RESUMEN

Reconfigurable polymer networks are gaining interest for their potential applications as self-healing, recyclable, and stimuli-responsive smart materials. Relating the bond strength of dynamic interactions to material properties including stress relaxation time and modulus is crucial for smart material design. In this work, in situ crosslinked transition metal-terpyridine reconfigurable networks were utilized to modulate the characteristic network stress relaxation time, τR. The use of stress relaxation experiments rather than oscillatory frequency sweeps allowed for the measurement of network bond dynamics across a wider dynamic range than has been previously reported. The stress relaxation time was shown to be tunable by metal center, counterion, and crosslink density. Remarkably, the network crosslinked with covalent-like ruthenium chloride-terpyridine interaction, while having a longer τR, was qualitatively similar to the other metal-ligand networks. Furthermore, the relaxation time was independent of crosslink density in strongly bonded networks, allowing for independent tunability of modulus and τR. In contrast, increasing crosslink density reduced τR in networks crosslinked with weaker interactions.

RESUMEN

Rapid expansion of soft solids subjected to a negative hydrostatic stress can occur through cavitation or fracture. Understanding how these two mechanisms relate to a material's molecular structure is important to applications in materials characterization, adhesive design, and tissue damage. Here, a recently improved needle-induced cavitation (NIC) protocol is applied to a set of model end-linked PEG gels with quantitatively linked elastic and fracture properties. This quantitative link between molecular scale structure and macroscopic properties is exploited to experimentally probe the relationship between cavitation, fracture, and molecular scale damage. This work indicates that rational tuning of the elastofracture length relative to the crack geometry can be used to alter the expansion mechanism from cavitation to fracture during NIC.

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RESUMEN

Advances in polymer chemistry over the last decade have enabled the synthesis of molecularly precise polymer networks that exhibit homogeneous structure. These precise polymer gels create the opportunity to establish true multiscale, molecular to macroscopic, relationships that define their elastic and failure properties. In this work, a theory of network fracture that accounts for loop defects is developed by drawing on recent advances in network elasticity. This loop-modified Lake-Thomas theory is tested against both molecular dynamics (MD) simulations and experimental fracture measurements on model gels, and good agreement between theory, which does not use an enhancement factor, and measurement is observed. Insight into the local and global contributions to energy dissipated during network failure and their relation to the bond dissociation energy is also provided. These findings enable a priori estimates of fracture energy in swollen gels where chain scission becomes an important failure mechanism.