Abstract
Fragility is an empirical property that describes how abruptly a glass-forming material solidifies upon supercooling. The degree of fragility carries important implications for the functionality and processability of a material, as well as for our fundamental understanding of the glass transition. However, the microstructural properties underlying fragility still remain poorly understood. Here, we explain the microstructure-fragility link in vitrimeric networks, a novel type of high-performance polymers with unique bond-swapping functionality and unusual glass-forming behavior. Our results are gained from coarse-grained computer simulations and first-principles mode-coupling theory (MCT) of star-polymer vitrimers. We first demonstrate that the vitrimer fragility can be tuned over an unprecedentedly broad range, from fragile to strong and even superstrong behavior, by decreasing the bulk density. Remarkably, this entire phenomenology can be reproduced by microscopic MCT, thus challenging the conventional belief that existing first-principles theories cannot account for nonfragile behaviors. Our MCT analysis allows us to rationally identify the microstructural origin of the fragile-to-superstrong crossover, which is rooted in the sensitivity of the static structure factor to temperature variations. On the molecular scale, this behavior stems from a change in dominant length scales, switching from repulsive excluded-volume interactions to intrachain attractions as the vitrimer density decreases. Finally, we develop a simplified schematic MCT model which corroborates our microscopically founded conclusions and which unites our findings with earlier MCT studies. Our work sheds additional light on the elusive structure-fragility link in glass-forming matter and provides a first-principles-based platform for designing amorphous materials with an on-demand dynamic response.