Effect of Loop Defects on the High Strain Rate Behavior of PEGDA Hydrogels: A Molecular Dynamics Study

K Luo and C Wangari and G Subhash and DE Spearot, JOURNAL OF PHYSICAL CHEMISTRY B, 124, 2029-2039 (2020).

DOI: 10.1021/acs.jpcb.9b11378

The high strain rate behavior of nonideal poly(ethylene glycol) diacrylate hydrogels under uniaxial tension and transient-state shear deformations is investigated using molecular dynamics (MD) simulations. This work specifically focuses on the influence of first-order loop defects, including their effect on topological evolutions. Two approaches are proposed to systematically introduce first-order loops, allowing separate and controllable investigations of effective cross- link functionality and cross-link density. MD simulations confirm that first-rder loop defects are elastically inactive, but the topological disruptions caused by the presence of loop defects influence mechanical behavior. For decreasing effective cross-link functionality but constant cross-link density, a weaker tensile stress-strain response and decreasing shear-thickening behavior are observed. This is due to nonaffine translation of cross-link junction positions during deformation. Hydrogels with lower cross-link density but constant effective functionality show a stronger stress-strain response and an earlier transition between entropic and enthalpic deformation regimes. This behavior is correlated to changes in mesh size caused by the introduction of loops within an elastically active network. However, the resulting range of cross-link densities is not sufficient to cause measurable changes in shear-thickening behavior. To conclude, reductions in effective cross-link functionality are more important to high strain rate behavior than reductions in cross-link density.

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