Interplay of Spatial and Topological Defects in Polymer Networks

B. Ruşen Argun and Antonia Statt
ACS Engineering Au 0, 0, pp

DOI: 10.1021/acsengineeringau.3c00072


Polymer networks are widely used in applications, and the formation of a network and its gel point can be predicted. However, the effects of spatial and topological heterogeneity on the resulting network structure and ultimately the mechanical properties, are less understood. To address this challenge, we generate in silico random networks of cross-linked polymer chains with controlled spatial and topological defects. While all fully reacted networks investigated in this study have the same number of end-functionalized polymer strands and cross-linkers, we vary the degree of spatial and topological heterogeneities systematically. We find that spatially heterogeneous cross-linker distributions result in a reduction in the network’s primary loops with increased spatial heterogeneity, the opposite trend as observed in homogeneous networks. By performing molecular dynamics simulations, we investigated the mechanical properties of the networks. Even though spatially heterogeneous networks have more elastically active strands and cross-linkers, they break at lower extensions than the homogeneous networks and sustain slightly lower maximum stresses. Their shear moduli are higher, i.e., stiffer, than theoretically predicted, and higher than their homogeneous gel counterparts. Our results highlight that topological loop defects and spatial heterogeneities result in significantly different network structures and, ultimately, different mechanical properties.


Details on the monomer pair interactions, code, and explanation for generating the cross-linker distribution, gel points and devulcanization data, loops during cross-linking, quantification of higher-order loops and topological defects, strand length distributions, local density distributions, second virial coefficient, and swelling ratios of the gels.