fracture mechanics of aged polymers: while the evolution of work-to-fracture can be predicted from well-established constitutive models that track network changes (crosslink density and chain scission), the evolution of fracture toughness has lacked predictive frameworks. The invariance of fractocohesive length enables direct calculation of fracture toughness at any aging state from the predicted work of fracture, eliminating the need for extensive fracture testing on aged elastomers and providing a crucial missing link for computational fracture predictions in aged elastomeric components.