Flow-Driven Stretch Fluctuations Govern the Nonlinear Viscoelasticity of Elongating Associative Polymer Networks

Liu, Songyue; O’Connor, Thomas C.

doi:10.1103/kgrd-8gkb

Flow-Driven Stretch Fluctuations Govern the Nonlinear Viscoelasticity of Elongating Associative Polymer Networks

Journal Article · Thu Aug 28 00:00:00 EDT 2025 · Physical Review Letters

DOI:https://doi.org/10.1103/kgrd-8gkb· OSTI ID:3025388

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Carnegie Mellon Univ., Pittsburgh, PA (United States)

We use nonequilibrium molecular dynamics simulations to verify recent tube-model predictions that associative polymer networks exhibit broad stretch fluctuations during elongational flow. Simulations further show that these fluctuating dynamics give rise to the rate-dependent extensional viscosity 𝜂_𝐸 measured in filament stretching experiments on H-bonding networks. Simulations model bivalent associative networks with a reactive bead-spring model for varying association strength and extensional strain rate. We observe that stretch fluctuations are driven by a new form of chain tumbling, where chains continually collapse and elongate as their associations break and reform within the advecting network. This produces a broad, nearly uniform distribution of chain stretch over a wide range of strain rates, manifesting as a rate-independent plateau in the extensional stress. Our results show that the nonlinear viscoelasticity of associative networks is dominated by large fluctuations in molecular response, which cannot be captured by current mean-field models.

View Accepted Manuscript (DOE)

Research Organization:: Carnegie Mellon Univ., Pittsburgh, PA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: NA0003525; SC0025643

OSTI ID:: 3025388

Journal Information:: Physical Review Letters, Journal Name: Physical Review Letters Journal Issue: 9 Vol. 135; ISSN 1079-7114; ISSN 0031-9007

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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