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Dynamic networks containing multiple bond types within a continuous network grant engineers another design parameter – relative bond fraction – by which to tune storage and dissipation of mechanical energy. However, the mechanisms governing emergent properties are difficult to deduce experimentally. Therefore, we here employ a network model with prescribed fractions of dynamic and stable bonds to predict relaxation characteristics of hybrid networks. We find that during stress relaxation, predominantly dynamic networks can exhibit long-term moduli through conformationally inhibited relaxation of stable bonds due to exclusion interactions with neighboring chains. Meanwhile, predominantly stable networks exhibit minor relaxation through non-affine reconfiguration of dynamic bonds. Given this, we introduce a single fitting parameter, ξ , to Transient Network Theory via a coupled rule of mixture, that characterizes the extent of stable bond relaxation. Treating ξ as a fitting parameter, the coupled rule of mixture's predicted stress response not only agrees with the network model's, but also unveils likely micromechanical traits of gels hosting multiple bond dissociation timescales.
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Dynamics of equilibrium-linked colloidal networks
Colloids that attractively bond to only a few neighbors (e.g., patchy particles) can form equilibrium gels with distinctive dynamic properties that are stable in time. Here, we use a coarse-grained model to explore the dynamics of linked networks of patchy colloids whose average valence is macroscopically, rather than microscopically, constrained. Simulation results for the model show dynamic hallmarks of equilibrium gel formation and establish that the colloid–colloid bond persistence time controls the characteristic slow relaxation of the self-intermediate scattering function. The model features re-entrant network formation without phase separation as a function of linker concentration, centered at the stoichiometric ratio of linker ends to nanoparticle surface bonding sites. Departures from stoichiometry result in linker-starved or linker-saturated networks with reduced connectivity and shorter characteristic relaxation times with lower activation energies. Underlying the re-entrant trends, dynamic properties vary monotonically with the number of effective network bonds per colloid, a quantity that can be predicted using Wertheim’s thermodynamic perturbation theory. These behaviors suggest macroscopic in situ strategies for tuning the dynamic response of colloidal networks.
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- Award ID(s):
- 1720595
- PAR ID:
- 10434668
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 157
- Issue:
- 18
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 184902
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0125125
