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Abstract The solution rheology of a fully synthetic, monodisperse mucin that mimics the glycosylated domains of natural mucins, poly(β‐Gal‐Thr)22, is studied to systematically explore relationships between polymer structure, solution conditions, and rheological properties. Using standard cone‐plate rheometry, shear thinning is observed over a range of concentrations, with an apparent yield stress—typical for gels—evident at the highest concentrations. This is surprising given the dilute, weakly interacting nature of the solutions and the lack of observable structure in cryogenic electron microscopy and particle tracking microrheology. However, interfacial rheometry demonstrates that the gel‐like behavior is attributable to a thin structured layer at the air–water interface, without any bulk gelation. This is attributed to an interfacial layer formed by inter‐mucin H‐bonds that yields when sheared. A computational model using kinetic Monte Carlo (kMC) simulations qualitatively reproduces the yield stress response of such a network through an intermolecular bonding potential. An analytical model of stochastic bond formation and breaking, validated by the kMC simulations, demonstrates that having multiple bonding sites per mucin with a force‐dependent debonding rate aligns with experiments, consistent with intermolecular interactions for other mucin proteins. This suggests that in mucin solutions, gelation may begin at the air–water interface, and emphasizes the need for multitechnique validation when exploring structural cues of mucus gelation through rheometry.
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Emergence of viscosity and dissipation via stochastic bonds
“Viscosity is the most ubiquitous dissipative mechanical behavior” (Maugin, 1999). Despite its ubiquity, even for those systems where the mechanisms causing viscous and other forms of dissipation are known there are only a few quantitative models that extract the macroscopic rheological response from these microscopic mechanisms. One such mechanism is the stochastic breaking and forming of bonds which is present in polymer networks with transient cross-links, strong inter-layer bonding between graphene sheets, and sliding dry friction. In this paper we utilize a simple yet flexible model to show analytically how stochastic bonds can induce an array of rheological behaviors at the macroscale. We find that varying the bond interactions induces a Maxwell-type macroscopic material behavior with Newtonian viscosity, shear thinning, shear thickening, or solid like friction when subjected to shear at constant rates. When bond rupture is independent of the force applied, Newtonian viscosity is the predominant behavior. When bond breaking is accelerated by the applied force, a shear thinning response becomes most prevalent. Further connections of the macroscopic response to the interaction potential and rates of bonding and unbonding are illustrated through phase diagrams and analysis of limiting cases. Finally, we apply this model to polymer networks and to experimental data on “solid bridges” in polydisperse granular media. We imagine possible applications to material design through engineering bonds with specific interactions to bring about a desired macroscopic behavior.
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- Award ID(s):
- 2047506
- PAR ID:
- 10314035
- Date Published:
- Journal Name:
- Journal of the mechanics and physics of solids
- Volume:
- 158
- ISSN:
- 0022-5096
- 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/10.1016/j.jmps.2021.104660
